KR102092271B1 - Transition metal compound and catalytic composition comprising thereof - Google Patents
Transition metal compound and catalytic composition comprising thereof Download PDFInfo
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- KR102092271B1 KR102092271B1 KR1020150181685A KR20150181685A KR102092271B1 KR 102092271 B1 KR102092271 B1 KR 102092271B1 KR 1020150181685 A KR1020150181685 A KR 1020150181685A KR 20150181685 A KR20150181685 A KR 20150181685A KR 102092271 B1 KR102092271 B1 KR 102092271B1
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- KR
- South Korea
- Prior art keywords
- formula
- transition metal
- metal compound
- carbon atoms
- carbons
- Prior art date
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- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- -1 cationic Lewis acid Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910052795 boron group element Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract description 18
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000003446 ligand Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000002877 alkyl aryl group Chemical group 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 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
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 3
- QNXUZAVLVVDACY-UHFFFAOYSA-N 2-hex-5-enyl-1,3,4,5-tetramethylcyclopenta-1,3-diene Chemical compound C(CCCC=C)C1=C(C(C(=C1C)C)C)C QNXUZAVLVVDACY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- MZEAYWBLQVLWFR-UHFFFAOYSA-N (3-hex-5-enyl-1,2,4,5-tetramethylcyclopenta-2,4-dien-1-yl)-trimethylsilane Chemical compound C(CCCC=C)C1=C(C(C(=C1C)C)(C)[Si](C)(C)C)C MZEAYWBLQVLWFR-UHFFFAOYSA-N 0.000 description 2
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- 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
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XIBZTAIPROXEDH-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 XIBZTAIPROXEDH-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- RIMXEJYJXDBLIE-UHFFFAOYSA-N 6-bromohex-1-ene Chemical compound BrCCCCC=C RIMXEJYJXDBLIE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 1
- XIOUGOKEVVETOO-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN XIOUGOKEVVETOO-UHFFFAOYSA-N 0.000 description 1
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 1
- PDSOPVWYHMINFY-UHFFFAOYSA-K [Cl-].C(CCCC=C)C1=C(C(C(=C1C)C)(C)[Ti+3])C.[Cl-].[Cl-] Chemical compound [Cl-].C(CCCC=C)C1=C(C(C(=C1C)C)(C)[Ti+3])C.[Cl-].[Cl-] PDSOPVWYHMINFY-UHFFFAOYSA-K 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003609 titanium 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
- 150000005671 trienes Chemical class 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F7/28—Titanium compounds
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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- 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
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- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- 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
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- 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
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Abstract
본 발명은 전이금속 화합물 및 이를 포함하는 촉매 조성물에 관한 것이다. 이에 따른, 전이금속 화합물은 선형 알케닐기가 결합되어 있지 않은 전이금속 화합물 대비 저밀도 영역의 높은 분자량을 가지는 올레핀계 중합체의 제조에 있어 중합 반응 촉매로 유용하게 사용될 수 있다.The present invention relates to a transition metal compound and a catalyst composition comprising the same. Accordingly, the transition metal compound can be usefully used as a polymerization reaction catalyst in the production of an olefin-based polymer having a high molecular weight in a low density region compared to a transition metal compound in which a linear alkenyl group is not bonded.
Description
본 발명은 신규한 구조의 전이금속 화합물, 이를 포함하는 촉매 조성물, 상기 촉매 조성물을 이용한 올레핀 중합체의 제조방법 및 올레핀 중합체에 관한 것이다.The present invention relates to a novel structured transition metal compound, a catalyst composition comprising the same, a method for preparing an olefin polymer using the catalyst composition, and an olefin polymer.
일반적으로 에틸렌 공중합체와 같은 올레핀 중합체는 중공 성형품, 압출 성형품, 필름, 시트 등의 재료로 사용되는 유용한 고분자 재료로, 지글러-나타(Ziegler-Natta) 촉매 시스템 존재하에 제조되어왔다. In general, olefin polymers such as ethylene copolymers are useful polymer materials used as materials for blow molded articles, extrusion molded articles, films, sheets, etc., and have been produced in the presence of a Ziegler-Natta catalyst system.
상기 지글러-나타 촉매는 불균일계 촉매로서 반응물질의 상(phase) 및 촉매의 상이 동일하지 않은, 예컨대 액상반응물-고체촉매 등과 같은 계에 사용되는 촉매이다. 이러한, 지글러-나타 촉매는 두 가지 성분으로 구성되는데, 통상 전이금속인 티타늄(Ti), 바나듐(V), 크롬(Cr), 몰리브덴(Mo), 지르코늄(Zr) 등의 할로겐 화합물(예를 들면, TiCl4), 알킬리튬 및 알킬알루미늄 등으로 이루어진다. The Ziegler-Natta catalyst is a heterogeneous catalyst and is a catalyst used in a system in which the phase of the reactant and the phase of the catalyst are not the same, for example, a liquid reactant-solid catalyst. The Ziegler-Natta catalyst is composed of two components, and is a halogen compound such as titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), or zirconium (Zr), which are usually transition metals. , TiCl 4 ), alkyl lithium and alkyl aluminum.
그러나, 상기 지글러-나타 촉매는 활성종 농도가 전이금속 원자에 대해 수% 내지 수십% 정도로서, 대부분의 전이금속 원자가 그 기능을 발휘하지 못함으로써 불균일계 촉매로서의 한계를 극복하지 못하는 단점이 있다. However, the Ziegler-Natta catalyst has a disadvantage in that the concentration of the active species is in the range of several to several tens of percent relative to the transition metal atom, and most transition metal atoms do not exert their functions and thus do not overcome the limitation as a heterogeneous catalyst.
최근, 이러한 단점을 극복할 수 있는 차세대 촉매로서, 메탈로센(metallocene) 화합물들이 주목을 받아오고 있다. 상기 메탈로센 화합물들은 4족 금속을 포함하는 균일계 촉매로서, 올레핀 중합에 있어서 바람직한 중합활성을 나타내는 것으로 알려져있다. 중합에 사용되는 대부분의 메탈로센 촉매는 티타늄, 지르코늄, 하프늄(Hf)과 같은 4족 금속원소와 지지리간드를 그 전구체로 하며, 두 개의 방향성 오원자 고리와 이탈기인 두 개의 할로겐 화합물로 이루어진다. 이들 중 중심 금속에 배위하는 지지리간드는 방향성의 사이클로펜타디에닐(cyclopentadienyl)기가 일반적이다. Recently, as a next-generation catalyst capable of overcoming these drawbacks, metallocene compounds have attracted attention. The metallocene compounds are homogeneous catalysts containing a Group 4 metal and are known to exhibit desirable polymerization activity in olefin polymerization. Most metallocene catalysts used in polymerization are composed of a group 4 metal element such as titanium, zirconium, and hafnium (Hf) and a supporting ligand as their precursors, and are composed of two aromatic compounds, two aromatic rings and leaving groups. Of these, the supporting ligands coordinated to the center metal are generally cyclic cyclopentadienyl groups.
이러한 메탈로센 촉매는 올레핀 중합 공정 등 다양하게 응용되고 있음에도 불구하고 촉매활성(특히, 100℃ 이상의 온도 조건의 용액 공정에서)에 몇몇 한계를 보여왔으며, 일례로 베타-하이드라이드 제거반응(beta-hydride elimination reaction)과 같은 비교적 빠른 말단종결반응(또는 사슬연쇄반응) 때문에, 일반적으로 100℃ 이상의 온도에서 20,000 이하의 분자량(Mn)을 나타내는 저분자량의 올레핀 중합체를 제조할 수 있는 것으로 알려져있다. 또한, 메탈로센 촉매의 활성종은 100℃ 이상의 온도에서 비활성화되는 경향이 있는 것으로 알려져있다. 따라서, 메탈로센 촉매의 적용성을 높이기 위해서는 전술한 바와 같은 한계를 극복할 방안이 필요한 실정이다. Although the metallocene catalyst has various applications such as an olefin polymerization process, it has shown some limitations in catalytic activity (especially in a solution process at a temperature of 100 ° C. or higher), for example, a beta-hydride removal reaction (beta- It is known that olefin polymers having a low molecular weight (Mn) having a molecular weight (Mn) of 20,000 or less at a temperature of 100 ° C. or higher can be produced due to a relatively fast termination reaction (or chain chain reaction) such as a hydride elimination reaction. In addition, it is known that the active species of the metallocene catalyst tend to be deactivated at a temperature of 100 ° C or higher. Therefore, in order to increase the applicability of the metallocene catalyst, there is a need for a method to overcome the limitations as described above.
한편, 상기 지지리간드인 사이클로펜타디에닐 그룹에 적당한 치환체나 새로운 형태의 리간드를 도입하면 중심금속 주위의 공간적 또는 전자적 환경이 변하게 되고, 이에 의해 촉매 자체의 성질도 변하게 된다. On the other hand, when a suitable substituent or a new type of ligand is introduced into the cyclopentadienyl group, which is a supporting ligand, the spatial or electronic environment around the central metal changes, thereby changing the properties of the catalyst itself.
