KR20150066484A - Metallocene compound - Google Patents
Metallocene compound Download PDFInfo
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- KR20150066484A KR20150066484A KR1020140174365A KR20140174365A KR20150066484A KR 20150066484 A KR20150066484 A KR 20150066484A KR 1020140174365 A KR1020140174365 A KR 1020140174365A KR 20140174365 A KR20140174365 A KR 20140174365A KR 20150066484 A KR20150066484 A KR 20150066484A
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- KR
- South Korea
- Prior art keywords
- group
- formula
- metallocene compound
- represented
- compound
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 101
- 239000000126 substance Substances 0.000 claims abstract description 9
- -1 triethylsilyl group Chemical group 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Chemical group 0.000 claims description 5
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 229910052732 germanium Chemical group 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 3
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- FGTJJHCZWOVVNH-UHFFFAOYSA-N tert-butyl-[tert-butyl(dimethyl)silyl]oxy-dimethylsilane Chemical group CC(C)(C)[Si](C)(C)O[Si](C)(C)C(C)(C)C FGTJJHCZWOVVNH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 36
- 239000003054 catalyst Substances 0.000 abstract description 32
- 229920000642 polymer Polymers 0.000 abstract description 24
- 150000001336 alkenes Chemical class 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 105
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- 239000003446 ligand Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 229910007926 ZrCl Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Chemical group 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002469 indenes Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000006138 lithiation reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 229960004132 diethyl ether Drugs 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- RXXXUIOZOITBII-UHFFFAOYSA-N indeno[1,2-g]indole Chemical class C1=C2C=CC=CC2=C2C1=C1N=CC=C1C=C2 RXXXUIOZOITBII-UHFFFAOYSA-N 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- 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
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QUUSLJRWTDZCBF-UHFFFAOYSA-N 2,3-dihydroindene-1,1-diol Chemical class C1=CC=C2C(O)(O)CCC2=C1 QUUSLJRWTDZCBF-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IZJBEFCHFXZWRN-UHFFFAOYSA-N CCCCN(CCCC)CCCC.CCCCN(CCCC)CCCC Chemical compound CCCCN(CCCC)CCCC.CCCCN(CCCC)CCCC IZJBEFCHFXZWRN-UHFFFAOYSA-N 0.000 description 1
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 description 1
- JEVCOCKVSCRHMR-UHFFFAOYSA-N CCN(CC)C1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCN(CC)C1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F JEVCOCKVSCRHMR-UHFFFAOYSA-N 0.000 description 1
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XIBZTAIPROXEDH-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 XIBZTAIPROXEDH-UHFFFAOYSA-N 0.000 description 1
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- VZNYXGQMDSRJAL-UHFFFAOYSA-N iodomethyl(trimethyl)silane Chemical compound C[Si](C)(C)CI VZNYXGQMDSRJAL-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 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
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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Abstract
Description
본 발명은 신규한 메탈로센 화합물에 관한 것이다.The present invention relates to a novel metallocene compound.
다우(Dow) 사가 1990년대 초반 [Me2Si(Me4C5)NtBu]TiCl2(Constrained-Geometry Catalyst, 이하에서 CGC로 약칭한다)를 발표하였는데(미국 특허 등록 제5,064,802호), 에틸렌과 알파-올레핀의 공중합 반응에서 상기 CGC가 기존까지 알려진 메탈로센 촉매들에 비해 우수한 측면은 크게 다음과 같이 두 가지로 요약할 수 있다: (1) 높은 중합 온도에서도 높은 활성도를 나타내면서 고분자량의 중합체를 생성하며, (2) 1-헥센 및 1-옥텐과 같은 입체적 장애가 큰 알파-올레핀의 공중합성도 매우 뛰어나다는 점이다. 그 외에도 중합 반응 시, CGC의 여러 가지 특성들이 점차 알려지면서 이의 유도체를 합성하여 중합 촉매로 사용하고자 하는 노력이 학계 및 산업계에서 활발히 이루어졌다.Dow has announced the early 1990s [Me 2 Si (Me 4 C 5 ) NtBu] TiCl 2 (hereinafter abbreviated as CGC) (U.S. Patent No. 5,064,802) - In the copolymerization of olefins, the CGC is superior to conventional metallocene catalysts in two major ways: (1) high molecular weight polymers with high activity even at high polymerization temperatures; , And (2) the copolymerization of alpha-olefins with large steric hindrance such as 1-hexene and 1-octene is also excellent. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.
