KR102050071B1 - Supported hybrid catalyst system for propylene polymerization and method for preparing propylene polymer with the catalyst system - Google Patents
Supported hybrid catalyst system for propylene polymerization and method for preparing propylene polymer with the catalyst system Download PDFInfo
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- KR102050071B1 KR102050071B1 KR1020150138729A KR20150138729A KR102050071B1 KR 102050071 B1 KR102050071 B1 KR 102050071B1 KR 1020150138729 A KR1020150138729 A KR 1020150138729A KR 20150138729 A KR20150138729 A KR 20150138729A KR 102050071 B1 KR102050071 B1 KR 102050071B1
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- South Korea
- Prior art keywords
- carbon atoms
- catalyst system
- formula
- aluminum
- supported catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 21
- 238000006116 polymerization reaction Methods 0.000 title claims description 18
- 239000008096 xylene Substances 0.000 claims abstract description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 95
- -1 4-tert-butylphenyl Chemical group 0.000 claims description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 239000000126 substance Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 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
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 84
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000012968 metallocene catalyst Substances 0.000 description 9
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 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
- 238000001816 cooling Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- OPRLLAPOGFQRMV-UHFFFAOYSA-N dichloromethyl-[6-[(2-methylpropan-2-yl)oxy]hexyl]silane Chemical compound C(C)(C)(C)OCCCCCC[SiH2]C(Cl)Cl OPRLLAPOGFQRMV-UHFFFAOYSA-N 0.000 description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- FUDWOKXLGOJFFQ-UHFFFAOYSA-N 4-(4-tert-butylphenyl)-2-methyl-1h-indene Chemical compound C1C(C)=CC2=C1C=CC=C2C1=CC=C(C(C)(C)C)C=C1 FUDWOKXLGOJFFQ-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- STKIWXGXQUBYEY-UHFFFAOYSA-N N,N-dibutylbutan-1-amine (2,3,4,5,6-pentafluorophenyl)aluminum(2+) [4-(trifluoromethyl)phenyl]aluminum(2+) Chemical compound CCCCN(CCCC)CCCC.FC(C(C=C1)=CC=C1[Al+2])(F)F.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 STKIWXGXQUBYEY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 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
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- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
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- 125000005103 alkyl silyl group Chemical group 0.000 description 1
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- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000010960 commercial process Methods 0.000 description 1
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- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LBEVBJIOGOYYCB-UHFFFAOYSA-L dichlorozirconium;oxolane Chemical compound Cl[Zr]Cl.C1CCOC1.C1CCOC1 LBEVBJIOGOYYCB-UHFFFAOYSA-L 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
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- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 1
- 208000006047 familial isolated pituitary adenoma Diseases 0.000 description 1
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- 208000036974 gastrointestinal defects and immunodeficiency syndrome 1 Diseases 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- GGFBICGBDXVAGX-UHFFFAOYSA-N propylaluminum Chemical compound [Al].[CH2]CC GGFBICGBDXVAGX-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003623 transition metal compounds 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
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명은 프로필렌 중합체 제조용 혼성 담지 촉매 시스템 및 이를 이용한 프로필렌 중합체의 제조 방법에 관한 것이다. 본 발명에 따른 상기 혼성 담지 촉매 시스템은 우수한 촉매 활성을 가지면서도, 특히 목적하는 기계적 물성에 맞도록 자일렌 가용분의 함량이 제어된 프로필렌 중합체의 제공을 가능케 한다.The present invention relates to a hybrid supported catalyst system for producing a propylene polymer and a method for producing a propylene polymer using the same. The hybrid supported catalyst system according to the present invention makes it possible to provide a propylene polymer having excellent catalytic activity and in particular having a controlled content of xylene solubles to suit the desired mechanical properties.
Description
본 발명은 프로필렌 중합용 혼성 담지 촉매 시스템 및 이를 이용한 프로필렌 중합체의 제조 방법에 관한 것이다.The present invention relates to a hybrid supported catalyst system for propylene polymerization and a method for producing a propylene polymer using the same.
올레핀 중합용 촉매 시스템은 지글러-나타 촉매 및 메탈로센 촉매으로 분류될 수 있으며, 이 두 가지의 촉매는 각각 특징에 맞게 발전되어 왔다.Catalyst systems for olefin polymerization can be classified into Ziegler-Natta catalysts and metallocene catalysts, both of which have been developed to suit their characteristics.
지글러-나타 촉매는 1950년대 발명된 이래 기존의 상업 프로세스에 널리 적용되어 왔다. 그러나, 지글러-나타 촉매는 활성점이 여러 개 혼재하는 다활성점 촉매이기 때문에, 이를 이용하여 형성된 중합체의 분자량 분포가 넓고, 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있다. 특히, 지글러-나타 촉매를 이용하여 형성된 프로필렌 중합체는 높은 자일렌 가용분 함량 (예를 들어 5 중량% 초과)을 갖기 때문에, 지글러-나타 촉매를 이용할 경우 녹는 점(Tm)이 낮은 프로필렌 중합체를 얻기 어려운 한계가 있다.Ziegler-Natta catalysts have been widely applied to existing commercial processes since the invention in the 1950s. However, since the Ziegler-Natta catalyst is a multi-active site catalyst having multiple active sites, the molecular weight distribution of the polymer formed using the same is wide, and the composition distribution of the comonomer is not uniform. In particular, since the propylene polymer formed using the Ziegler-Natta catalyst has a high xylene soluble content (for example greater than 5% by weight), a propylene polymer having a low melting point (Tm) is obtained when using the Ziegler-Natta catalyst. There are hard limits.
메탈로센 촉매는 전이금속 화합물이 주성분인 주촉매와 알루미늄이 주성분인 조촉매의 조합으로 이루어지는데, 이러한 촉매는 균일계 착체 촉매로 단일 활성점 촉매이다. 그에 따라, 메탈로센 촉매는 분자량 분포가 접고 공단량체의 조성 분포가 균일한 중합체의 형성을 가능케 한다. 또한, 메탈로센 촉매는 리간드의 구조 및 중합 조건을 변경함으로써 중합체의 입체 규칙도, 공중합 특성, 분자량, 결정화도 등을 변화시킬 수 있는 특성을 갖는다.The metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst mainly composed of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single active site catalyst. As such, the metallocene catalyst enables the formation of polymers having a folded molecular weight distribution and a uniform compositional distribution of comonomers. In addition, the metallocene catalyst has a property of changing the steric regularity, copolymerization property, molecular weight, crystallinity, etc. of the polymer by changing the structure and polymerization conditions of the ligand.
그 중 안사-메탈로센 촉매는 브릿지 그룹에 의해 서로 연결된 두 개의 리간드를 포함하는 유기금속 촉매로서, 상기 브릿지 그룹에 의해 리간드의 회전이 방지되며 메탈 센터의 활성 및 구조가 결정된다.Among them, the ansa-metallocene catalyst is an organometallic catalyst including two ligands connected to each other by a bridge group. The ligand group prevents the rotation of the ligand and determines the activity and structure of the metal center.
특히, 프로필렌의 중합에 있어서, 안사-메탈로센 촉매는 자일렌 가용분 함량이 낮은 중합체 (예를 들어 1 중량% 미만)를 형성시켜, 녹는 점이 낮은 프로필렌 중합체의 제조에 유리한 장점을 갖는다. 그러나, 이러한 안사-메탈로센 촉매를 이용하여 형성된 프로필렌 중합체는 자일렌 가용분 함량이 너무 낮아 열봉합 특성 등의 기계적 물성을 발현하기 어려운 한계가 있다.In particular, in the polymerization of propylene, the ansa-metallocene catalyst has the advantage of producing a low melting point propylene polymer by forming a polymer having a low content of xylene solubles (for example less than 1% by weight). However, the propylene polymer formed by using the ansa-metallocene catalyst has a limitation in that the xylene soluble content is too low to express mechanical properties such as heat sealing properties.
이처럼 종래의 촉매 시스템으로는 자일렌 가용분의 함량이 너무 높거나 또는 너무 낮은 프로필렌 중합체가 형성되기 때문에, 적정 수준의 녹는 점과 기계적 물성의 발현이 가능한 프로필렌 중합체를 얻을 수 있는 방법의 개발이 필요한 실정이다.Since a propylene polymer having too high or too low content of xylene solubles is formed in the conventional catalyst system, it is necessary to develop a method for obtaining a propylene polymer capable of exhibiting an appropriate level of melting point and mechanical properties. It is true.
본 발명은 목적하는 기계적 물성에 맞도록 자일렌 가용분의 함량이 제어된 프로필렌 중합체의 제공을 가능케 하는 촉매 시스템을 제공하기 위한 것이다.The present invention aims to provide a catalyst system that enables the provision of propylene polymers in which the content of xylene solubles is controlled to suit the desired mechanical properties.
또한, 본 발명은 상기 촉매 시스템을 이용한 프로필렌 중합체의 제조 방법을 제공하기 위한 것이다.The present invention also provides a process for producing a propylene polymer using the catalyst system.
본 발명에 따르면, According to the invention,
담체 및 상기 담체 상에 담지된 메탈로센 화합물을 포함하고;A carrier and a metallocene compound supported on the carrier;
상기 메탈로센 화합물은, 하기 화학식 1로 표시되는 메조 형태의 메탈로센 화합물과, 하기 화학식 2a로 표시되는 화합물 및 하기 화학식 2b로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 라세믹 형태의 메탈로센 화합물을 1: 2 내지 1: 7의 몰 비로 포함하는, 프로필렌 중합용 혼성 담지 촉매 시스템이 제공된다:The metallocene compound is at least one metal of racemic form selected from the group consisting of a metallocene compound having a meso form represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2a, and a compound represented by the following Chemical Formula 2b. A hybrid supported catalyst system for propylene polymerization is provided, comprising a rosene compound in a molar ratio of 1: 2 to 1: 7.