예를 들면, 안사 메탈로센 화합물(Ansa-metallocene complex)들의 리간드 구조를 C2- 또는 Cs-대칭(symmetry)으로 조절함으로써 이소탁틱 폴리프로필렌(Isotatic polypropylene)을 얻을 수 있다. For example, isotactic polypropylene can be obtained by adjusting the ligand structure of the Ansa-metallocene complexes to C2- or Cs-symmetry.
또한, 조촉매로 사용되는 유기 알루미늄 화합물과 상호작용할 수 있는 아민 그룹이 치환된 지르코노센(Zirconocene) 화합물을 사용하여 중합반응을 수행하면 두 가지 모드(bimodal)의 분자량 분포를 갖는 폴리에틸렌을 생성할 수 있다. In addition, when a polymerization reaction is performed using a zirconocene compound substituted with an amine group capable of interacting with an organoaluminum compound used as a cocatalyst, polyethylene having two molecular weight distributions is produced. You can.
더 나아가, 상기 지지리간드의 치환체에 변화를 주면 생성되는 고분자들의 분자량을 조절할 수 있다. 따라서, 지지리간드인 사이클로펜타디에닐의 변화는 중합행동(Polymerization behavior) 및 생성되는 중합체의 물성에 영향을 줄 수 있다. Furthermore, the molecular weight of the resulting polymers can be controlled by changing the substituents of the supporting ligands. Therefore, a change in the support ligand cyclopentadienyl may affect the polymerization behavior and the properties of the resulting polymer.
일례로, aryldiasenido 또는 phosphiniminato 리간드가 도입된 사이클로펜타디에틸 티타늄 화합물이(Journal of Organometallic Chemistry, 159(1978), pp 47-52) 연구된 바 있으며, 미국등록특허 제5,625,016호에는 비가교 4족 금속, 벌키(치환된) 모노사이클로펜타디에닐 리간드, 아미도 리간드[-N(R)2] 및 두 개의 활성화 반응성 리간드로부터 제조된 촉매 시스템의 존재 하에 올레핀 중합, 특히 에틸렌-프로필렌 고무 또는 에틸렌-프로필렌-디엔 공중합체의 제조방법이 개시되어 있고, 미국등록특허 제5,264,405호에는 알루미녹산으로 활성화된 가교된 모노사이클로펜타디에닐 티타늄 화합물을 기초로한 고분자량 및 고 알파-올레핀 함량의 에틸렌-올레핀 공중합체의 제조용 촉매 시스템을 개시하고 있으며, 상기 모노사이클로펜타디에닐기는 메틸기로 치환되고 지방족 또는 지환식 하이드로카빌 리간드를 갖는 아미도기와 1차, 2차 또는 3차 탄소 결합된 구조를 개시하고 있다. For example, a cyclopentadiethyl titanium compound introduced with aryldiasenido or phosphiniminato ligand (Journal of Organometallic Chemistry, 159 (1978), pp 47-52) has been studied, and US Patent No. 5,625,016 has a non-crosslinked Group 4 metal. , Olefin polymerization in the presence of catalyst systems prepared from bulky (substituted) monocyclopentadienyl ligands, amido ligands [-N (R) 2 ] and two activated reactive ligands, in particular ethylene-propylene rubber or ethylene-propylene -A method of manufacturing a diene copolymer is disclosed, and U.S. Patent No. 5,264,405 discloses an ethylene-olefin copolymer of high molecular weight and high alpha-olefin content based on a crosslinked monocyclopentadienyl titanium compound activated with aluminoxane. Disclosed is a catalyst system for the production of coalescence, wherein the monocyclopentadienyl group is substituted with a methyl group and is aliphatic or alicyclic. Id Rocca bill amido group and having a primary ligand, discloses a secondary or tertiary carbon bonded structure.
상기와 같이 지지리간드의 변형을 통한 새로운 형태의 메탈로센 촉매의 개발은 공중합체나 작용기를 가지는 고분자 또는 높은 분자량의 고분자 등과 같이 실제로 유용한 고부가가치의 고분자들의 생산을 가능하게 하는 방안으로 연구되고 있다. As described above, the development of a new type of metallocene catalyst through the modification of the supporting ligand has been studied as a method to enable production of high value-added polymers that are actually useful, such as a polymer having a copolymer or a functional group or a polymer having a high molecular weight. .
그러나, 이를 위한 지지리간드, 즉 사이클로펜타디에틸 그룹의 화학적 변형은 매우 길고 복잡한 합성과정을 필요로 할뿐 아니라 합성과정에 소요되는 비용도 증가하기 때문에 상업화에 장애가 된다. 따라서, 간단한 합성과정을 통해서 촉매를 변형시킴으로써, 시간적 또는 경제적 이점을 가지면서 새로운 물성을 가지는 메탈로센 촉매의 개발이 요구되고 있다.However, the chemical modification of the supporting ligand for this, that is, the cyclopentadiethyl group, is not only a very long and complicated synthesis process, but also increases the cost of the synthesis process, which hinders commercialization. Accordingly, there is a need to develop a metallocene catalyst having a new physical property while having a time or economic advantage by modifying the catalyst through a simple synthesis process.
본 발명은 종래기술의 문제를 해결하기 위하여 안출된 것으로, 신규한 구조의 전이금속 화합물을 제공하는 것을 목적으로 한다. The present invention was devised to solve the problems of the prior art, and aims to provide a transition metal compound having a novel structure.
본 발명의 다른 목적은 상기 전이금속 화합물을 포함하는 촉매 조성물을 제공하는 것이다. Another object of the present invention is to provide a catalyst composition comprising the transition metal compound.
본 발명의 또 다른 목적은 상기 촉매 조성물을 이용하여 제조된 올레핀계중합체 및 올레핀계 중합체의 제조방법을 제공하는 것이다.Another object of the present invention is to provide an olefin-based polymer prepared using the catalyst composition and a method for preparing the olefin-based polymer.
상기의 과제를 해결하기 위하여, 본 발명은 하기 화학식 1로 표시되는 전이금속 화합물을 제공한다.In order to solve the above problems, the present invention provides a transition metal compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R5는 서로 독립적으로 수소; 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 7 내지 20의 알킬아릴; 또는 탄소수 7 내지 20의 아릴알킬이고,R 1 to R 5 are independently of each other hydrogen; Alkyl having 1 to 20 carbons; Alkenyl having 2 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,
R1 내지 R5 중 적어도 하나 이상은 탄소수 2 내지 20의 알케닐이고,At least one of R 1 to R 5 is alkenyl having 2 to 20 carbons,
R6 내지 R8은 서로 독립적으로 수소; 시아노; 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 6 내지 20의 알킬아릴; 탄소수 7 내지 20의 아릴알킬; 탄소수 1 내지 20의 알킬 아미도; 탄소수 6 내지 20의 아릴 아미도; 또는 탄소수 1 내지 20의 알킬리덴이며,R 6 to R 8 are independently of each other hydrogen; Cyano; Alkyl having 1 to 20 carbons; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or an alkylidene having 1 to 20 carbon atoms,
R9 및 R10은 서로 독립적으로 수소; 시아노; 할로겐; 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 7 내지 20의 알킬아릴; 탄소수 7 내지 20의 아릴알킬; 탄소수 1 내지 20의 알킬아미도; 탄소수 6 내지 20의 아릴아미도; 또는 탄소수 1 내지 20의 알킬리덴이며, R 9 and R 10 are independently of each other hydrogen; Cyano; halogen; Alkyl having 1 to 20 carbons; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido having 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene having 1 to 20 carbon atoms,
Q는 Si, C, N, P 또는 S 이고,Q is Si, C, N, P or S,
M은 4족 전이금속이다.M is a Group 4 transition metal.
또한, 본 발명은 상기의 전이금속 화합물을 포함하는 촉매 조성물을 제공한다. In addition, the present invention provides a catalyst composition comprising the transition metal compound.
아울러, 본 발명은 상기의 전이금속 화합물을 이용한 올레핀계 중합체의 제조방법을 제공하는 것이다.In addition, the present invention provides a method for producing an olefin-based polymer using the transition metal compound.
본 발명의 신규한 구조의 전이금속 화합물은 선형 알케닐기가 결합되어 있지 않은 전이금속 화합물 대비 저밀도 영역의 높은 분자량을 가지는 올레핀계 중합체의 제조에 있어 중합 반응 촉매로 유용하게 사용될 수 있고, 밀도에 차별성을 가지는 올레핀계 중합체를 제조할 수 있다.The transition metal compound of the novel structure of the present invention can be usefully used as a polymerization reaction catalyst in the production of an olefin-based polymer having a high molecular weight in a low-density region as compared to a transition metal compound in which a linear alkenyl group is not bonded, and is differentiated in density. It can manufacture an olefin-based polymer having.