리간드로 시클로펜타디에닐기를 한 개 또는 두 개 가지고 있는 4족 전이금속 화합물을 메틸알루미녹산이나 보론 화합물로 활성화시켜 올레핀 중합의 촉매로 이용할 수 있다. 이러한 촉매는 종래의 지글러-나타 촉매가 구현할 수 없는 독특한 특성을 보여준다.A Group 4 transition metal compound having one or two cyclopentadienyl groups as ligands can be activated with methylaluminoxane or a boron compound to be used as a catalyst for olefin polymerization. These catalysts exhibit unique properties that conventional Ziegler-Natta catalysts can not achieve.
즉, 이러한 촉매를 이용하여 얻은 중합체는 분자량 분포가 좁고 알파올레핀이나 시클릭올레핀과 같은 제2 단량체에 대한 반응성이 더 좋고, 중합체의 제2 단량체 분포도 균일하다. 또한, 메탈로센 촉매 내의 시클로펜타디에닐 리간드의 치환체를 변화시켜 줌으로써 알파올레핀을 중합할 때 고분자의 입체 선택성을 조절할 수 있으며, 에틸렌과 다른 올레핀을 공중합할 때 공중합 정도, 분자량, 및 제2 단량체 분포 등을 용이하게 조절할 수 있다.That is, the polymer obtained using such a catalyst has a narrow molecular weight distribution and better reactivity with the second monomer such as alpha olefin or cyclic olefin, and the second monomer distribution of the polymer is uniform. Further, by changing the substituent of the cyclopentadienyl ligand in the metallocene catalyst, the stereoselectivity of the polymer can be controlled when the alpha olefin is polymerized, and the degree of copolymerization, the molecular weight, and the molecular weight of the second monomer Distribution and the like can be easily controlled.
한편, 메탈로센 촉매는 종래의 지글러-나타 촉매에 비해 가격이 비싸기 때문에 활성이 좋아야 경제적인 가치가 있다. 제2 단량체에 대한 반응성이 좋으면 적은 양의 제2 단량체의 투입으로도 제2 단량체가 많이 들어간 중합체를 얻을 수 있는 이점이 있다.On the other hand, since metallocene catalysts are more expensive than conventional Ziegler-Natta catalysts, they are economically worthy of good activity. If the reactivity to the second monomer is good, there is an advantage that a polymer containing a large amount of the second monomer can be obtained even by introducing a small amount of the second monomer.
여러 연구자들이 다양한 촉매를 연구한 결과, 일반적으로 브리지된 촉매가 제2 단량체에 대해 반응성이 좋다는 것이 판명되었다. 지금까지 연구된 브리지된 촉매는 브리지 형태에 따라 크게 세 가지로 분류될 수 있다. 하나는 알킬 할라이드와 같은 친전자체와 인덴이나 플루오렌 등과의 반응에 의해 두 개의 시클로펜타디에닐 리간드가 알킬렌디브리지로 연결된 촉매이고, 둘째는 -SiR2-에 의해서 연결된 실리콘 브리지된 촉매, 및 셋째는 풀벤과 인덴이나 플루오렌 등과의 반응으로부터 얻어진 메틸렌브리지된 촉매가 그것이다.A number of researchers have studied various catalysts, and it has generally been found that the bridged catalyst is more reactive to the second monomer. The bridged catalyst studied so far can be roughly classified into three types according to the bridge type. One is a catalyst in which two cyclopentadienyl ligands are linked by an alkylene di-bridge through the reaction of an electrophile such as an alkyl halide with indene or fluorene, the second is a silicon bridged catalyst connected by -SiR 2 - Is a methylene bridged catalyst obtained from the reaction of fulvene with indene or fluorene.
그러나, 상기 시도들 중에서 실제로 상업 공장에 적용되고 있는 촉매들은 소수이며, 보다 향상된 중합 성능을 보여주는 촉매의 제조가 여전히 요구된다.
However, among the above attempts, the catalysts actually applied to commercial plants are few, and the production of catalysts showing improved polymerization performance is still required.
본 발명은 활성이 우수하고 저분자량의 올레핀계 중합체를 생성할 수 있는 메탈로센 화합물을 제공하고자 한다. The present invention provides a metallocene compound capable of producing an olefin polymer having excellent activity and a low molecular weight.
특히, 수소 반응성이 낮아 수소가 존재하는 상황에서도 높은 활성이 유지되며 저분자량의 올레핀계 중합체를 중합할 수 있는 메탈로센 화합물을 제공하고자 한다.