[화학식 1][Formula 1]
[화학식 2a] [Formula 2a]
[화학식 2b] [Formula 2b]
상기 화학식 1, 2a 및 2b에서,In Chemical Formulas 1, 2a and 2b,
X1 및 X2는 각각 독립적으로 할로겐이고,X 1 and X 2 are each independently halogen,
R1 및 R1'는 각각 독립적으로 탄소수 1 내지 20의 알킬로 치환된 탄소수 6 내지 20의 아릴이고,R 1 and R 1 ′ are each independently aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms,
R2, R3, R4, R2', R3', 및 R4'는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 1 내지 20의 알킬실릴, 탄소수 1 내지 20의 실릴알킬, 탄소수 1 내지 20의 알콕시실릴, 탄소수 1 내지 20의 에테르, 탄소수 1 내지 20의 실릴에테르, 탄소수 1 내지 20의 알콕시, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬이고,R 2 , R 3 , R 4 , R 2 ' , R 3' , and R 4 ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms Silyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silyl ether, C1-C20 alkoxy, C6-C20 aryl, C7-C20 Alkylaryl of 20 or arylalkyl of 7 to 20 carbon atoms,
A는 각각 독립적으로 탄소, 실리콘 또는 게르마늄이고,Each A is independently carbon, silicon or germanium,
R5 및 R5'는 각각 독립적으로 탄소수 1 내지 20의 알콕시로 치환된 탄소수 1 내지 20의 알킬이고,R 5 and R 5 ' are each independently alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbon atoms,
R6 및 R6'는 각각 독립적으로 탄소수 1 내지 20의 알킬 또는 탄소수 2 내지 20의 알케닐이다.R 6 and R 6 ' are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.
그리고, 본 발명에 따르면, 상기 혼성 담지 촉매 시스템의 존재 하에 프로필렌을 포함한 올레핀 단량체를 중합시키는 단계를 포함하는, 프로필렌 중합체의 제조 방법이 제공된다.And, according to the present invention, there is provided a process for producing a propylene polymer, comprising the step of polymerizing an olefin monomer comprising propylene in the presence of the hybrid supported catalyst system.
이하, 본 발명의 구현 예들에 올레핀의 올리고머화 방법에 대하여 보다 상세하게 설명한다.Hereinafter, embodiments of the present invention will be described in more detail with respect to the oligomerization method of the olefin.
그에 앞서, 본 명세서 전체에서 명시적인 언급이 없는 한, 전문용어는 단지 특정 실시예를 언급하기 위한 것이며, 본 발명을 한정하는 것을 의도하지 않는다. Prior to this, the terminology is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention unless explicitly stated throughout this specification.
그리고, 여기서 사용되는 단수 형태들은 문구들이 이와 명백히 반대의 의미를 나타내지 않는 한 복수 형태들도 포함한다. 본 명세서에서 사용되는 '포함'의 의미는 특정 특성, 영역, 정수, 단계, 동작, 요소 및/또는 성분을 구체화하며, 다른 특정 특성, 영역, 정수, 단계, 동작, 요소, 성분 및/또는 군의 존재나 부가를 제외시키는 것은 아니다.As used herein, the singular forms “a,” “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite. As used herein, the meaning of "includes" specifies a particular property, region, integer, step, operation, element, and / or component, and other specific properties, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or addition of.
그리고, 본 명세서에서 용어 "라세믹 형태" (racemic form)는 두 개의 사이클로펜타디에닐 부분 상의 동일한 치환체가 지르코늄(Zr) 또는 하프늄(Hf)을 함유한 평면 및 상기 사이클로펜타디에닐 부분의 중앙에 대해 반대편 상에 있는 형태를 의미한다.And the term "racemic form" is used herein to refer to a plane in which the same substituents on two cyclopentadienyl moieties contain zirconium (Zr) or hafnium (Hf) and to the center of the cyclopentadienyl moiety. On the other side.
그리고, 본 명세서에서 용어 "메조 형태" (meso form)는 두 개의 사이클로펜타디에닐 부분 상의 동일한 치환체가 지르코늄(Zr) 또는 하프늄(Hf)을 함유한 평면 및 상기 사이클로펜타디에닐 부분의 중앙에 대해 동일편 상에 있는 형태를 의미한다.And the term "meso form" is used herein to refer to a plane in which the same substituents on two cyclopentadienyl moieties contain zirconium (Zr) or hafnium (Hf) and to the center of the cyclopentadienyl moiety. It means the form on the same piece.
I. 프로필렌 중합용 혼성 담지 촉매 시스템I. Hybrid supported catalyst system for propylene polymerization
발명의 일 구현 예에 따르면,According to one embodiment of the invention,
담체 및 상기 담체 상에 담지된 메탈로센 화합물을 포함하고;A carrier and a metallocene compound supported on the carrier;
상기 메탈로센 화합물은, 하기 화학식 1로 표시되는 메조 형태의 메탈로센 화합물과, 하기 화학식 2a로 표시되는 화합물 및 하기 화학식 2b로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 라세믹 형태의 메탈로센 화합물을 1: 2 내지 1: 7의 몰 비로 포함하는, 프로필렌 중합용 혼성 담지 촉매 시스템이 제공된다:The metallocene compound is at least one metal of racemic form selected from the group consisting of a metallocene compound having a meso form represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2a, and a compound represented by the following Chemical Formula 2b. A hybrid supported catalyst system for propylene polymerization is provided, comprising a rosene compound in a molar ratio of 1: 2 to 1: 7.
[화학식 1] [Formula 1]
[화학식 2a][Formula 2a]
[화학식 2b] [Formula 2b]
상기 화학식 1, 2a 및 2b에서,In Chemical Formulas 1, 2a and 2b,
X1 및 X2는 각각 독립적으로 할로겐이고,X 1 and X 2 are each independently halogen,
R1 및 R1'는 각각 독립적으로 탄소수 1 내지 20의 알킬로 치환된 탄소수 6 내지 20의 아릴이고,R 1 and R 1 ′ are each independently aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms,
R2, R3, R4, R2', R3', 및 R4'는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 1 내지 20의 알킬실릴, 탄소수 1 내지 20의 실릴알킬, 탄소수 1 내지 20의 알콕시실릴, 탄소수 1 내지 20의 에테르, 탄소수 1 내지 20의 실릴에테르, 탄소수 1 내지 20의 알콕시, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬이고,R 2 , R 3 , R 4 , R 2 ' , R 3' , and R 4 ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms Silyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silyl ether, C1-C20 alkoxy, C6-C20 aryl, C7-C20 Alkylaryl of 20 or arylalkyl of 7 to 20 carbon atoms,
A는 각각 독립적으로 탄소, 실리콘 또는 게르마늄이고,Each A is independently carbon, silicon or germanium,
R5 및 R5'는 각각 독립적으로 탄소수 1 내지 20의 알콕시로 치환된 탄소수 1 내지 20의 알킬이고,R 5 and R 5 ' are each independently alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbon atoms,
R6 및 R6'는 각각 독립적으로 탄소수 1 내지 20의 알킬 또는 탄소수 2 내지 20의 알케닐이다.R 6 and R 6 ' are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.
프로필렌 중합체는 입체규칙성(tacticity)에 따라 아이소택틱(isotactic), 신디오택틱(syndiotactic) 또는 아택틱(atactic)으로 분류될 수 있다. 그 중 아택틱 프로필렌 중합체는 무질서한 입체규칙성에 따른 물성의 한계로 인해 상업적 이용이 제한된 반면에, 아이소택틱 프로필렌 중합체는 결정성을 가져 상업적으로 널리 이용되고 있다.Propylene polymers can be classified as isotactic, syndiotactic or atactic, depending on their tacticity. Among these, atactic propylene polymers have limited commercial use due to the limitation of physical properties due to disordered stereoregularity, while isotactic propylene polymers have crystallinity and are widely used commercially.
이러한 아이소택틱 프로필렌 중합체는 지글러-나타의 연구에 의해 상용화 가능하게 되었다. 그런데, 지글러-나타 촉매를 이용하여 형성된 아이소택틱 프로필렌 중합체는 고유동 제품의 호모 폴리프로필렌 또는 낮은 녹는 점을 갖는 랜덤 공중합체에 적용될 경우 자일렌 가용분(즉, 아이소택틱 중합체에 포함되어 있는 아택틱 부분의 함량)이 통상적으로 5 중량%를 초과하기 때문에 상업적으로 활용하기 어려운 한계가 있다.Such isotactic propylene polymers have been made commercially viable by the Ziegler-Natta study. However, isotactic propylene polymers formed using Ziegler-Natta catalysts are used in xylene solubles (i.e., isotactic polymers) when applied to homopolypropylene or high melting random copolymers of high flow products. The content of the atactic moiety) is typically more than 5% by weight, which makes it difficult to use commercially.
이러한 지글러-나타 촉매에 비하여, 메탈로센 촉매, 특히 라세믹 형태의 안사-메탈로센 촉매는 자일렌 가용분의 함량이 1 중량% 미만인 프로필렌 중합체의 형성을 가능케 한다. 그러나, 너무 낮은 자일렌 가용분을 갖는 프로필렌 중합체는 열봉합 특성 등의 기계적 물성을 발현하기 어려운 한계가 있다.Compared to these Ziegler-Natta catalysts, metallocene catalysts, especially ansa-metallocene catalysts in racemic form, enable the formation of propylene polymers having a content of xylene solubles of less than 1% by weight. However, a propylene polymer having too low xylene solubles has a limit in that it is difficult to express mechanical properties such as heat sealing properties.
그런데, 본 발명자들의 계속적인 연구 결과, 라세믹 형태의 메탈로센 화합물과 메조 형태의 메탈로센 화합물이 특정 몰 비로 적용된 촉매 시스템을 이용할 경우, 목적하는 기계적 물성에 맞도록 자일렌 가용분의 함량이 제어된 프로필렌 중합체의 제공을 가능케 함이 확인되었다.However, as a result of continuous research by the present inventors, when using a catalyst system in which a racemic metallocene compound and a meso-type metallocene compound are applied at a specific molar ratio, the content of soluble xylenes to suit the desired mechanical properties It has been found possible to provide this controlled propylene polymer.