이하, 본 발명에 대한 이해를 돕기 위해 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
본 발명 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the present invention and claims should not be interpreted as being limited to a conventional or dictionary meaning, and the inventor can appropriately define the concept of terms in order to explain his or her invention in the best way. Based on the principle that it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.
본 발명은 하기 화학식 1로 표시되는 전이금속 화합물을 제공한다.The present invention provides a transition metal compound represented by Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R5는 서로 독립적으로 수소; 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 7 내지 20의 알킬아릴; 또는 탄소수 7 내지 20의 아릴알킬이고,R 1 to R 5 are independently of each other hydrogen; Alkyl having 1 to 20 carbons; Alkenyl having 2 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,
R1 내지 R5 중 적어도 하나 이상은 탄소수 2 내지 20의 알케닐이고,At least one of R 1 to R 5 is alkenyl having 2 to 20 carbons,
R6 내지 R8은 서로 독립적으로 수소; 시아노; 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 6 내지 20의 알킬아릴; 탄소수 7 내지 20의 아릴알킬; 탄소수 1 내지 20의 알킬 아미도; 탄소수 6 내지 20의 아릴 아미도; 또는 탄소수 1 내지 20의 알킬리덴이며,R 6 to R 8 are independently of each other hydrogen; Cyano; Alkyl having 1 to 20 carbons; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or an alkylidene having 1 to 20 carbon atoms,
R9 및 R10은 서로 독립적으로 수소; 시아노; 할로겐; 탄소수 1 내지 20의 알킬; 탄소수 2 내지 20의 알케닐; 탄소수 6 내지 20의 아릴; 탄소수 7 내지 20의 알킬아릴; 탄소수 7 내지 20의 아릴알킬; 탄소수 1 내지 20의 알킬아미도; 탄소수 6 내지 20의 아릴아미도; 또는 탄소수 1 내지 20의 알킬리덴이며, R 9 and R 10 are independently of each other hydrogen; Cyano; halogen; Alkyl having 1 to 20 carbons; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido having 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene having 1 to 20 carbon atoms,
Q는 P이고,Q is P,
M은 4족 전이금속이다.M is a Group 4 transition metal.
상기 화학식 1로 표시되는 전이금속 화합물은 적어도 하나의 불포화 탄화수소기, 즉 알케닐기가 치환된 시클로펜타디엔 리간드가 4족 전이금속과 배위결합되고, 상기 4족 전이금속에 치환된 포스핀이미드(phosphinimide) 유래기가 안정적으로 결합된 구조를 나타낸다. 이에, 상기 전이금속 화합물을 촉매의 일 성분으로 사용할 경우 상기 촉매의 활성이 증가할 수 있고, 저밀도의 고분자량을 갖는 올레핀계 중합체를 제조할 수 있다. 따라서, 높은 중합 온도에서도 고활성, 고분자량 및 높은 공중합성 등의 특징을 갖는 올레핀계 중합체를 제조하는 것이 가능할 수 있다. 특히, 촉매의 구조적인 특징상 선형 저밀도 폴리에틸렌뿐만 아니라 많은 양의 알파-올레핀이 도입 가능하기 때문에 저밀도 영역의 중합체(엘라스토머)도 제조할 수 있다. In the transition metal compound represented by Formula 1, at least one unsaturated hydrocarbon group, that is, a cyclopentadiene ligand substituted with an alkenyl group is coordinated with a Group 4 transition metal, and a phosphineimide substituted with the Group 4 transition metal ( phosphinimide) indicates a structure in which the origin group is stably bound. Accordingly, when the transition metal compound is used as a component of the catalyst, the activity of the catalyst may increase, and an olefin-based polymer having a low density and high molecular weight may be prepared. Therefore, it may be possible to produce an olefin-based polymer having characteristics such as high activity, high molecular weight and high copolymerization even at a high polymerization temperature. In particular, due to the structural characteristics of the catalyst, not only linear low-density polyethylene but also large amounts of alpha-olefin can be introduced, so that a polymer (elastomer) in a low-density region can be produced.
본 발명에 있어서, 알킬은 직쇄 또는 분지쇄일 수 있다. In the present invention, the alkyl can be straight or branched chain.
본 발명에 있어서, 아릴은 단환 또는 다환의 아릴을 포함하며, 구체적으로 페닐, 나프틸, 안트릴, 페난트릴, 크라이세닐, 파이레닐 등이 포함될 수 있다. In the present invention, aryl includes monocyclic or polycyclic aryl, and may specifically include phenyl, naphthyl, anthryl, phenanthryl, chrysenyl, pyrenyl, and the like.
구체적으로, 본 발명의 일 실시예에 따르면, 상기 화학식 1에서 R1 내지 R5는 서로 독립적으로 수소; 탄소수 1 내지 10의 알킬; 탄소수 2 내지 10의 알케닐; 탄소수 6 내지 10의 아릴; 탄소수 7 내지 10의 알킬아릴; 또는 탄소수 7 내지 10의 아릴알킬이고, 여기에서 상기 R1 내지 R5 중 적어도 하나 이상은 탄소수 2 내지 10의 알케닐이고, R6 내지 R8은 서로 독립적으로 수소; 시아노; 탄소수 1 내지 20의 알킬; 탄소수 1 내지 20의 알킬 아미도, 탄소수 2 내지 10의 알케닐; 탄소수 6 내지 10의 아릴; 또는 탄소수 6 내지 10의 알킬아릴이고, R9 및 R10은 서로 독립적으로 할로겐; 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐 또는 탄소수 6 내지 10의 아릴이며, Q는 P인 것일 수 있다. Specifically, according to an embodiment of the present invention, R 1 to R 5 in Formula 1 are independently of each other hydrogen; Alkyl having 1 to 10 carbons; Alkenyl having 2 to 10 carbon atoms; Aryl having 6 to 10 carbon atoms; Alkylaryl having 7 to 10 carbon atoms; Or arylalkyl having 7 to 10 carbon atoms, wherein at least one of R 1 to R 5 is alkenyl having 2 to 10 carbon atoms, and R 6 to R 8 are independently of each other hydrogen; Cyano; Alkyl having 1 to 20 carbons; Alkyl amido having 1 to 20 carbon atoms, alkenyl having 2 to 10 carbon atoms; Aryl having 6 to 10 carbon atoms; Or an alkylaryl having 6 to 10 carbon atoms, R 9 and R 10 are independently of each other halogen; Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or aryl having 6 to 10 carbons, and Q may be P.
더욱 구체적으로, 상기 화학식 1에서 R1 내지 R5는 서로 독립적으로 수소 또는 탄소수 1 내지 6의 알킬이고, 여기에서 상기 R1 내지 R5 중 적어도 하나 이상은 탄소수 2 내지 6의 알케닐이고, R6 내지 R8은 서로 독립적으로 수소; 시아노; 탄소수 1 내지 20의 알킬; 탄소수 1 내지 20의 알킬 아미도 또는 탄소수 6 내지 10의 아릴이고, R9 및 R10은 서로 독립적으로 할로겐; 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐 또는 탄소수 6 내지 10의 아릴이며, Q는 P인 것일 수 있다. More specifically, in Formula 1, R 1 to R 5 are each independently hydrogen or alkyl having 1 to 6 carbons, wherein at least one of R 1 to R 5 is alkenyl having 2 to 6 carbons, R 6 to R 8 are independently of each other hydrogen; Cyano; Alkyl having 1 to 20 carbons; Alkyl amido having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms, and R 9 and R 10 are each independently halogen; Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or aryl having 6 to 10 carbons, and Q may be P.
더욱 구체적으로는, 상기 화학식 1에서 R1 내지 R5는 서로 독립적으로 탄소수 1 내지 6의 알킬이고, 여기에서 상기 R1 내지 R5 중 적어도 하나 이상은 탄소수 2 내지 6의 알케닐이고, R6 내지 R8은 서로 독립적으로 탄소수 1 내지 20의 알킬; 또는 탄소수 6 내지 20의 알킬아미도이고, R9 및 R10은 서로 독립적으로 할로겐; 탄소수 1 내지 6의 알킬이며, Q는 P인 것일 수 있다. More specifically, in Formula 1, R 1 to R 5 are each independently alkyl having 1 to 6 carbon atoms, wherein at least one of R 1 to R 5 is alkenyl having 2 to 6 carbon atoms, and R 6 To R 8 are independently of each other alkyl having 1 to 20 carbons; Or an alkylamido having 6 to 20 carbon atoms, and R 9 and R 10 are each independently halogen; Alkyl having 1 to 6 carbon atoms, and Q may be P.
본 발명의 일 실시예에 따르면, 상기 화학식 1에서 M은 Ti, Hf 또는 Zr인 것일 수 있으며, 구체적으로는 M은 Ti인 것일 수 있다. According to an embodiment of the present invention, in Chemical Formula 1, M may be Ti, Hf, or Zr, and specifically, M may be Ti.
또한, 본 발명의 일 실시예에 따른 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 내지 화학식 4로 표시되는 화합물 중 어느 하나로 표시되는 것일 수 있다. In addition, the compound represented by Formula 1 according to an embodiment of the present invention may be represented by any one of the compounds represented by Formulas 2 to 4 below.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
한편, 본 발명의 일 실시예에 따른 상기 화학식 1로 표시되는 전이금속 화합물은 치환된 사이클로펜타디에닐 리간드를 제조하고, 치환된 포스핀이미드(Phosphinimide)를 반응시킨 후 4족 금속 화합물을 반응시킴으로써 제조하는 것일 수 있다. Meanwhile, the transition metal compound represented by Chemical Formula 1 according to an embodiment of the present invention prepares a substituted cyclopentadienyl ligand, reacts a substituted phosphinimide, and then reacts a Group 4 metal compound. It may be manufactured by.
구체적으로는, 상기 치환된 사이클로펜타디에닐 리간드는 하기의 반응식 1에 의하여 제조할 수 있다. Specifically, the substituted cyclopentadienyl ligand can be prepared according to Reaction Scheme 1 below.
[반응식 1][Scheme 1]
또한, 본 발명은 상기 화학식 1로 표시되는 전이금속 화합물을 포함하는 촉매 조성물을 제공한다. In addition, the present invention provides a catalyst composition comprising a transition metal compound represented by the formula (1).
본 발명의 일 실시예에 따른 상기 촉매 조성물은 조촉매를 더 포함할 수 있다. The catalyst composition according to an embodiment of the present invention may further include a co-catalyst.
구체적으로, 상기 조촉매는 하기 화학식 5 내지 화학식 7 중 적어도 하나일 수 있다. Specifically, the cocatalyst may be at least one of the following Chemical Formulas 5 to 7.
[화학식 5][Formula 5]
-[Al(R22)-O]a- - [Al (R 22) -O ] a -
상기 식에서, R22은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이며; a는 2 이상의 정수이며;In the above formula, R 22 are each independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
[화학식 6][Formula 6]
D(R22)3 D (R 22 ) 3
상기 식에서, D가 알루미늄 또는 보론이며; R22이 각각 독립적으로 상기에 정의된 대로이며;Wherein D is aluminum or boron; R 22 are each independently as defined above;
[화학식 7][Formula 7]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]- [LH] + [Z (A ) 4] - or [L] + [Z (A ) 4] -
상기 식에서, L이 중성 또는 양이온성 루이스 산이고; H가 수소 원자이며; Z가 13족 원소이고; A는 각각 독립적으로 1 이상의 수소 원자가 치환기로 치환될 수 있는 탄소수 6 내지 20의 아릴 또는 탄소수 1 내지 20의 알킬이며; 상기 치환기는 할로겐, 탄소수 1 내지 20의 하이드로카르빌, 탄소수 1 내지 20의 알콕시, 또는 탄소수 6 내지 20의 아릴옥시이다.Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group 13 element; A is each independently aryl having 6 to 20 carbons or alkyl having 1 to 20 carbons, in which one or more hydrogen atoms may be substituted with substituents; The substituent is halogen, hydrocarbyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or aryloxy having 6 to 20 carbons.
상기 화학식 5로 표시되는 화합물은 알킬알루미녹산일 수 있으며, 구체적으로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등일 수 있다. 더욱 구체적으로는, 상기 화학식 5로 표시되는 화합물은 메틸알루미녹산일 수 있다. The compound represented by Chemical Formula 5 may be alkyl aluminoxane, specifically methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like. More specifically, the compound represented by Chemical Formula 5 may be methyl aluminoxane.
상기 화학식 6으로 표시되는 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등일 수 있다. 구체적으로는, 상기 화학식 6으로 표시되는 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄 중에서 선택된 것일 수 있다.The compound represented by Chemical Formula 6 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tri Pentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, Triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like. Specifically, the compound represented by Chemical Formula 6 may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.
상기 화학식 7로 표시되는 화합물은 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리부틸암모니움테트라펜타플루오로페닐보론, N,N-디에틸아닐리디움테트라페틸보론, N,N-디에틸아닐리디움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플루오로페닐보론, 디에틸암모니움테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄, 트리부틸암모니움테트라펜타플루오로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플루오로페닐알루미늄, 디에틸암모니움테트라펜타텐트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론,트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리부틸암모니움테트라펜타플루오로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플루오로페닐보론, 디에틸암모니움테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리페닐카보니움테트라(p-트리플루오로메틸페닐)보론, 트리페닐카보니움테트라펜타플루오로페닐보론 등일 수 있다.The compound represented by Formula 7 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, Trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluoro Lophenylboron, N, N-diethylanilidiumtetrafetylboron, N, N-diethylaniliniumtetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium Tetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, Trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl Aluminium, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (p-trifluoromethylphenyl) aluminum, tributylammoniumtetrapentafluorophenylaluminum, N, N-diethylanil Lineium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentanetraphenylaluminum, triphenylphosphonium Tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, tri Tylammonium tetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra (p-tolyl) boron, triethylammoniumtetra (o, p-dimethylphenyl ) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammonium Tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, di It may be ethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, triphenyl carbonium tetra (p-trifluoromethylphenyl) boron, triphenyl carbonium tetrapentafluorophenyl boron, and the like.
한편, 상기 촉매 조성물은 특별히 제한되는 것은 아니나, 예컨대 하기 방법 1 및 방법 2를 통해 제조되는 것일 수 있다. Meanwhile, the catalyst composition is not particularly limited, but may be, for example, prepared through the following method 1 and method 2.
상기 방법 1은, 상기 화학식 1로 표시되는 전이금속 화합물과 상기 화학식 5 또는 화학식 6으로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 상기 혼합물에 상기 화학식 7로 표시되는 화합물을 첨가하는 단계를 통하여 수행하는 것일 수 있다. Method 1 comprises the steps of contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 5 or Formula 6 to obtain a mixture; And adding the compound represented by Chemical Formula 7 to the mixture.
상기 방법 2는, 상기 화학식 1로 표시되는 전이금속 화합물과 상기 화학식 10으로 표시되는 화합물을 접촉시켜 수행하는 것일 수 있다. Method 2 may be performed by contacting the transition metal compound represented by Chemical Formula 1 with a compound represented by Chemical Formula 10.
상기 방법 1의 경우, 상기 화학식 1의 전이금속 화합물 대비 상기 화학식 5 또는 화학식 6으로 표시되는 화합물의 몰비는 각각 1:2 내지 1:5,000일 수 있으며, 구체적으로는 1:10 내지 1:1,000일 수 있고, 더욱 구체적으로는 1:20 내지 1:500일 수 있다.In the case of Method 1, the molar ratio of the compound represented by Formula 5 or Formula 6 compared to the transition metal compound of Formula 1 may be 1: 2 to 1: 5,000, respectively, specifically 1:10 to 1: 1,000 days It may be, and more specifically 1: 20 to 1: 500.
한편, 상기 화학식 1의 전이금속 화합물 대비 상기 화학식 7로 표시되는 화합물의 몰비는 1:1 내지 1:25일 수 있으며, 구체적으로는 1:1 내지 1:10일 수 있고, 더욱 구체적으로는 1:1 내지 1:5일 수 있다.Meanwhile, the molar ratio of the compound represented by Chemical Formula 7 to the transition metal compound of Chemical Formula 1 may be 1: 1 to 1:25, specifically 1: 1 to 1:10, and more specifically 1 It may be 1: 1 to 1: 5.
상기 화학식 1의 전이금속 화합물 대비 상기 화학식 5 또는 화학식 6으로 표시되는 화합물의 몰비가 1:2 미만일 경우에는 알킬화제의 양이 매우 작아 금속 화합물의 알킬화가 완전히 진행되지 못하는 문제가 있고 1:5,000 초과인 경우에는 금속 화합물의 알킬화는 이루어지지만, 남아있는 과량의 알킬화제와 상기 화학식 10의 활성화제 간의 부반응으로 인하여 알킬화된 금속 화합물의 활성화가 완전히 이루어지지 못하는 문제가 발생할 수 있다. 또한 상기 화학식 1의 전이금속 화합물 대비 상기 화학식 7로 표시되는 화합물의 비가 1:1 미만일 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 발생할 수 있고 1:25 초과인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적으로 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 발생할 수 있다.When the molar ratio of the compound represented by the formula (5) or formula (6) to the transition metal compound of the formula (1) is less than 1: 2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound is not completely progressed, and it is greater than 1: 5,000. In the case, the alkylation of the metal compound is performed, but a problem that the activation of the alkylated metal compound may not be completely performed may occur due to a side reaction between the remaining excess alkylating agent and the activator of Chemical Formula 10. In addition, when the ratio of the compound represented by the formula (7) to the transition metal compound of the formula (1) is less than 1: 1, the amount of the activator is relatively small, so that the activation of the metal compound is not completely achieved, resulting in a decrease in the activity of the resulting catalyst composition. May occur and the activation of the metal compound may be completely performed when it is greater than 1:25, but a problem may arise in which the unit price of the catalyst composition is not economically economical or the purity of the resulting polymer decreases with the remaining excess activator.