일반적으로 라세믹 형태의 메탈로센 화합물은 아이소택틱 프로필렌 중합체의 제조를 가능케 하여 상업적으로 선호되어온 반면, 메조 형태의 메탈로센 화합물은 아택틱 프로필렌 중합체를 형성시키기 때문에 극히 제한적으로 이용되거나 기피되어 왔다.In general, racemic form metallocene compounds have been commercially preferred to allow the preparation of isotactic propylene polymers, while meso form metallocene compounds are extremely limited or avoided because they form atactic propylene polymers. come.
그런데, 본 발명자들의 연구 결과에 따르면, 라세믹 형태 및 메조 형태의 혼합물로 얻어지는 메탈로센 화합물로부터 상기 메조 형태의 화합물을 정제하여 분리한 후, 상기 메조 형태의 화합물과 상기 라세믹 형태의 화합물을 1: 2 내지 1: 7의 몰 비로 촉매 시스템에 적용할 경우, 1 내지 5 중량%의 자일렌 가용분을 갖는 프로필렌 중합체가 제공될 수 있고, 특히 상기 메조 형태 및 라세믹 형태의 화합물의 몰 비에 따라 자일렌 가용분의 함량을 상기 범위에서 쉽게 제어할 수 있음이 확인되었다.However, according to the results of the present inventors, after purifying and separating the meso form compound from the metallocene compound obtained in a mixture of racemic form and meso form, the meso form compound and the racemic compound are When applied to the catalyst system in a molar ratio of 1: 2 to 1: 7, propylene polymers having 1 to 5% by weight of xylene solubles can be provided, in particular molar ratios of the compounds in the meso and racemic forms It was confirmed that the content of xylene solubles can be easily controlled in the above range.
특히, 상술한 효과의 발현을 위하여, 상기 촉매 시스템에는 상기 화학식 1로 표시되는 메조 형태의 메탈로센 화합물과; 상기 화학식 2a로 표시되는 화합물 및 상기 화학식 2b로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 라세믹 형태의 메탈로센 화합물이 적합하게 이용될 수 있다.In particular, in order to express the above-mentioned effects, the catalyst system includes a metallocene compound of meso form represented by Chemical Formula 1; One or more racemic metallocene compounds selected from the group consisting of a compound represented by Formula 2a and a compound represented by Formula 2b may be suitably used.
상기 화학식 1, 2a 및 2b로 표시되는 화합물은 두 개의 인데닐 그룹을 리간드로 포함하는 안사-메탈로센 구조를 갖는다.The compounds represented by Formulas 1, 2a, and 2b have an ansa-metallocene structure containing two indenyl groups as ligands.
상기 화학식 1, 2a 및 2b로 표시되는 화합물은 상기 리간드를 연결하는 브릿지 그룹에 산소-주게로써 루이스 염기의 역할을 할 수 있는 작용기가 치환되어 있어, 촉매로서의 활성이 극대화될 수 있다.Compounds represented by Formulas 1, 2a and 2b are substituted with a functional group capable of acting as a Lewis base as an oxygen donor to the bridge group connecting the ligand, the activity as a catalyst can be maximized.
또한, 상기 리간드에 치환되어 있는 벌키 그룹(R1 및 R1')은 입체 장애를 부여함에 따라, 촉매의 합성 과정에서 기본적으로 메조 형태의 메탈로센 화합물의 형성을 억제할 수 있다.In addition, the bulky groups (R 1 and R 1 ′ ) substituted in the ligand impart steric hindrance, thereby basically suppressing the formation of the meso form metallocene compound in the synthesis of the catalyst.
특히, 발명의 구현 예에 따르면, 라세믹 형태 및 메조 형태의 혼합물로 얻어지는 메탈로센 화합물을 톨루엔, 벤젠, 디클로로메탄 등의 용매 및 -20 ℃ 내지 상온의 온도 하에서 선택적인 재결정 처리를 할 경우, 상기 혼합물로부터 메조 형태의 메탈로센 화합물을 선택적으로 분리할 수 있다. In particular, according to an embodiment of the invention, when the metallocene compound obtained in a mixture of racemic and meso form is subjected to selective recrystallization treatment under a solvent such as toluene, benzene, dichloromethane and the temperature of -20 ℃ to room temperature, The metallocene compound in meso form can be selectively separated from the mixture.
그에 따라, 촉매 시스템에 적용되는 메조 형태의 메탈로센 화합물과 라세믹 형태의 메탈로센 화합물의 몰 비를 보다 정밀하게 제어할 수 있고, 이를 통해 프로필렌 중합체의 자일렌 가용분을 목적하는 기계적 물성에 맞도록 쉽고 제어할 수 있다.Accordingly, the molar ratio of the meso form metallocene compound and the racemic form metallocene compound to be applied to the catalyst system can be more precisely controlled, and thus the desired mechanical properties of the xylene soluble component of the propylene polymer can be controlled. Easy to control and fit.
나아가, 상기 화학식 1 및 화학식 2a로 표시되는 화합물은 금속 원자로 지르코늄(Zr)을 포함함으로써 높은 촉매 활성을 나타낼 수 있다. 그리고, 상기 화학식 2b로 표시되는 화합물은 금속 원자로 하프늄(Hf)을 포함함으로써 높은 분자량의 프로필렌 중합체를 형성시킬 수 있다.Furthermore, the compounds represented by Formula 1 and Formula 2a may exhibit high catalytic activity by including zirconium (Zr) as a metal atom. In addition, the compound represented by Chemical Formula 2b may form a high molecular weight propylene polymer by including hafnium (Hf) as a metal atom.
그리고, 통상의 촉매로 공단량체의 함량을 높여 올레핀계 중합체를 제조할 경우 중합체의 녹는 점이 감소하는 대신 멜트 플로우 인덱스 값이 커져 제조 공정상의 어려움이 나타날 수 있다. 하지만, 발명의 구현 예와 같이 상기 화학식 1, 2a 및 2b로 표시되는 화합물을 적용한 촉매 시스템은 녹는 점이 낮으면서도 멜트 플로우 인덱스 값이 작은 프로필렌 중합체의 형성을 가능케 한다.In addition, when the olefin-based polymer is manufactured by increasing the content of the comonomer with a conventional catalyst, the melt flow index value is increased instead of decreasing the melting point of the polymer, which may cause difficulties in the manufacturing process. However, the catalyst system to which the compounds represented by Chemical Formulas 1, 2a and 2b are applied as in the embodiment of the present invention enables the formation of a propylene polymer having a low melting point and a low melt flow index value.
한편, 발명의 구현 예에 따른 혼성 담지 촉매 시스템은 담체 및 상기 담체 상에 담지된 메탈로센 화합물을 포함한다.Meanwhile, the hybrid supported catalyst system according to the embodiment of the present invention includes a carrier and a metallocene compound supported on the carrier.
상기 담체로는 표면에 하이드록시기를 함유하는 것으로서, 바람직하게는 건조되어 표면에 수분이 제거된, 반응성이 큰 하이드록시기와 실록산기를 갖는 것일 수 있다. 비제한적인 예로, 상기 담체는 고온에서 건조된 실리카, 실리카-알루미나, 및 실리카-마그네시아 등일 수 있다. 그리고, 상기 담체는 Na2O와 같은 산화물, K2CO3와 같은 탄산염, BaSO4와 같은 황산염, Mg(NO3)2와 같은 질산염 성분을 함유할 수 있다.The carrier contains a hydroxyl group on the surface, and preferably may be one having a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture from the surface. By way of non-limiting example, the carrier may be silica, silica-alumina, silica-magnesia, etc. dried at high temperature. The carrier may contain an oxide such as Na 2 O, a carbonate such as K 2 CO 3 , a sulfate such as BaSO 4 , and a nitrate component such as Mg (NO 3 ) 2 .
그리고, 상기 혼성 담지 촉매 시스템에는 메조 형태의 메탈로센 화합물과 라세믹 형태의 메탈로센 화합물이 특정한 몰 비로 포함된다.The hybrid supported catalyst system includes a metallocene compound in a meso form and a metallocene compound in a racemic form in a specific molar ratio.
발명의 구현 예에 따르면, 상기 메조 형태의 메탈로센 화합물로는 상기 화학식 1로 표시되는 메탈로센 화합물이 바람직하게 적용될 수 있다. 그리고, 상기 라세믹 형태의 메탈로센 화합물로는 상기 화학식 2a로 표시되는 화합물 및 상기 화학식 2b로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 화합물이 바람직하게 적용될 수 있다.According to an embodiment of the invention, the metallocene compound represented by Formula 1 may be preferably applied as the metallocene compound in the meso form. As the racemic metallocene compound, at least one compound selected from the group consisting of a compound represented by Formula 2a and a compound represented by Formula 2b may be preferably applied.
특히, 상기 메조 형태의 메탈로센 화합물과 상기 라세믹 형태의 메탈로센 화합물은 1: 2 내지 1: 7, 또는 1: 2.5 내지 1: 7, 또는 1: 2.5 내지 1: 6.5, 또는 1: 3 내지 1: 6.5, 또는 1: 3 내지 1: 6의 몰 비로 포함될 수 있다. 즉, 최적의 촉매 활성을 나타낼 수 있으면서도 1 내지 5 중량%의 자일렌 가용분을 갖는 프로필렌 중합체의 제공을 위하여, 상기 메조 및 라세믹 형태의 메탈로센 화합물의 몰 비는 상기 범위 내에서 조절되는 것이 바람직하다.In particular, the metallocene compound of the meso form and the metallocene compound of the racemic form are 1: 2 to 1: 7, or 1: 2.5 to 1: 7, or 1: 2.5 to 1: 6.5, or 1: 3 to 1: 6.5, or 1: 3 to 1: 6 in a molar ratio. That is, the molar ratio of the metallocene compound of the meso and racemic forms is controlled within the above range in order to provide a propylene polymer having 1 to 5% by weight of xylene solubles while still exhibiting optimum catalytic activity. It is preferable.
발명의 구현 예에 따르면, 상기 화학식 1, 2a 및 2b에서, 상기 X1 및 X2는 각각 독립적으로 할로겐이고; 바람직하게는 각각 Cl일 수 있다.According to an embodiment of the present invention, in Chemical Formulas 1, 2a and 2b, X 1 and X 2 are each independently halogen; Preferably each may be Cl.
그리고, 상기 화학식 1, 2a 및 2b에서, 상기 R1 및 R1'는 각각 독립적으로 탄소수 1 내지 20의 알킬로 치환된 탄소수 6 내지 20의 아릴이고; 바람직하게는 각각 터트-부틸로 치환된 페닐일 수 있고; 보다 바람직하게는 4-터트-부틸페닐일 수 있다.In Formulas 1, 2a and 2b, R 1 and R 1 ' are each independently aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms; Preferably phenyl each substituted with tert-butyl; More preferably 4-tert-butylphenyl.
상기 화학식 1, 2a 및 2b에서, 상기 R2, R3, R4, R2', R3', 및 R4'는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 1 내지 20의 알킬실릴, 탄소수 1 내지 20의 실릴알킬, 탄소수 1 내지 20의 알콕시실릴, 탄소수 1 내지 20의 에테르, 탄소수 1 내지 20의 실릴에테르, 탄소수 1 내지 20의 알콕시, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬이고; 바람직하게는 각각 수소일 수 있다.In Formulas 1, 2a, and 2b, R 2 , R 3 , R 4 , R 2 ' , R 3' , and R 4 ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, and having 2 to 20 carbon atoms. Alkenyl, alkylsilyl having 1 to 20 carbon atoms, silylalkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, Aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Preferably each may be hydrogen.
상기 화학식 1, 2a 및 2b에서, 상기 A는 각각 독립적으로 탄소, 실리콘 또는 게르마늄이고; 바람직하게는 각각 실리콘일 수 있다.In Chemical Formulas 1, 2a and 2b, A is independently carbon, silicon, or germanium; Preferably each may be silicon.
상기 화학식 1, 2a 및 2b에서, 상기 R5 및 R5'는 각각 독립적으로 탄소수 1 내지 20의 알콕시로 치환된 탄소수 1 내지 20의 알킬이고; 바람직하게는 6-터트-부톡시헥실일 수 있다.In Formulas 1, 2a and 2b, R 5 and R 5 ' are each independently alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms; Preferably 6-tert-butoxyhexyl.
상기 화학식 1, 2a 및 2b에서, 상기 R6 및 R6'는 각각 독립적으로 탄소수 1 내지 20의 알킬 또는 탄소수 2 내지 20의 알케닐이고; 바람직하게는 각각 메틸일 수 있다.In Chemical Formulas 1, 2a and 2b, R 6 and R 6 ' are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms; Preferably each may be methyl.
발명의 구현 예에 따르면, 상기 화학식 1로 표시되는 메조 형태의 메탈로센 화합물의 대표적인 예는 다음과 같다:According to an embodiment of the invention, representative examples of the metallocene compound of the meso form represented by Formula 1 are as follows:
그리고, 상기 화학식 2a로 표시되는 라세믹 형태의 메탈로센 화합물의 대표적인 예는 다음과 같다:A representative example of the racemic metallocene compound represented by Formula 2a is as follows:
그리고, 상기 화학식 2b로 표시되는 라세믹 형태의 메탈로센 화합물의 대표적인 예는 다음과 같다:A representative example of the racemic metallocene compound represented by Formula 2b is as follows:
발명의 구현 예에 따르면, 상기 혼성 담지 촉매 시스템에서 상기 메탈로센 화합물은 상기 담체에 대하여 1: 0.001 내지 1: 1의 질량비로 담지될 수 있다. 즉, 상기 질량비로 담체와 메탈로센 화합물을 포함할 때 적절한 촉매 활성을 나타내고, 촉매 활성의 유지 및 경제성 측면에서 유리할 수 있다.According to an embodiment of the invention, the metallocene compound in the hybrid supported catalyst system may be supported in a mass ratio of 1: 0.001 to 1: 1 with respect to the carrier. That is, when the carrier and the metallocene compound are included in the above mass ratio, the catalyst exhibits proper catalytic activity and may be advantageous in terms of maintaining and economical catalytic activity.
한편, 상기 화학식 1 및 2a로 표시되는 메탈로센 화합물은 다음과 같은 방법으로 제조될 수 있다.Meanwhile, the metallocene compounds represented by Chemical Formulas 1 and 2a may be prepared by the following method.
상기 Step 1은 화학식 1-2의 화합물과 화학식 1-3의 화합물을 반응시켜 화학식 1-4의 화합물을 제조하는 단계이다. 상기 Step 1의 반응은 알킬리튬 (예를 들어, n-부틸리튬)을 촉매로 -200 내지 0℃의 온도 하에서 수행될 수 있으며, 용매로 톨루엔, THF 등이 사용될 수 있다. 이때 생성물에서 유기층을 분리한 후, 분리된 유기층을 진공 건조하고 과량의 반응물을 제거하는 것이 바람직하다.Step 1 is a step of preparing a compound of Formula 1-4 by reacting a compound of Formula 1-2 with a compound of Formula 1-3. The reaction of Step 1 may be performed under a temperature of -200 to 0 ° C using an alkyl lithium (eg, n-butyllithium) as a catalyst, and toluene, THF, etc. may be used as a solvent. At this time, after separating the organic layer from the product, it is preferable to vacuum-dry the separated organic layer and remove excess reactant.
상기 Step 2는 화학식 1-4의 화합물과 화학식 1-5의 화합물을 반응시켜 화학식 1 및 2a의 화합물을 제조하는 단계이다. 상기 Step 2의 반응은 알킬리튬 (예를 들어, n-부틸리튬)을 촉매로 -200 내지 0℃의 온도 하에서 수행될 수 있으며, 용매로 에테르, 헥산 등이 사용될 수 있다.Step 2 is a step of preparing a compound of Formula 1 and 2a by reacting a compound of Formula 1-4 and a compound of Formula 1-5. The reaction of Step 2 may be performed under a temperature of -200 to 0 ° C with an alkyl lithium (eg, n-butyllithium) as a catalyst, and ether, hexane, etc. may be used as a solvent.
상기 Step 2에서 화학식 1 및 2a의 화합물은 혼합물의 형태로 얻어진다. 특히 발명의 구현 예에 따르면, 상기 혼합물을 톨루엔, 벤젠, 디클로로메탄 등의 용매 및 -20 ℃ 내지 상온의 온도 하에서 선택적인 재결정 처리를 하는 간단한 방법으로, 상기 혼합물로부터 화학식 1의 메조 형태의 화합물을 선택적으로 분리할 수 있다.In Step 2, the compounds of Formulas 1 and 2a are obtained in the form of a mixture. In particular, according to an embodiment of the invention, a simple method of selectively recrystallization of the mixture with a solvent such as toluene, benzene, dichloromethane and the like at a temperature of -20 ° C to room temperature, the compound of formula 1 Can be selectively separated.
상기 제법과 유사하게, 상기 화학식 2b로 표시되는 메탈로센 화합물은 다음과 같은 방법으로 제조될 수 있다.Similar to the preparation method, the metallocene compound represented by Formula 2b may be prepared by the following method.
상기 Step 1'는 화학식 2-2의 화합물과 화학식 2-3의 화합물을 반응시켜 화학식 2-4의 화합물을 제조하는 단계이다. 상기 Step 1'의 반응은 알킬리튬 (예를 들어, n-부틸리튬)을 촉매로 -200 내지 0℃의 온도 하에서 수행될 수 있으며, 용매로 톨루엔, THF 등이 사용될 수 있다. 이때 생성물에서 유기층을 분리한 후, 분리된 유기층을 진공 건조하고 과량의 반응물을 제거하는 것이 바람직하다.Step 1 ′ is a step of preparing a compound of Formula 2-4 by reacting a compound of Formula 2-2 with a compound of Formula 2-3. The reaction of Step 1 ′ may be performed under a temperature of −200 to 0 ° C. using an alkyl lithium (eg, n-butyllithium) as a catalyst, and toluene, THF, or the like may be used as a solvent. At this time, after separating the organic layer from the product, it is preferable to vacuum-dry the separated organic layer and remove excess reactant.
상기 Step 2'는 화학식 2-4의 화합물과 화학식 2-5의 화합물을 반응시켜 화학식 2b 및 2m의 화합물을 제조하는 단계이다. 상기 Step 2'의 반응은 알킬리튬 (예를 들어, n-부틸리튬)을 촉매로 -200 내지 0℃의 온도 하에서 수행될 수 있으며, 용매로 에테르, 헥산 등이 사용될 수 있다.Step 2 'is a step of preparing a compound of Formula 2b and 2m by reacting the compound of Formula 2-4 and the compound of Formula 2-5. The reaction of Step 2 'may be performed under a temperature of -200 to 0 ° C using an alkyl lithium (for example, n-butyllithium) as a catalyst, and ether, hexane, etc. may be used as a solvent.
상기 Step 2'에서 화학식 2b 및 2m의 화합물은 혼합물의 형태로 얻어진다. 특히 발명의 구현 예에 따르면, 상기 혼합물을 톨루엔, 벤젠, 디클로로메탄 등의 용매 및 -20 ℃ 내지 상온의 온도 하에서 선택적인 재결정 처리를 하는 간단한 방법으로, 상기 혼합물로부터 화학식 2m의 메조 형태의 화합물을 선택적으로 분리할 수 있다.In Step 2 ', the compounds of Formulas 2b and 2m are obtained in the form of a mixture. In particular, according to an embodiment of the invention, a simple method of selectively recrystallization of the mixture under a solvent such as toluene, benzene, dichloromethane and the temperature of -20 ℃ to room temperature, from the mixture of the meso form of the compound of formula 2m Can be selectively separated.