상기 방법 2의 경우 상기 화학식 1의 전이금속 화합물 대비 화학식 7로 표시되는 화합물의 몰비는 1:1 내지 1:500일 수 있으며, 구체적으로는 1:1 내지 1:50일 수 있고, 더욱 구체적으로는 1:2 내지 1:25일 수 있다. 상기 몰비가 1:1 미만일 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 1:500 초과인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 발생할 수 있다.In the case of Method 2, the molar ratio of the compound represented by Formula 7 to the transition metal compound of Formula 1 may be 1: 1 to 1: 500, specifically 1: 1 to 1:50, and more specifically May be 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activator is relatively small, and thus the activation of the metal compound is not completely achieved, resulting in a decrease in the activity of the resulting catalyst composition, and when it is greater than 1: 500, the activation of the metal compound Although completely made, it is possible that the cost of the catalyst composition is not economical or the purity of the resulting polymer is reduced due to the excess amount of the activator remaining.
상기 조성물의 제조 시에 반응 용매로서 펜탄, 헥산, 헵탄 등과 같은 탄화수소계 용매나, 벤젠, 톨루엔 등과 같은 방향족계 용매가 사용될 수 있으나, 반드시 이에 한정되지는 않으며 당해 기술 분야에서 사용 가능한 모든 용매가 사용될 수 있다.When preparing the composition, a hydrocarbon-based solvent such as pentane, hexane, heptane, or the like, or an aromatic-based solvent such as benzene or toluene may be used, but not limited thereto, and all solvents usable in the art may be used. You can.
또한, 상기 화학식 1의 전이금속 화합물과 조촉매는 담체에 담지된 형태로도 이용할 수 있다. 담체로는 실리카나 알루미나가 사용될 수 있다. In addition, the transition metal compound of Formula 1 and the cocatalyst can also be used in a form supported on a carrier. Silica or alumina can be used as the carrier.
아울러, 본 발명은 상기 화학식 1로 표시되는 전이금속 화합물을 포함하는 촉매 조성물을 이용한 올레핀계 중합체의 제조방법을 제공한다. In addition, the present invention provides a method for producing an olefin-based polymer using a catalyst composition comprising a transition metal compound represented by Formula 1 above.
본 발명의 일 실시예에 따른 상기 제조방법은 상기 화학식 1로 표시되는 전이금속 화합물; 및 상기 화학식 5 내지 화학식 7로 표시되는 화합물로부터 선택되는 하나 이상의 화합물을 포함하는 촉매 조성물을 하나 이상의 올레핀계 단량체와 접촉시켜 폴리올레핀 호모 중합체 또는 공중합체를 제조할 수 있다. The manufacturing method according to an embodiment of the present invention is a transition metal compound represented by the formula (1); And a catalyst composition comprising at least one compound selected from the compounds represented by Chemical Formulas 5 to 7 with one or more olefinic monomers to prepare a polyolefin homopolymer or copolymer.
상기 제조방법은 용액공정일 이용한 것일 수 있으며, 상기 촉매 조성물을 실리카와 같은 무기 담체와 함께 사용하는 경우에는 슬러리 또는 기상공정을 통해 수행할 수 있다. The manufacturing method may be a solution process, and when the catalyst composition is used together with an inorganic carrier such as silica, it may be performed through a slurry or gas phase process.
상기 촉매 조성물은 탄소수 5 내지 12의 지방족 탄화수소 용매, 예를 들면 펜탄, 헥산, 헵탄, 노난, 데칸, 및 이들의 이성질체와 톨루엔, 벤젠과 같은 방향족 탄화수소 용매, 디클로로메탄, 클로로벤젠과 같은 염소원자로 치환된 탄화수소 용매 등에 용해하거나 희석하여 사용할 수 있다. 여기에 사용되는 용매는 소량의 알킬알루미늄을 처리함으로써 촉매 독으로 작용하는 소량의 물 또는 공기 등을 제거하여 사용하는 것이 바람직하며, 조촉매를 더 사용하여 실시하는 것도 가능하다.The catalyst composition is substituted with an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene and benzene, and chlorine atoms such as dichloromethane and chlorobenzene. It can be used after being dissolved or diluted in a hydrocarbon solvent. The solvent used herein is preferably used by removing a small amount of water or air acting as a catalyst poison by treating a small amount of alkyl aluminum, and it is also possible to further use a cocatalyst.
상기 촉매 조성물을 사용하여 중합 가능한 올레핀계 단량체의 예로는 에틸렌, 알파-올레핀, 사이클릭 올레핀 등이 있으며, 이중 결합을 2개 이상 가지고 있는 디엔 올레핀계 단량체 또는 트리엔 올레핀계 단량체 등도 중합 가능하다. 상기 단량체의 구체적인 예로는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-아이코센, 노보넨, 노보나디엔, 에틸리덴노보넨, 페닐노보넨, 비닐노보넨, 디사이클로펜타디엔, 1,4-부타디엔, 1,5-펜타디엔, 1,6-헥사디엔, 스티렌, 알파-메틸스티렌, 디비닐벤젠, 3-클로로메틸스티렌 등이 있으며, 이들 단량체를 2 종 이상 혼합하여 공중합할 수도 있다.Examples of olefinic monomers that can be polymerized using the catalyst composition include ethylene, alpha-olefins, cyclic olefins, and diene olefinic monomers or triene olefinic monomers having two or more double bonds. Specific examples of the monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-icocene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and two or more of these monomers may be mixed and copolymerized.
특히, 본 발명의 제조방법에서 상기 촉매 조성물은 90℃ 이상의 높은 반응온도에서도 에틸렌과 1-옥텐과 같은 입체적 장애가 큰 단량체의 공중합 반응에서 높은 분자량을 가지면서도 저밀도 공중합체를 제조할 수 있다. In particular, in the production method of the present invention, the catalyst composition may produce a low-density copolymer while having a high molecular weight in the copolymerization reaction of a monomer having a large steric hindrance such as ethylene and 1-octene even at a reaction temperature of 90 ° C. or higher.
또한, 본 발명의 일 실시예에 따르면, 상기 화학식 1의 전이금속 화합물을포함하는 촉매 조성물을 이용하여 중합체를 형성하는 경우, Tm(용융온도)이 낮아질 수 있다.In addition, according to an embodiment of the present invention, when forming a polymer using a catalyst composition comprising the transition metal compound of Formula 1, Tm (melting temperature) may be lowered.
여기에서, 상기 Tm은 PerkinElmer사에서 제조한 시차주사열량계(DSC: Differential Scanning Calorimeter 6000)를 이용하여 얻을 수 있으며, 중합체 온도를 100℃까지 증가시킨 후, 1분 동안 그 온도에서 유지하고 그 다음 -100℃까지 내리고, 다시 온도를 증가시켜 DSC 곡선의 꼭대기를 녹는점(용융온도)으로 측정할 수 있다 Here, the Tm can be obtained by using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerkinElmer. After increasing the polymer temperature to 100 ° C., it is maintained at that temperature for 1 minute and then − It can be measured by melting the top of the DSC curve (melting temperature) by lowering it to 100 ° C and increasing the temperature again.
본 발명의 일 실시예에 따르면, 본 발명의 제조 방법에 의하여 제조된 중합체는 Tm이 109℃ 이하일 수 있다. According to an embodiment of the present invention, the polymer prepared by the production method of the present invention may have a Tm of 109 ° C or less.
이하, 하기 실시예에 의거하여 본 발명을 보다 구체적으로 설명한다. 이들 실시예는 본 발명의 이해를 돕기 위한 것으로서 본 발명의 범위가 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. These examples are intended to aid the understanding of the present invention, and the scope of the present invention is not limited by them.
유기 시약 및 용매는 특별한 언급이 없으면 알드리치(Aldrich)사에서 구입하여 표준 방법으로 정제하여 사용하였다. 합성의 모든 단계에서 공기와 수분의 접촉을 차단하여 실험의 재현성을 높였다. Organic reagents and solvents were purchased from Aldrich unless otherwise specified and purified by standard methods. Blocking the contact of air and moisture at all stages of synthesis increased the reproducibility of the experiment.
합성예Synthetic example
1) 2-(헥스-5-엔-1-일)-1,3,4,5-테트라메틸사이클로펜타-1,3-디엔의 제조1) Preparation of 2- (hex-5-en-1-yl) -1,3,4,5-tetramethylcyclopenta-1,3-diene
진공 건조된 슈랭크 플라스크에 마그네슘(Mg turnning) 797 mg(32.784 mmol)을 넣고 진공건조를 10분동안 하였다. 이후 테트라하이드로퓨란(THF) 20 ml와 1,2-디브로모에탄 0.23 ml(2.73 mmol)을 순차적으로 천천히 적가하고 힛건으로 열을 가한 후 20분 동안 교반하였다. 용액의 색깔이 회색이 되는 것을 확인한 후, 6-브로모헥스-1-엔 4.9 g(30.05 mmol)과 테트라하이드로퓨란 50 ml을 천천히 적가하고 30분 동안 상온에서 교반하였다. 이후, 트리메틸실릴 클로라이드 4.1 ml(27.32 mmol)을 0℃에서 천천히 적가하고 1시간 동안 상온에서 교반하였따. NMR로 원료물질이 없어지는 것을 확인한 후, 6N HCl 70 ml를 0℃에서 천천히 적가하고 상온에서 2시간 동안 교반하였다. NMR, TLC로 생성물을 확인한 후 헥산 20 ml을 적가하고 교반하여 물충을 분리하여 제거하고 MgSO4로 수분을 제거하여 유기층을 얻었다. 이후, 감압여과를 통해 crude 생성물 4.5 g(수율 70%)을 얻었다. 얻어진 상기 crude 생성물을 실리카 컬럼(Hexane:EA=30:1)을 이용하여 액체상태인 하기 화학식 (i)의 2-(헥스-5-엔-1-일)-1,3,4,5-테트라메틸사이클로펜타-1,3-디엔 4.3 g(수율 70%)을 얻었다. 정제된 2-(헥스-5-엔-1-일)-1,3,4,5-테트라메틸사이클로펜타-1,3-디엔의 1H 핵자기공명 분광학적 데이터는 아래와 같다.Magnesium (Mg turnning) 797 mg (32.784 mmol) was added to a vacuum-dried Schrank flask, and vacuum drying was performed for 10 minutes. Subsequently, 20 ml of tetrahydrofuran (THF) and 0.23 ml (2.73 mmol) of 1,2-dibromoethane were slowly added dropwise sequentially, followed by heating with a dry gun and stirring for 20 minutes. After confirming that the color of the solution was gray, 4.9 g (30.05 mmol) of 6-bromohex-1-ene and 50 ml of tetrahydrofuran were slowly added dropwise and stirred at room temperature for 30 minutes. Thereafter, 4.1 ml (27.32 mmol) of trimethylsilyl chloride was slowly added dropwise at 0 ° C. and stirred at room temperature for 1 hour. After confirming that the raw material disappeared by NMR, 70 ml of 6N HCl was slowly added dropwise at 0 ° C and stirred at room temperature for 2 hours. After confirming the product by NMR and TLC, 20 ml of hexane was added dropwise and stirred to separate and remove water worms, and water was removed with MgSO 4 to obtain an organic layer. Thereafter, 4.5 g (70% yield) of crude product was obtained through filtration under reduced pressure. 2- (hex-5-en-1-yl) -1,3,4,5- of the following formula (i) in liquid form using the silica product (Hexane: EA = 30: 1) as the obtained crude product. 4.3 g (70% yield) of tetramethylcyclopenta-1,3-diene was obtained. The 1 H nuclear magnetic resonance spectroscopy data of the purified 2- (hex-5-en-1-yl) -1,3,4,5-tetramethylcyclopenta-1,3-diene are as follows.
1H-NMR (500 MHz, in Benzene): δ 5.87-5.74(m, 1H), 4.99 (d, 1H), 2.64-1.04(m, 9H), 1.82(s, 6H), 1.78(s, 8H). 1 H-NMR (500 MHz, in Benzene): δ 5.87-5.74 (m, 1H), 4.99 (d, 1H), 2.64-1.04 (m, 9H), 1.82 (s, 6H), 1.78 (s, 8H) ).
2) (3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-디엔-1-일)티타늄 클로라이드의 제조2) Preparation of (3- (hex-5-en-1-yl) -1,2,4,5-tetramethylcyclopenta-2,4-dien-1-yl) titanium chloride
1)에서 제조된 2-(헥스-5-엔-1-일)-1,3,4,5-테트라메틸사이클로펜타-1,3-디엔 2.85 g(13.95 mmol)을 테트라하이드로퓨란 30 ml에 녹인 후 -20℃에서 n-부틸리튬 5.8 ml(14.64 mmol, 1.05 eq)를 천천히 적가하였다. 그 후 천천히 승온시켜 상온에서 12시간 동안 교반하였다. NMR로 출발물질이 없어진 것을 확인한 후 상온에서 테트라메틸실릴클로라이드(TMSCl) 2.67 ml(20.93 mmol, 1.5 eq)를 천천히 적가하고 상온에서 12시간 동안 교반하였다. NMR로 출발물질이 없어진 것을 확인하고 감압여과하여 용매를 제거하고 반응 생성물을 헥산 30 ml에 녹이고 여과하여 리튬클로라이드를 제거하였다. 이후 감압여과하여 헥산을 제거하고 (3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-디엔-1-일)트리메틸실란 2.27 g을 얻었다. 얻어진 (3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-디엔-1-일)트리메틸실란 2.27 g(8.21 mmol)을 톨루엔 40 ml에 녹인 후, 상온에서 TiCl4 8.22 ml(8.22 mmol, 1M in 톨루엔)을 천천히 교반하면서 첨가하고, 80℃에서 5시간 동안 교반하였다. NMR로 출발물질이 없어진 것을 확인하고 감압여과하여 톨루엔을 제저하여 진한 붉은색의 끈적이는 액체 상태의 하기 화학식 (ii)의 (3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-티타늄 클로라이드 2.2 g(수율 75%)을 수득하였다. 정제된 (3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-티타늄(IV) 클로라이드의 1H 핵자기공명 분광학적 데이터는 아래와 같다.2.85 g (13.95 mmol) of 2- (hex-5-en-1-yl) -1,3,4,5-tetramethylcyclopenta-1,3-diene prepared in 1) in 30 ml of tetrahydrofuran After melting, 5.8 ml (14.64 mmol, 1.05 eq) of n-butyllithium was slowly added dropwise at -20 ° C. Then, the mixture was slowly heated and stirred at room temperature for 12 hours. After confirming that the starting material disappeared by NMR, 2.67 ml (20.93 mmol, 1.5 eq) of tetramethylsilyl chloride (TMSCl) was slowly added dropwise at room temperature and stirred at room temperature for 12 hours. After confirming that the starting material disappeared by NMR, the solvent was removed by filtration under reduced pressure, and the reaction product was dissolved in 30 ml of hexane and filtered to remove lithium chloride. After filtration under reduced pressure, hexane was removed and 2.27 g of (3- (hex-5-en-1-yl) -1,2,4,5-tetramethylcyclopenta-2,4-dien-1-yl) trimethylsilane Got 2.27 g (8.21 mmol) of (3- (hex-5-en-1-yl) -1,2,4,5-tetramethylcyclopenta-2,4-dien-1-yl) trimethylsilane obtained toluene 40 After dissolving in ml, 8.22 ml (8.22 mmol, 1M in toluene) of TiCl 4 at room temperature was added with slow stirring, and stirred at 80 ° C. for 5 hours. After confirming that the starting material was disappeared by NMR, and filtering under reduced pressure, toluene was removed to obtain a dark red sticky liquid (3- (hex-5-en-1-yl) -1,2,4 of formula (ii) Obtained 2.2 g (yield 75%) of, 5-tetramethylcyclopenta-2,4-titanium chloride Purified (3- (hex-5-en-1-yl) -1,2,4,5- The 1 H nuclear magnetic resonance spectroscopy data of tetramethylcyclopenta-2,4-titanium (IV) chloride are as follows.
1H-NMR (500 MHz, in benzene): δ 5.69-5.59(m, 1H), 4.97-4.94(m, 2H), 2.64-2.61(m, 2H), 1.99(s, 6H), 1.90(s, 6H), 1.86-1.81(m, 2H), 1.26-0.84(m, 5H). 1 H-NMR (500 MHz, in benzene): δ 5.69-5.59 (m, 1H), 4.97-4.94 (m, 2H), 2.64-2.61 (m, 2H), 1.99 (s, 6H), 1.90 (s , 6H), 1.86-1.81 (m, 2H), 1.26-0.84 (m, 5H).