한편, 발명의 구현 예에 따르면, 상기 혼성 담지 촉매 시스템은 하기 화학식 3 내지 5로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 조촉매를 추가로 포함할 수 있다:Meanwhile, according to an embodiment of the present invention, the hybrid supported catalyst system may further include one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5:
[화학식 3][Formula 3]
-[Al(R31)-O]c--[Al (R 31 ) -O] c-
상기 화학식 3에서, In Chemical Formula 3,
c는 2 이상의 정수이고, c is an integer of 2 or more,
R31은 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌이고;Each R 31 is independently halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen;
[화학식 4][Formula 4]
D(R41)3 D (R 41 ) 3
상기 화학식 4에서, In Chemical Formula 4,
D는 알루미늄 또는 보론이고, D is aluminum or boron,
R41은 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌이고;Each R 41 is independently halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen;
[화학식 5][Formula 5]
[L-H]+[Q(E)4]- [LH] + [Q (E) 4 ] -
상기 화학식 5에서,In Chemical Formula 5,
L은 중성 루이스 염기이고, L is a neutral Lewis base,
[L-H]+는 브론스테드 산이며, [LH] + is Bronsted acid,
Q는 +3 형식 산화 상태의 붕소 또는 알루미늄이고, Q is boron or aluminum in the +3 type oxidation state,
E는 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 하이드로카빌, 알콕시 또는 페녹시 작용기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴, 또는 탄소수 1 내지 20의 알킬이다.E is each independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms, which is unsubstituted or substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy functional group.
구체적으로, 상기 화학식 3으로 표시되는 화합물은 메틸알루미녹산, 에틸알루미녹산, 부틸알루미녹산, 아이소부틸알루미녹산 등의 알킬알루미녹산일 수 있다. 또한, 상기 화학식 3의 화합물로는 상기 메틸알루미녹산의 메틸기의 일부가 다른 알킬기로 치환된 화합물인 개질된 메틸알루미녹산(MMAO)이 사용될 수 있다. 일 예로, 상기 개질된 메틸알루미녹산은 상기 메틸알루미녹산의 메틸기 중 40 mol% 이하, 또는 5 mol% 내지 35 mol%가 탄소수 3 내지 10의 직쇄 또는 분지쇄의 알킬기로 치환된 화합물일 수 있다. 상업적으로 입수 가능한 상기 개질된 메틸알루미녹산의 예로는 MMAO-12, MMAO-3A 및 MMAO-7 등을 들 수 있다.Specifically, the compound represented by Formula 3 may be alkyl aluminoxane, such as methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, and isobutyl aluminoxane. In addition, a modified methyl aluminoxane (MMAO) which is a compound in which a part of the methyl group of the methyl aluminoxane is substituted with another alkyl group may be used as the compound of Formula 3. For example, the modified methyl aluminoxane may be a compound in which 40 mol% or less, or 5 mol% to 35 mol% of the methyl group of the methyl aluminoxane is substituted with a linear or branched alkyl group having 3 to 10 carbon atoms. Commercially available examples of such modified methylaluminoxanes include MMAO-12, MMAO-3A, MMAO-7 and the like.
그리고, 상기 화학식 4로 표시되는 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 디메틸이소부틸알루미늄, 디메틸에틸알루미늄, 디에틸클로로알루미늄, 트리이소프로필알루미늄, 트리아이소부틸알루미늄, 트리-s-부틸알루미늄, 트리씨클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등일 수 있다.And, the compound represented by the formula (4) is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro aluminum, triiso Propyl aluminum, triisobutyl 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.
또한, 상기 화학식 5로 표시되는 화합물은 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-디에틸아닐리니움테트라페닐 보론, 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 등 일 수 있다.In addition, the compound represented by the formula (5) is 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 tetraphenyl boron, N, N- Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetra Phenyl 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 tetra (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 tetrapentaflo Rhophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylalu Titanium, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, etc. have.
바람직하게는, 상기 조촉매로는 트리메틸 알루미늄(trimethyl aluminium), 트리에틸 알루미늄(triethyl aluminium), 트리이소프로필 알루미늄(triisopropyl aluminium), 트리이소부틸 알루미늄(triisobutyl aluminum), 에틸알루미늄 세스퀴클로라이드(ethylaluminum sesquichloride), 디에틸알루미늄 클로라이드(diethylaluminum chloride), 에틸 알루미늄 디클로라이드(ethyl aluminium dichloride), 메틸알루미녹산(methylaluminoxane), 및 개질된 메틸알루미녹산(modified methylaluminoxane)으로 이루어진 군에서 선택된 1종 이상의 화합물이 바람직하게 적용될 수 있다.Preferably, as the cocatalyst, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesquichloride ), Diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane are preferably one or more compounds selected from the group consisting of Can be applied.
그리고, 상기 조촉매의 함량은 촉매 활성 등을 고려하여 결정될 수 있다. 발명의 구현 예에 따르면, 상기 조촉매는 상기 메탈로센 화합물에 대하여 1: 1 내지 1: 10000, 또는 1: 1 내지 1: 5000, 또는 1: 1 내지 1: 3000의 몰 비로 포함될 수 있다.In addition, the content of the promoter may be determined in consideration of the catalytic activity and the like. According to an embodiment of the invention, the promoter may be included in a molar ratio of 1: 1 to 1: 10000, or 1: 1 to 1: 5000, or 1: 1 to 1: 3000 with respect to the metallocene compound.
한편, 상기 혼성 담지 촉매 시스템은, 담체 상에 조촉매를 담지시키는 단계; 상기 담체에 상기 화학식 1로 표시되는 메조 형태의 메탈로센 화합물을 담지시키는 단계; 및 상기 화학식 2a로 표시되는 화합물 및 상기 화학식 2b로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 라세믹 형태의 메탈로센 화합물을 담지시키는 단계를 포함하여 제조될 수 있다. 다만, 상기 메탈로센 화합물의 담지 순서는 필요에 따라 바뀔 수 있다.On the other hand, the hybrid supported catalyst system, the step of supporting the promoter on the carrier; Supporting a metallocene compound of meso form represented by Chemical Formula 1 on the carrier; And supporting the metallocene compound of at least one racemic form selected from the group consisting of the compound represented by Formula 2a and the compound represented by Formula 2b. However, the supporting order of the metallocene compound may be changed as necessary.
상기 혼성 담지 촉매 시스템의 제조에는 펜탄, 헥산, 헵탄과 같은 탄화수소계 용매; 또는 벤젠, 톨루엔과 같은 방향족계 용매가 사용될 수 있다.Preparation of the hybrid supported catalyst system includes a hydrocarbon solvent such as pentane, hexane, heptane; Or aromatic solvents such as benzene and toluene may be used.
II. 프로필렌 중합체의 제조 방법II. Process for producing propylene polymer
한편, 발명의 다른 일 구현 예에 따르면, 상술한 혼성 담지 촉매 시스템의 존재 하에 프로필렌을 포함한 올레핀 단량체를 중합시키는 단계를 포함하는, 프로필렌 중합체의 제조 방법이 제공된다.On the other hand, according to another embodiment of the invention, there is provided a method for producing a propylene polymer, comprising the step of polymerizing an olefin monomer comprising propylene in the presence of the hybrid supported catalyst system described above.
상기 프로필렌 중합체의 제조 방법은 상술한 혼성 담지 촉매 시스템의 존재 하에 프로필렌을 포함한 올레핀 단량체를 원료로 통상적인 장치 및 접촉 기술을 적용하여 수행될 수 있다.The process for producing the propylene polymer may be carried out by applying conventional apparatus and contacting techniques with olefin monomers including propylene as raw materials in the presence of the above described hybrid supported catalyst system.
비제한적인 예로, 상기 프로필렌 중합체의 제조 방법은 연속식 슬러리 중합 반응기, 루프 슬러리 반응기, 기상 반응기, 또는 용액 반응기를 이용하여 프로필렌을 호모 중합하거나 또는 프로필렌과 공단량체를 공중합하여 수행될 수 있다. 상기 공단량체로는 에틸렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-아이토센 등이 사용될 수 있다.As a non-limiting example, the process for producing the propylene polymer can be carried out by homopolymerizing propylene using a continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor or by copolymerizing propylene and comonomers. The comonomers include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 -Tetradecene, 1-hexadecene, 1-aitocene and the like can be used.
상기 제조 방법에서, 상기 혼성 담지 촉매 시스템은 펜탄, 헥산, 헵탄, 노난, 데칸, 톨루엔, 벤젠, 디클로로메탄, 클로로벤젠 등의 용매에 용해 또는 희석된 상태된 이용될 수 있다.In the above production method, the hybrid supported catalyst system may be used dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
그리고, 상기 프로필렌 중합체의 제조 방법은 20 내지 500 ℃ 또는 20 내지 200 ℃의 온도, 및 1 내지 100 kgf/㎠ 또는 1 내지 70 kgf/㎠의 압력 하에서, 1 내지 24 시간 또는 1 내지 10 시간 동안 수행될 수 있다.In addition, the method for preparing the propylene polymer is carried out at a temperature of 20 to 500 ° C. or 20 to 200 ° C., and a pressure of 1 to 100 kgf / cm 2 or 1 to 70 kgf / cm 2 for 1 to 24 hours or 1 to 10 hours. Can be.
필요에 따라, 상기 중합은 수소 첨가 또는 미첨가 조건 하에서 수행될 수 있다.If desired, the polymerization can be carried out under hydrogenated or unadded conditions.
특히, 상기 제조 방법에서 상기 혼성 담지 촉매 시스템에 포함된 메탈로센 화합물의 몰 비는 1: 2 내지 1: 7로 조절될 수 있다. 그에 따라, 상기 방법으로 제조되는 프로필렌 중합체에는 자일렌 가용분(xylene solubles)의 함량이 1 내지 5 중량%, 또는 1.5 내지 5 중량%, 또는 1.5 내지 4.9 중량%의 범위에서 부여될 수 있다.In particular, the molar ratio of the metallocene compound included in the hybrid supported catalyst system in the production method may be adjusted to 1: 2 to 1: 7. Accordingly, the propylene polymer prepared by the above method may be given a content of xylene solubles in the range of 1 to 5% by weight, or 1.5 to 5% by weight, or 1.5 to 4.9% by weight.