제조 Produce 실시예Example 1 One
100 ml 쉬렝크 플라스크에서 상기 합성예에서 제조된 (3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-티타늄(IV) 클로라이드 1.0 g(2.80 mmol)과 1,1,1-트리사이클로헥실-N-(트리메틸실릴)-5-포스핀이민(1,1,1-tricyclohexyl-N-(trimethylsilyl)-5-phohphineimine) 1.03 g(2.80 mmol)을 톨루엔 15 ml에 녹인 후 80℃에서 12시간 동안 교반하였다. NMR로 출발물질이 없어진 것을 확인한 후 여과하여 톨루엔을 제거하고 반응물을 수득하였다. 수득된 반응물을 톨루엔 15 ml에 녹인 후 상온에서 브롬화메틸마그네슘(MeMgBr) 1.90 ml(5.60 mmol, 2.0 eq)를 천천히 적가하고 상온에서 12시간 동안 교반하였다. NMR로 출발물질이 없어진 것을 확인하고 감압여과하여 톨루엔을 분리제거하고 반응물을 헥산 20 ml에 녹였다. 이후, 여과하여 고체를 제거하고 용액층을 감압여과하여 헥산을 제거한 후 갈색의 점도가 높은 액체상태의 하기 화학식 2의 전이금속 화합물 1.29 g(수율 80%)을 수득하였다. 정제된 화학식 2의 전이금속 화합물의 1H 핵자기공명 분광학적 데이터는 아래와 같다.(3- (hex-5-en-1-yl) -1,2,4,5-tetramethylcyclopenta-2,4-titanium (IV) chloride 1.0 prepared in Synthesis Example in a 100 ml Schlenk flask g (2.80 mmol) and 1,1,1-tricyclohexyl-N- (trimethylsilyl) -5-phosphinimine (1,1,1-tricyclohexyl-N- (trimethylsilyl) -5-phohphineimine) 1.03 g ( 2.80 mmol) was dissolved in 15 ml of toluene and stirred for 12 hours at 80 ° C. After confirming that the starting material had disappeared by NMR, toluene was removed by filtration to obtain a reaction product. In methyl magnesium bromide (MeMgBr) 1.90 ml (5.60 mmol, 2.0 eq) was slowly added dropwise and stirred for 12 hours at room temperature After confirming that the starting material disappeared by NMR, toluene was filtered off under reduced pressure to remove and remove the reaction from 20 ml of hexane. Then, the solid was removed by filtration, and the solution layer was filtered under reduced pressure to remove hexane, and then the brown viscosity. To a high liquid to give a transition metal compound 1.29 g (80% yield) of the general formula (2). 1 H-NMR spectroscopic data of the transition metal compound of formula (II) is purified as follows.
[화학식 2][Formula 2]
1H-NMR (500 MHz, in benzene): δ 5.81-5.69(m, 1H), 4.94(d, 1H), 2.56-2.51(m, 2H), 2.11(s, 6H), 2.07(s, 6H), 2.50-1.00(m, 39H), 0.42(s, 6H). 1 H-NMR (500 MHz, in benzene): δ 5.81-5.69 (m, 1H), 4.94 (d, 1H), 2.56-2.51 (m, 2H), 2.11 (s, 6H), 2.07 (s, 6H ), 2.50-1.00 (m, 39H), 0.42 (s, 6H).
제조 Produce 실시예Example 2 2
1,1,1-트리사이클로헥실-N-(트리메틸실릴)-5-포스핀이민 대신에 1,1,1-트리다이에틸아민-N-(트리메틸실릴)-5-포스핀이민(1,1,1-trididethylamine-N-(trimethylsilyl)-5-phosphineimine)을 사용한 것을 제외하고는 동일한 방법을 통하여 하기 화학식 3의 전이금속 화합물을 수득하였다. 정제된 화학식 3의 1H 핵자기공명 분광학적 데이터는 아래와 같다.1,1,1-tridiethylamine-N- (trimethylsilyl) -5-phosphineimine (1, instead of 1,1,1-tricyclohexyl-N- (trimethylsilyl) -5-phosphineimine The transition metal compound of Chemical Formula 3 was obtained through the same method, except that 1,1-trididethylamine-N- (trimethylsilyl) -5-phosphineimine) was used. The purified 1 H nuclear magnetic resonance spectroscopy data of Chemical Formula 3 is as follows.
[화학식 3][Formula 3]
1H-NMR (500 MHz, in benzene): δ 5.79-5.71 (m, 1H), 5.00 (d, 1H), 4.94 (d, 1H), 3.11-3.05 (m, 12H), 2.52-2.49 (m, 2H), 2.09 (s, 6H), 2.04 (s, 6H), 1.62-1.40 (m, 6H), 1.03-0.93 (d, 18H), 0.40 (s, 6H). 1 H-NMR (500 MHz, in benzene): δ 5.79-5.71 (m, 1H), 5.00 (d, 1H), 4.94 (d, 1H), 3.11-3.05 (m, 12H), 2.52-2.49 (m , 2H), 2.09 (s, 6H), 2.04 (s, 6H), 1.62-1.40 (m, 6H), 1.03-0.93 (d, 18H), 0.40 (s, 6H).
제조 Produce 실시예Example 3 3
1,1,1-트리사이클로헥실-N-(트리메틸실릴)-5-포스핀이민 대신에 1,1,1-트리터셔리부틸-N-(트리메틸실릴)-5-포스핀이민(1,1,1-tri-t-butyl-N-(trimethylsilyl)-5-phosphineimine)을 사용한 것을 제외하고는 동일한 방법을 통하여 하기 화학식 4 전이금속 화합물을 수득하였다. 정제된 화학식 4의 1H 핵자기공명 분광학적 데이터는 아래와 같다.Instead of 1,1,1-tricyclohexyl-N- (trimethylsilyl) -5-phosphineimine, 1,1,1-tritarybutyl-N- (trimethylsilyl) -5-phosphineimine (1, The following transition metal compound was obtained through the same method, except that 1,1-tri-t-butyl-N- (trimethylsilyl) -5-phosphineimine) was used. The purified 1 H nuclear magnetic resonance spectroscopy of Chemical Formula 4 is as follows.
[화학식 4][Formula 4]
1H-NMR (500 MHz, in benzene): δ 5.81-5.69 (m, 1H), 4.99 (d, 1H), 4.95 (d, 1H), 2.58-2.50 (m, 2H), 2.10 (s, 6H), 2.08 (s, 6H), 1.42-1.00 (m, 6H), 1.29 (d, 27H), 0.41 (s, 6H). 1 H-NMR (500 MHz, in benzene): δ 5.81-5.69 (m, 1H), 4.99 (d, 1H), 4.95 (d, 1H), 2.58-2.50 (m, 2H), 2.10 (s, 6H ), 2.08 (s, 6H), 1.42-1.00 (m, 6H), 1.29 (d, 27H), 0.41 (s, 6H).
제조 Produce 비교예Comparative example 1 One
(3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-티타늄(IV) 클로라이드 대신에 (1,2,3,4,5-펜타메틸사이클로펜타-2,4-디엔-1-일)티타늄(IV) 클로라이드를 사용한 것을 제외하고는 제조 실시예 1와 동일한 방법을 통하여 하기 화학식 (iii)으로 표시되는 전이금속 화합물을 수득하였다. 정제된 화학식 (iii)으로 표시되는 전이금속 화합물의 1H 핵자기공명 분광학적 데이터는 아래와 같다.(3- (hex-5-en-1-yl) -1,2,4,5-tetramethylcyclopenta-2,4-titanium (IV) chloride instead of (1,2,3,4,5- A transition metal compound represented by the following formula (iii) was obtained through the same method as in Production Example 1, except that pentamethylcyclopenta-2,4-dien-1-yl) titanium (IV) chloride was used. The 1 H nuclear magnetic resonance spectroscopy data of the transition metal compound represented by the purified formula (iii) are as follows.
1H-NMR (500 MHz, in benzene): δ 2.07 (s, 15H), 1.98-1.03 (m, 33H), 0.42 (s, 6H). 1 H-NMR (500 MHz, in benzene): δ 2.07 (s, 15H), 1.98-1.03 (m, 33H), 0.42 (s, 6H).
제조 Produce 비교예Comparative example 2 2
(3-(헥스-5-엔-1-일)-1,2,4,5-테트라메틸사이클로펜타-2,4-티타늄(IV) 클로라이드 대신에 (1,2,3,4,5-펜타메틸사이클로펜타-2,4-디엔-1-일)티타늄(IV) 클로라이드를 사용한 것을 제외하고는 제조 실시예 2와 동일한 방법을 통하여 하기 화학식 (iv)로 표시되는 전이금속 화합물을 수득하였다. 정제된 화학식 (iv)로 표시되는 전이금속 화합물의 1H 핵자기공명 분광학적 데이터는 아래와 같다.(3- (hex-5-en-1-yl) -1,2,4,5-tetramethylcyclopenta-2,4-titanium (IV) chloride instead of (1,2,3,4,5- A transition metal compound represented by the following formula (iv) was obtained through the same method as in Production Example 2, except that pentamethylcyclopenta-2,4-dien-1-yl) titanium (IV) chloride was used. The 1 H nuclear magnetic resonance spectroscopy data of the transition metal compound represented by the purified formula (iv) are as follows.
1H-NMR (500 MHz, in benzene): δ 3.09-3.03 (m, 12H), 2.04 (s, 15H), 0.95 (t, 18H), 0.40 (s, 6H). 1 H-NMR (500 MHz, in benzene): δ 3.09-3.03 (m, 12H), 2.04 (s, 15H), 0.95 (t, 18H), 0.40 (s, 6H).