이처럼 상기 제조 방법은 목적하는 기계적 물성에 맞도록 자일렌 가용분의 함량이 제어된 프로필렌 중합체의 제조에 적합하게 적용될 수 있다.As such, the production method may be suitably applied to the production of propylene polymer in which the content of xylene solubles is controlled to suit the desired mechanical properties.
본 발명에 따른 상기 혼성 담지 촉매 시스템은 우수한 촉매 활성을 가지면서도, 특히 목적하는 기계적 물성에 맞도록 자일렌 가용분의 함량이 제어된 프로필렌 중합체의 제공을 가능케 한다.The hybrid supported catalyst system according to the present invention makes it possible to provide a propylene polymer having excellent catalytic activity and in particular having a controlled content of xylene solubles to suit the desired mechanical properties.
이하, 발명의 이해를 돕기 위하여 바람직한 실시예들을 제시한다. 그러나 하기의 실시예들은 발명을 예시하기 위한 것일 뿐, 발명을 이들만으로 한정하는 것은 아니다.Hereinafter, preferred embodiments will be presented to aid in understanding the invention. However, the following examples are only to illustrate the invention, not limited to the invention only.
합성예Synthesis Example 1 One
rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드의 제조Preparation of rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride
[단계 1][Step 1]
2-메틸-4-터트-부틸페닐인덴 (20.0 g, 76 mmol)을 톨루엔/THF=10/1 용액 (230 mL)에 용해시킨 후, n-부틸리튬 용액 (2.5 M, 헥산 용매, 22 g)을 0℃에서 천천히 적가한 다음, 상온에서 하루 동안 교반하였다. 2-methyl-4-tert-butylphenylindene (20.0 g, 76 mmol) was dissolved in toluene / THF = 10/1 solution (230 mL), then n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at 0 ° C. and then stirred at room temperature for one day.
그 후, -78℃에서 상기 혼합 용액에 (6-t-부톡시헥실)디클로로메틸실란 (1.27 g)을 천천히 적가하였고, 약 10분 동안 교반한 뒤 상온에서 하루 동안 교반하였다. 그 후, 물을 가하여 유기층을 분리한 다음, 용매를 감압 증류하여 [(6-t-부톡시헥실)(메틸)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]실란을 얻었다.Thereafter, (6-t-butoxyhexyl) dichloromethylsilane (1.27 g) was slowly added dropwise to the mixed solution at -78 ° C, and stirred for about 10 minutes, followed by stirring at room temperature for one day. Then, water was added to separate the organic layer, and then the solvent was distilled under reduced pressure to obtain [(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl). ] Silane was obtained.
1H NMR (500 MHz, CDCl3, 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40-1.62 (20H, m), 2.19-2.23 (6H, m), 3.30-3.34 (2H, m), 3.73-3.83 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m) 1 H NMR (500 MHz, CDCl 3 , 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40 -1.62 (20H, m), 2.19-2.23 (6H, m), 3.30-3.34 (2H, m), 3.73-3.83 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m)
[단계 2][Step 2]
상기 단계 1에서 얻은 [(6-t-부톡시헥실)(메틸)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]실란을 톨루엔/THF=5/1 용액 (95 mL)에 용해시킨 후, n-부틸리튬 용액 (2.5 M, 헥산 용매, 22 g)을 -78℃에서 천천히 적가한 후, 상온에서 하루 동안 교반하였다.[(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] silane obtained in step 1 was dissolved in toluene / THF = 5/1 solution ( 95 mL), n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78 ° C, and then stirred at room temperature for one day.
반응액에 비스(N,N'-디페닐-1,3-프로판디아미도)디클로로지르코늄 비스(테트라하이드로퓨란) [Zr(C5H6NCH2CH2NC5H6)Cl2(C4H8O)2]을 톨루엔 (229 mL)에 용해시킨 후, -78℃에서 천천히 적가하고 상온에서 하루 동안 교반하였다. Bis (N, N'-diphenyl-1,3-propanediazido) dichlorozirconium bis (tetrahydrofuran) [Zr (C 5 H 6 NCH 2 CH 2 NC 5 H 6 ) Cl 2 (C 4 H 8 O) 2 ] was dissolved in toluene (229 mL), and then slowly added dropwise at -78 ° C, and stirred at room temperature for one day.
반응액을 -78℃로 냉각시킨 후, HCl 에테르 용액 (1 M, 183 mL)을 천천히 적가하고, 0℃에서 1시간 동안 교반하였다. 이후 여과하고 진공 건조한 다음, 헥산을 넣고 교반하여 결정을 석출시켰다. After cooling the reaction solution to -78 ° C, HCl ether solution (1 M, 183 mL) was slowly added dropwise and stirred at 0 ° C for 1 hour. After filtration and vacuum drying, hexane was added and stirred to precipitate crystals.
석출된 결정을 여과 및 감압 건조하여, 하기 화학식으로 표시되는 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드를 얻었다 (20.5 g).The precipitated crystals were filtered and dried under reduced pressure to obtain rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl represented by the following formula. )] Zirconium dichloride was obtained (20.5 g).
(rac) 
1H NMR (500 MHz, CDCl3, 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s), 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d), 7.59 (2H, d), 7.65 (2H, d) 1 H NMR (500 MHz, CDCl 3 , 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s) , 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d ), 7.59 (2H, d), 7.65 (2H, d)
합성예Synthesis Example 2 2
meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드의 제조Preparation of meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride
[단계 1][Step 1]
상기 합성예 1의 단계 1에서 얻은 [(6-t-부톡시헥실)(메틸)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]실란을 톨루엔/THF=5/1 용액 (95 mL)에 용해시킨 후, n-부틸리튬 용액 (2.5 M, 헥산 용매, 22 g)을 -78℃에서 천천히 적가한 후, 상온에서 하루 동안 교반하였다.[(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] silane obtained in Step 1 of Synthesis Example 1 was toluene / THF = 5 After dissolving in a / 1 solution (95 mL), n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78 ° C, and then stirred at room temperature for one day.
반응액에 1 당량의 지르코늄 테트라클로라이드(ZrCl4)를 -78℃에서 천천히 투입하고, 상온에서 하루 동안 교반하였다.1 equivalent of zirconium tetrachloride (ZrCl 4 ) was slowly added to the reaction solution at -78 ° C, and stirred for 1 day at room temperature.
반응액의 용매를 감압 증류한 다음, 디콜로로메탄 100 mL를 넣고 용해시킨 후 여과하였다. 여액의 용매를 다시 감압 증류하고, 톨루엔 30 mL를 넣고 상온에서 1 시간 교반한 다음, 생성된 결정을 여과 및 건조하여 하기 화학식으로 표시되는 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드를 얻었다.The solvent of the reaction solution was distilled under reduced pressure, 100 mL of dichloromethane was added, dissolved, and filtered. The solvent of the filtrate was distilled under reduced pressure again, 30 mL of toluene was added thereto, stirred at room temperature for 1 hour, and the resulting crystals were filtered and dried to form meso-[(6-t-butoxyhexylmethylsilane-diyl) ) -Bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride was obtained.
(meso)
합성예Synthesis Example 3 3
rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드, 및 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드의 제조rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride, and meso-[(6-t- Preparation of Butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride
[단계 1][Step 1]
3 L의 쉬링크 플라스크(schlenk flask)에 2-메틸-4-(4-t-부틸페닐)-인덴 150 g을 넣고, 톨루엔/THF (10:1, 1.73 L) 용액을 넣어 상온에서 용해시켰다. 상기 용액을 -20℃로 냉각시킨 후에 n-부틸리튬 용액 (n-BuLi, 2.5 M in hexane) 240 mL을 서서히 적가하고 상온에서 3시간 동안 교반하였다. 150 g of 2-methyl-4- (4-t-butylphenyl) -indene was added to a 3 L Schlenk flask, and a toluene / THF (10: 1, 1.73 L) solution was added to dissolve at room temperature. . After cooling the solution to −20 ° C., 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours.
이어서, 반응액을 -20℃로 냉각시킨 다음, (6-t-부톡시헥실)디클로로메틸실란 82 g과 CuCN 512 mg을 서서히 적가하였다. 반응액을 상온으로 승온시킨 후, 12시간 동안 교반하고, 물 500 mL를 첨가하였다. 그 후에, 유기층을 분리하고, MgSO4로 탈수 및 여과 처리하였다. 여액을 감압 증류하여 노란색 오일 형태의 [(6-t-부톡시헥실)(메틸)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]실란을 얻었다.Subsequently, the reaction solution was cooled to −20 ° C., and then 82 g of (6-t-butoxyhexyl) dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was warmed to room temperature, stirred for 12 hours, and 500 mL of water was added. After that, the organic layer was separated, dehydrated with MgSO 4 and filtered. The filtrate was distilled under reduced pressure to obtain [(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] silane in the form of a yellow oil.
1H NMR (500 MHz, CDCl3, 7.26 ppm): -0.09 - -0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m), 3.20-3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m) 1 H NMR (500 MHz, CDCl 3 , 7.26 ppm): -0.09--0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m ), 3.20-3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m)
[단계 2][Step 2]
3 L의 쉬링크 플라스크(schlenk flask)에 앞서 제조한 [(6-t-부톡시헥실)(메틸)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]실란을 넣고, 디에틸에테르 1 L를 넣어 상온에서 용해시켰다. 상기 용액을 -20℃로 냉각시킨 후, n-부틸리튬 용액 (n-BuLi, 2.5 M in hexane) 240 mL를 서서히 적가하고 상온에서 3시간 동안 교반하였다. [(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] silane was prepared previously in a 3 L schlenk flask. 1 L of diethyl ether was added and dissolved at room temperature. After cooling the solution to −20 ° C., 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours.
그 후에, 반응액을 -78℃로 냉각시킨 다음, 하프늄 클로라이드 92 g을 넣었다. 반응 용액을 상온으로 승온시킨 후 12시간 동안 교반하고, 용매를 감압 하에서 제거하였다. 디클로로메탄 1 L를 넣은 다음, 녹지 않은 무기염 등을 여과하여 제거하였다. Thereafter, the reaction solution was cooled to −78 ° C., and 92 g of hafnium chloride was added thereto. The reaction solution was warmed to room temperature, stirred for 12 hours, and the solvent was removed under reduced pressure. 1 L of dichloromethane was added, and the insoluble inorganic salts were filtered off.
여액을 감압 건조하고, 다시 디클로로메탄 300 mL를 넣고 결정을 석출시켰다. 석출된 결정을 여과 및 건조하여, 하기 화학식으로 표시되는 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드, 및 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드의 혼합물을 얻었다 (80 g).The filtrate was dried under reduced pressure, and 300 mL of dichloromethane was added again to precipitate crystals. The precipitated crystals were filtered and dried, and rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl) represented by the following formula: ] A mixture of hafnium dichloride and meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium dichloride (80 g).
(meso) 
1H NMR (500 MHz, CDCl3, 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s), 7.05-7.71 (14H, m) 1 H NMR (500 MHz, CDCl 3 , 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s) , 7.05-7.71 (14H, m)
[단계 3][Step 3]
상기 단계 2에서 얻은 생성물을 제외한 여액에서 용매를 감압 건조한 다음, 톨루엔 100 mL를 넣고 상온에서 1 시간 동안 결정을 석출시켰다. 생성된 결정을 여과 및 건조하여 상기 meso-[(6-t-부톡시헥실메틸실란디일)-비스(2-메틸-4-(4-t-부틸페닐)인데닐)]하프늄 디클로라이드를 선택적으로 분리하였다.The solvent was dried under reduced pressure in the filtrate except the product obtained in step 2, 100 mL of toluene was added thereto, and crystals were precipitated at room temperature for 1 hour. The resulting crystals were filtered and dried to remove the meso-[(6-t-butoxyhexylmethylsilandiyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride. Selective separation.
실시예EXAMPLE 1 One
실리카 3 g을 쉬링크 플라스크에 미리 칭량한 후, 메틸알루미녹산(MAO) 52 mmol을 넣어 90℃에서 24시간 동안 반응시켰다. 침전 후 상층부를 제거하고 톨루엔으로 2회 세척하였다.After weighing 3 g of silica in a shrink flask, 52 mmol of methylaluminoxane (MAO) was added thereto and reacted at 90 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene.
여기에, 상기 합성예 3에서 얻은 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드 (90 마이크로몰, 톨루엔 용액)를 첨가하고, 75℃에서 5시간 동안 반응시켰다. 반응 종료 후 침전이 끝나면, 상층부 용액을 제거하고 남은 반응 생성물을 톨루엔으로 1회 세척하였다.Here, rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] halfium dichloride (Prepared in Synthesis Example 3) 90 micromoles, toluene solution) was added and reacted at 75 ° C. for 5 hours. After the completion of the reaction, when the precipitation was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.
이어서, 상기 합성예 2에서 얻은 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드 (30 마이크로몰, 톨루엔 용액)를 첨가하고, 75℃에서 2시간 동안 반응시켰다. 반응 종료 후 침전이 끝나면, 상층부 용액을 제거하고 남은 반응 생성물을 톨루엔으로 1회 세척하였다.Then, meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride obtained in Synthesis Example 2 was 30 micromoles, toluene solution) was added and reacted at 75 ° C. for 2 hours. After the completion of the reaction, when the precipitation was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.
반응 생성물을 헥산으로 재차 세척하고 진공 건조하여 고체 입자 형태의 혼성 담지 촉매 (meso: rac = 1: 3)를 얻었다.The reaction product was washed again with hexane and dried in vacuo to give a hybrid supported catalyst in the form of solid particles (meso: rac = 1: 3).
실시예EXAMPLE 2 2
메탈로센 화합물의 함량을, 95 마이크로몰의 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드, 및 25 마이크로몰의 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드로 변경한 것을 제외하고, 상기 실시예 1과 동일한 방법으로 혼성 담지 촉매 (meso: rac = 1: 3.8)를 얻었다.The content of the metallocene compound is 95 micromoles of rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium Dichloride, and 25 micromoles of meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride A hybrid supported catalyst (meso: rac = 1: 3.8) was obtained in the same manner as in Example 1, except that the change was made.
실시예EXAMPLE 3 3
메탈로센 화합물의 함량을, 100 마이크로몰의 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드, 및 20 마이크로몰의 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드로 변경한 것을 제외하고, 상기 실시예 1과 동일한 방법으로 혼성 담지 촉매 (meso: rac = 1: 5)를 얻었다.The content of the metallocene compound was determined by adding 100 micromoles of rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium Dichloride and 20 micromoles of meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride A hybrid supported catalyst (meso: rac = 1: 5) was obtained in the same manner as in Example 1, except for the change.
실시예EXAMPLE 4 4
메탈로센 화합물의 함량을, 75 마이크로몰의 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드, 및 15 마이크로몰의 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드로 변경한 것을 제외하고, 상기 실시예 1과 동일한 방법으로 혼성 담지 촉매 (meso: rac = 1: 5)를 얻었다.The content of the metallocene compound was determined to be 75 micromoles of rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] hafnium Dichloride and 15 micromoles of meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride A hybrid supported catalyst (meso: rac = 1: 5) was obtained in the same manner as in Example 1, except for the change.
실시예EXAMPLE 5 5
실리카 3 g을 쉬링크 플라스크에 미리 칭량한 후, 메틸알루미녹산(MAO) 52 mmol을 넣어 90℃에서 24시간 동안 반응시켰다. 침전 후 상층부를 제거하고 톨루엔으로 2회 세척하였다.After weighing 3 g of silica in a shrink flask, 52 mmol of methylaluminoxane (MAO) was added thereto and reacted at 90 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene.
여기에, 상기 합성예 3에서 얻은 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드 (75 마이크로몰, 톨루엔 용액) 및 상기 합성예 1에서 얻은 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드 (15 마이크로몰, 톨루엔 용액)를 첨가하고, 75℃에서 5시간 동안 반응시켰다. 반응 종료 후 침전이 끝나면, 상층부 용액을 제거하고 남은 반응 생성물을 톨루엔으로 1회 세척하였다.Here, rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] halfium dichloride (Prepared in Synthesis Example 3) 75 micromoles, toluene solution) and rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl) obtained in Synthesis Example 1 ] Zirconium dichloride (15 micromoles, toluene solution) was added and reacted at 75 ° C. for 5 hours. After the completion of the reaction, when the precipitation was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.
이어서, 상기 합성예 2에서 얻은 meso-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]지르코륨 디클로라이드 (15 마이크로몰, 톨루엔 용액)를 첨가하고, 75℃에서 2시간 동안 반응시켰다. 반응 종료 후 침전이 끝나면, 상층부 용액을 제거하고 남은 반응 생성물을 톨루엔으로 1회 세척하였다.Then, meso-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride obtained in Synthesis Example 2 was 15 micromoles, toluene solution) were added and reacted at 75 ° C. for 2 hours. After the completion of the reaction, when the precipitation was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.
반응 생성물을 헥산으로 재차 세척하고 진공 건조하여 고체 입자 형태의 혼성 담지 촉매 (meso: rac = 1: 6)를 얻었다.The reaction product was washed again with hexane and dried in vacuo to give a hybrid supported catalyst in the form of solid particles (meso: rac = 1: 6).
비교예Comparative example 1 One
실리카 3 g을 쉬링크 플라스크에 미리 칭량한 후, 메틸알루미녹산(MAO) 52 mmol을 넣어 90℃에서 24시간 동안 반응시켰다. 침전 후 상층부를 제거하고 톨루엔으로 2회 세척하였다.After weighing 3 g of silica in a shrink flask, 52 mmol of methylaluminoxane (MAO) was added thereto and reacted at 90 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene.
여기에, 상기 합성예 3에서 얻은 rac-[(6-t-부톡시헥실메틸실란-디일)-비스(2-메틸-4-(4-터트-부틸페닐)인데닐)]하프늄 디클로라이드 (90 마이크로몰, 톨루엔 용액)를 첨가하고, 75℃에서 5시간 동안 반응시켰다. 반응 종료 후 침전이 끝나면, 상층부 용액을 제거하고 남은 반응 생성물을 톨루엔으로 1회 세척하였다.Here, rac-[(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] halfium dichloride (Prepared in Synthesis Example 3) 90 micromoles, toluene solution) was added and reacted at 75 ° C. for 5 hours. After the completion of the reaction, when the precipitation was completed, the upper layer solution was removed and the remaining reaction product was washed once with toluene.
반응 생성물을 헥산으로 재차 세척하고 진공 건조하여 고체 입자 형태의 담지 촉매를 얻었다.The reaction product was washed again with hexane and dried in vacuo to give a supported catalyst in the form of solid particles.
시험예Test Example 1 One
2 L 스테인레스 반응기를 65℃에서 진공 건조한 후 냉각하고, 실온에서 트리에틸알루미늄 1.5 mmol 및 프로필렌 770 g을 순차적으로 투입하였다. 이를 10분 동안 교반한 후, 상기 실시예 및 비교예에서 제조한 각각의 촉매 30 mg을 TMA 처방된 헥산 20 mL에 녹여 질소 압력으로 반응기에 투입하였다. 이후 에틸렌을 총 15 g 투입하면서 반응기 온도를 70℃까지 천천히 승온한 다음, 1시간 동안 중합하였다. 반응 종료 후 미반응된 프로필렌과 에틸렌을 벤트하였다.The 2 L stainless reactor was vacuum dried at 65 ° C. and then cooled, and 1.5 mmol of triethylaluminum and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, 30 mg of each catalyst prepared in Examples and Comparative Examples was dissolved in 20 mL of TMA prescribed hexane and introduced into the reactor at nitrogen pressure. Then, the reactor temperature was slowly raised to 70 ° C. while adding 15 g of ethylene in total, and then polymerized for 1 hour. After the reaction was completed, unreacted propylene and ethylene were vented.