실시예 1 Example 1
2 L 오토클레이브 반응기에 헥산 용매(1.0 L)와 1-옥텐(320 ml)을 가한 후, 반응기의 온도를 150℃로 예열하였다. 그와 동시에 반응기의 압력을 에틸렌(35bar)으로 미리 채워 놓았다. 디메틸아닐리늄 테트라키스(펜타플루오로페닐) 보레이트 조촉매(20 μmol)와 트리이소부틸알루미늄 화합물로 처리된 상기 제조 실시예 1의 화학식 2로 표시되는 전이금속 화합물(1.0 μmol)을 고압 아르곤 압력을 가하여 반응기에 넣었다(Al:Ti의 몰비=10:1). 이어서, 공중합 반응을 8분간 진행하였다. 다음으로, 남은 에틸렌 가스를 빼내고 고분자 용액을 과량의 에탄올에 가하여 침전을 유도하였다. 침전된 고분자를 에탄올로 2 내지 3회 세척한 후, 90℃ 진공 오븐에서 12시간 이상 건조하여 중합체를 수득하였다.After adding hexane solvent (1.0 L) and 1-octene (320 ml) to the 2 L autoclave reactor, the temperature of the reactor was preheated to 150 ° C. At the same time, the pressure of the reactor was pre-filled with ethylene (35 bar). Dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst (20 μmol) and a triisobutylaluminum compound treated with a transition metal compound represented by the formula (2) of formula 1 (1.0 μmol) under high pressure argon pressure Was added and put into a reactor (molar ratio of Al: Ti = 10: 1). Subsequently, the copolymerization reaction was performed for 8 minutes. Next, the remaining ethylene gas was drained and a polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed 2-3 times with ethanol, and then dried in a vacuum oven at 90 ° C. for 12 hours or more to obtain a polymer.
실시예 2Example 2
상기 제조 실시예 1의 전이금속 화합물 대신에 제조 실시예 2의 화학식 3으로 표시되는 전이금속 화합물을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 중합체를 수득하였다. A polymer was obtained through the same method as in Example 1, except that the transition metal compound represented by Chemical Formula 3 of Preparation Example 2 was used instead of the transition metal compound of Preparation Example 1.
비교예 1Comparative Example 1
상기 제조 실시예 1의 전이금속 화합물 대신에 제조 비교예의 화학식 (iii)의 전이금속 화합물을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 중합체를 수득하였다. A polymer was obtained through the same method as in Example 1, except that the transition metal compound of Chemical Formula (iii) of Production Comparative Example was used instead of the transition metal compound of Preparation Example 1.
비교예 2Comparative Example 2
상기 제조 실시예 1의 전이금속 화합물 대신에 제조 비교예 2의 화학식 (iv)의 전이금속 화합물을 사용한 것을 제외하고는 상기 실시예 2와 동일한 방법을 통하여 중합체를 수득하였다.A polymer was obtained through the same method as in Example 2, except that the transition metal compound of Formula (iv) of Preparation Comparative Example 2 was used instead of the transition metal compound of Preparation Example 1.
실험예Experimental example
상기 실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 각 중합체의 천정온도(Tc) 및 용융온도(Melting temperature, Tm)를 비교분석하였다. 측정 결과를 하기 표 1에 나타내었다.The ceiling temperature (Tc) and the melting temperature (Tm) of each of the polymers prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were comparatively analyzed. The measurement results are shown in Table 1 below.
천정온도(Tc) 및 용융온도(Melting temperature, Tm)는 PerkinElmer 사에서 제조한 시차주사열량계(DSC: Differential Scanning Calorimeter 6000)을 이용하여 측정하였다. 구체적으로, 측정 용기에 상기 실시예 1, 실시예 2, 비교예 1 및 비교예 2의 각 중합체를 약 0.5 mg 내지 10 mg로 각각 충진하고, 질소 가스 유량을 20 ml/min으로 조절한 후, 상기 각 중합체의 열이력을 동일하게 하기 위하여 각 중합체를 0℃에서 150℃의 온도까지 20 ℃/min의 속도로 승온시켰다. 그 후 다시 150℃에서 -100℃의 온도까지 10 ℃/min의 속도로 냉각한 후 다시 -100℃에서 150℃의 온도까지 10 ℃/min의 속도로 승온시키면서 DSC로 측정한 열류량(heat flow)의 가열 곡선의 피크, 즉 가열시의 흡열 피크 온도를 용융온도로 하여 측정하였다.The ceiling temperature (Tc) and the melting temperature (Tm) were measured using a differential scanning calorimeter (DSC) manufactured by PerkinElmer. Specifically, each of the polymers of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were filled into a measuring container at about 0.5 mg to 10 mg, and the nitrogen gas flow rate was adjusted to 20 ml / min. Each polymer was heated at a rate of 20 ° C / min from 0 ° C to 150 ° C in order to make the heat history of each polymer the same. Then, after cooling again at a rate of 10 ° C / min from a temperature of 150 ° C to -100 ° C, the temperature of heat flow measured by DSC while heating again at a rate of 10 ° C / min from a temperature of -100 ° C to 150 ° C The peak of the heating curve, ie, the endothermic peak temperature during heating, was measured as the melting temperature.
상기 표 1에 나타난 바와 같이 본 발명의 일 실시예에 따른 전이금속 화합물을 촉매로 사용하여 제조된 실시예 1 및 실시예 2의 중합체가 비교예 1 및 비교예 2의 중합체 대비 천정온도 및 용융온도가 전반적으로 감소된 것을 확인하였다. As shown in Table 1, the polymers of Examples 1 and 2 prepared by using the transition metal compound according to an embodiment of the present invention as a catalyst compared to the polymers of Comparative Examples 1 and 2 compared to the ceiling temperature and melting temperature It was confirmed that the overall decrease.
구체적으로, 실시예 1 및 실시예 2의 중합체는 비교예 1 및 비교예 2의 중합체 대비 천정온도가 약 3%~4% 감소하였으며, 용융온도가 약 2% 감소하였다. 이는, 본 발명에 따른 전이금속 화합물을 촉매로 이용하여 제조된 중합체의 경우 종래의 통상적인 전이금속 화합물을 촉매로 이용하여 제조된 중합체 대비 저밀도 영역의 높은 분자량을 가질 수 있음을 의미하는 결과이다.Specifically, the polymers of Examples 1 and 2 had a ceiling temperature decrease of about 3% to 4% compared to the polymers of Comparative Example 1 and Comparative Example 2, and a melting temperature of about 2%. This is a result which means that the polymer prepared by using the transition metal compound according to the present invention as a catalyst can have a high molecular weight in a low density region compared to a polymer prepared by using a conventional conventional transition metal compound as a catalyst.
Claims (12)
[화학식 2]
[화학식 3]
[화학식 4]
A transition metal compound represented by the following Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4:
[Formula 2]
[Formula 3]
[Formula 4]
Catalyst composition comprising the transition metal compound of claim 1.
상기 조성물은 1 종 이상의 조촉매를 더 포함하는 것인 촉매 조성물.
The method according to claim 7,
The composition is a catalyst composition that further comprises at least one co-catalyst.
상기 조촉매는 하기 화학식 5 내지 7로 표시되는 화합물 중에서 선택된 1종 이상인 것인 촉매 조성물:
[화학식 5]
-[Al(R22)-O]a-
상기 식에서, R22은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이며; a는 2 이상의 정수이며;
[화학식 6]
D(R22)3
상기 식에서, D가 알루미늄 또는 보론이며; R22은 서로 독립적으로 상기에 정의된 대로이며;
[화학식 7]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]-
상기 식에서, L이 중성 또는 양이온성 루이스 산이고; H가 수소 원자이며; Z가 13족 원소이고; A는 각각 독립적으로 1 이상의 수소 원자가 치환기로 치환될 수 있는 탄소수 6 내지 20의 아릴 또는 탄소수 1 내지 20의 알킬이며; 상기 치환기는 할로겐, 탄소수 1 내지 20의 하이드로카르빌, 탄소수 1 내지 20의 알콕시, 또는 탄소수 6 내지 20의 아릴옥시이다.
The method according to claim 8,
The cocatalyst is one or more catalyst compositions selected from compounds represented by the following Chemical Formulas 5 to 7:
[Formula 5]
- [Al (R 22) -O ] a -
In the above formula, R 22 are each independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
[Formula 6]
D (R 22 ) 3
Wherein D is aluminum or boron; R 22 are independently of each other as defined above;
[Formula 7]
[LH] + [Z (A ) 4] - or [L] + [Z (A ) 4] -
Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group 13 element; A is each independently aryl having 6 to 20 carbons or alkyl having 1 to 20 carbons, in which one or more hydrogen atoms may be substituted with substituents; The substituent is halogen, hydrocarbyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or aryloxy having 6 to 20 carbons.
상기 촉매 조성물은 반응 용매를 더 포함하는 것을 특징으로 하는 촉매 조성물.
The method according to claim 7,
The catalyst composition further comprises a reaction solvent.
Method of producing an olefin-based polymer comprising the step of performing a polymerization reaction in the presence of the catalyst composition of claim 7.
상기 중합체는 폴리올레핀의 호모중합체 또는 공중합체인 것인 올레핀계 중합체의 제조방법. The method according to claim 11,
The polymer is a method for producing an olefin-based polymer that is a homopolymer or copolymer of polyolefin.
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