시험예Test Example 2 2
상기 시험예 1에 따른 프로필렌 중합체의 제조에서 다음과 같은 물성을 측정하였다.In preparing the propylene polymer according to Test Example 1, the following physical properties were measured.
(1) 촉매 활성: 단위 시간(h)을 기준으로 사용된 촉매 함량 (촉매의 mmol 및 g)당 생성된 중합체의 무게(kg)의 비로 계산하였다.(1) Catalyst activity: calculated as the ratio of the weight of the resulting polymer (kg) per catalyst content (mmol and g of catalyst) used, based on unit time (h).
(2) 중합체의 녹는점(Tm): 시차주사열량계(Differential Scanning Calorimeter, DSC, 장치명: DSC 2920, 제조사: TA instrument)를 이용하여 중합체의 녹는점을 측정하였다. 구체적으로 중합체를 220℃까지 가열한 후 5분 동안 그 온도를 유지하였고, 다시 20℃까지 내린 후 다시 온도를 증가시켰으며, 이때 온도의 상승속도와 하강속도는 각각 10℃/min으로 조절하였다.(2) Melting point (Tm) of the polymer: The melting point of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ° C., and then maintained at that temperature for 5 minutes. The temperature was lowered to 20 ° C. and then increased again. At this time, the rate of rise and fall of the temperature was adjusted to 10 ° C./min.
(3) 중합체의 자일렌 가용분(XS): 샘플에 자일렌을 넣고 135℃에서 1 시간 동안 가열하고, 30 분 동안 냉각하여 전처리하였다. OminiSec (Viscotek사 FIPA 장비)에서 1 ml/min Flow rate으로 전처리한 샘플을 측정한 후 Refractive index 피크 면적을 계산하였다.(3) Xylene soluble fraction of polymer (XS): Xylene was added to a sample, heated at 135 ° C. for 1 hour, cooled for 30 minutes, and pretreated. Refractive index peak areas were calculated after measuring samples pretreated at 1 ml / min flow rate in OminiSec (Viscotek FIPA equipment).
(kg PP/g Cat.*hr)Catalytic activity
(kg PP / g Cat. * hr)
(℃)Tm of polymer
(℃)
(중량%)XS of the polymer
(weight%)
상기 표 1을 참고하면, 비교예 1은 중합체의 자일렌 가용분이 1 중량% 미만으로 제한된 반면, 실시예들은 중합에 이용된 메조 및 라세믹 형태의 메탈로센 화합물의 몰 비에 따라 중합체의 자일렌 가용분이 1.8 내지 4.9 중량%의 범위에서 제어될 수 있음이 확인되었다. Referring to Table 1, Comparative Example 1 is limited to xylene soluble content of the polymer to less than 1% by weight, while the examples are the xyl of the polymer according to the molar ratio of the metallocene compound of the meso and racemic form used in the polymerization It was found that the soluble solubles could be controlled in the range of 1.8 to 4.9 wt%.
Claims (9)
상기 메탈로센 화합물은, 하기 화학식 1로 표시되는 메조 형태의 메탈로센 화합물과, 하기 화학식 2a로 표시되는 화합물 및 하기 화학식 2b로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 라세믹 형태의 메탈로센 화합물을 1: 3 내지 1: 6의 몰 비로 포함하는, 프로필렌 중합용 혼성 담지 촉매 시스템:
[화학식 1]
[화학식 2a]
[화학식 2b]
상기 화학식 1, 2a 및 2b에서,
X1 및 X2는 각각 독립적으로 할로겐이고,
R1 및 R1'는 각각 독립적으로 탄소수 1 내지 20의 알킬로 치환된 탄소수 6 내지 20의 아릴이고,
R2, R3, R4, R2', R3', 및 R4'는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 1 내지 20의 알킬실릴, 탄소수 1 내지 20의 실릴알킬, 탄소수 1 내지 20의 알콕시실릴, 탄소수 1 내지 20의 에테르, 탄소수 1 내지 20의 실릴에테르, 탄소수 1 내지 20의 알콕시, 탄소수 6 내지 20의 아릴, 탄소수 7 내지 20의 알킬아릴, 또는 탄소수 7 내지 20의 아릴알킬이고,
A는 각각 독립적으로 탄소, 실리콘 또는 게르마늄이고,
R5는 탄소수 1 내지 20의 알콕시로 치환된 탄소수 1 내지 20의 알킬이고,
R6은 탄소수 1 내지 20의 알킬 또는 탄소수 2 내지 20의 알케닐이다.
A carrier and a metallocene compound supported on the carrier;
The metallocene compound is at least one metal of racemic form selected from the group consisting of a metallocene compound having a meso form represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2a, and a compound represented by the following Chemical Formula 2b. A hybrid supported catalyst system for propylene polymerization, comprising a rosene compound in a molar ratio of 1: 3 to 1: 6:
[Formula 1]
[Formula 2a]
[Formula 2b]
In Chemical Formulas 1, 2a and 2b,
X 1 and X 2 are each independently halogen,
R 1 and R 1 ′ are each independently aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms,
R 2 , R 3 , R 4 , R 2 ' , R 3' , and R 4 ' are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms Silyl, C1-C20 silylalkyl, C1-C20 alkoxysilyl, C1-C20 ether, C1-C20 silyl ether, C1-C20 alkoxy, C6-C20 aryl, C7-C20 Alkylaryl of 20 or arylalkyl of 7 to 20 carbon atoms,
Each A is independently carbon, silicon or germanium,
R 5 is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbon atoms,
R 6 is alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons.
상기 R1 및 R1'는 각각 4-터트-부틸페닐인, 프로필렌 중합용 혼성 담지 촉매 시스템.
The method of claim 1,
The R 1 and R 1 ' are each 4-tert-butylphenyl, hybrid supported catalyst system for propylene polymerization.
상기 R2, R3, R4, R2', R3', 및 R4'는 각각 수소인, 프로필렌 중합용 혼성 담지 촉매 시스템.
The method of claim 1,
The R 2 , R 3 , R 4 , R 2 ' , R 3' , and R 4 ' are each hydrogen, supported hybrid catalyst system for propylene polymerization.
상기 A는 실리콘인, 프로필렌 중합용 혼성 담지 촉매 시스템.
The method of claim 1,
A is a hybrid supported catalyst system for propylene polymerization, wherein A is silicon.
상기 R5는 6-터트-부톡시헥실이고, 상기 R6은 메틸인, 프로필렌 중합용 혼성 담지 촉매 시스템.
The method of claim 1,
Wherein R 5 is 6-tert-butoxyhexyl, and R 6 is methyl, the hybrid supported catalyst system for propylene polymerization.
상기 혼성 담지 촉매 시스템은 하기 화학식 3 내지 5로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 조촉매를 추가로 포함하는, 프로필렌 중합용 혼성 담지 촉매 시스템:
[화학식 3]
-[Al(R31)-O]c-
상기 화학식 3에서,
c는 2 이상의 정수이고,
R31은 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌이고;
[화학식 4]
D(R41)3
상기 화학식 4에서,
D는 알루미늄 또는 보론이고,
R41은 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌이고;
[화학식 5]
[L-H]+[Q(E)4]-
상기 화학식 5에서,
L은 중성 루이스 염기이고,
[L-H]+는 브론스테드 산이며,
Q는 +3 형식 산화 상태의 붕소 또는 알루미늄이고,
E는 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 하이드로카빌, 알콕시 또는 페녹시 작용기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴, 또는 탄소수 1 내지 20의 알킬이다.
The method of claim 1,
The hybrid supported catalyst system further comprises at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5, hybrid supported catalyst system for propylene polymerization:
[Formula 3]
-[Al (R 31 ) -O] c-
In Chemical Formula 3,
c is an integer of 2 or more,
Each R 31 is independently halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen;
[Formula 4]
D (R 41 ) 3
In Chemical Formula 4,
D is aluminum or boron,
Each R 41 is independently halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen;
[Formula 5]
[LH] + [Q (E) 4 ] -
In Chemical Formula 5,
L is a neutral Lewis base,
[LH] + is Bronsted acid,
Q is boron or aluminum in the +3 type oxidation state,
E is each independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms, which is unsubstituted or substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy functional group.
상기 조촉매는 트리메틸 알루미늄(trimethyl aluminium), 트리에틸 알루미늄(triethyl aluminium), 트리이소프로필 알루미늄(triisopropyl aluminium), 트리이소부틸 알루미늄(triisobutyl aluminum), 에틸알루미늄 세스퀴클로라이드(ethylaluminum sesquichloride), 디에틸알루미늄 클로라이드(diethylaluminum chloride), 에틸 알루미늄 디클로라이드(ethyl aluminium dichloride), 메틸알루미녹산(methylaluminoxane), 및 개질된 메틸알루미녹산(modified methylaluminoxane)으로 이루어진 군에서 선택된 1종 이상의 화합물인, 프로필렌 중합용 혼성 담지 촉매 시스템.
The method of claim 6,
The promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesquichloride, diethyl aluminum Hybrid supported catalyst for propylene polymerization, at least one compound selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane system.
A process for producing a propylene polymer comprising polymerizing an olefin monomer comprising propylene in the presence of a hybrid supported catalyst system according to claim 1.
상기 프로필렌 중합체는 1 내지 5 중량%의 자일렌 가용분(xylene solubles)을 갖는, 프로필렌 중합체의 제조 방법.
The method of claim 8,
Wherein said propylene polymer has from 1 to 5 weight percent xylene solubles.
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