In particular, it is intended to provide a metallocene compound capable of polymerizing an olefin polymer having a low molecular weight while maintaining high activity even in the presence of hydrogen because of low hydrogen reactivity.
본 발명은 하기 화학식 1로 표시되는 메탈로센 화합물을 제공한다.The present invention provides a metallocene compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
M은 4족 전이금속이고;M is a Group 4 transition metal;
B는 탄소, 실리콘 또는 게르마늄이고;B is carbon, silicon or germanium;
Q1 및 Q2는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, C7 내지 C20의 아릴알킬기, C1 내지 C20의 알콕시기, C2 내지 C20의 알콕시알킬기, C3 내지 C20의 헤테로시클로알킬기, 또는 C5 내지 C20의 헤테로아릴기이고;Q 1 and Q 2 are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, 니트로기, 아미도기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 알콕시기, 또는 C1 내지 C20의 술폰네이트기이고;X 1 and X 2 are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C1 및 C2는 서로 동일하거나 상이하고, 각각 독립적으로 하기 화학식 2a, 화학식 2b, 화학식 2c, 또는 화학식 2d 중 하나로 표시되고, 단, C1 및 C2 중 하나 이상은 화학식 2a로 표시되며;C 1 And C 2 are the same or different from each other, and each independently represents one of the following formulas (2a), (2b), (2c), or (2d), provided that at least one of C 1 and C 2 is represented by formula (2a);
[화학식 2a](2a)
[화학식 2b](2b)
[화학식 2c][Chemical Formula 2c]
[화학식 2d](2d)
상기 화학식 2a, 2b, 2c, 및 2d에서, In the above formulas (2a), (2b), (2c) and (2d)
R1 내지 R28은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 실릴알킬기, C1 내지 C20의 알콕시실릴기, C1 내지 C20의 에테르기, C1 내지 C20의 실릴에테르기, C1 내지 C20의 알콕시기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이고,R 1 to R 28 are the same or different from each other and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, A C1 to C20 silyl ether group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, ,
R'1 내지 R'3은 서로 동일하거나 상이하고, 각각 독립적으로, 수소, 할로겐, C1 내지 C20의 알킬기, C2내지 C20의 알케닐기, C6 내지 C20의 아릴기이며,R'1 to R'3 are the same or different from each other and each independently represent hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group,
상기 R1 내지 R28 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있다.
The R 1 to R 28 Two or more of which are adjacent to each other may be connected to form a substituted or unsubstituted aliphatic or aromatic ring.
본 발명에 따른 메탈로센 화합물은 올레핀계 중합체의 제조 시 사용할 수 있고, 활성이 우수하며, 구조적, 전기적 입체장애 효과로 인하여 유사한 구조의 촉매 조성물을 사용할 때에 비하여 상대적으로 낮은 분자량의 올레핀계 중합체를 제조할 수 있다. The metallocene compound according to the present invention can be used in the production of an olefinic polymer, has excellent activity, and has a relatively low molecular weight olefinic polymer as compared with a catalyst composition having a similar structure due to structural and electrical steric hindrance effects Can be manufactured.
또한 촉매의 수명(life time)이 길어 반응기 내에 오랜 체류 시간에도 활성이 유지될 수 있다.
In addition, since the lifetime of the catalyst is long, the activity can be maintained even in a long residence time in the reactor.
본 발명에서, 제 1, 제 2 등의 용어는 다양한 구성요소들을 설명하는데 사용되며, 상기 용어들은 하나의 구성 요소를 다른 구성 요소로부터 구별하는 목적으로만 사용된다. In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.
또한, 본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다", "구비하다" 또는 "가지다" 등의 용어는 실시된 특징, 숫자, 단계, 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 구성 요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 메탈로센 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다.The metallocene compound according to the present invention is characterized by being represented by the following general formula (1).
[화학식 1] [Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
M은 4족 전이금속이고;M is a Group 4 transition metal;
B는 탄소, 실리콘 또는 게르마늄이고;B is carbon, silicon or germanium;
Q1 및 Q2는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, C7 내지 C20의 아릴알킬기, C1 내지 C20의 알콕시기, C2 내지 C20의 알콕시알킬기, C3 내지 C20의 헤테로시클로알킬기, 또는 C5 내지 C20의 헤테로아릴기이고;Q 1 and Q 2 are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, 니트로기, 아미도기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 알콕시기, 또는 C1 내지 C20의 술폰네이트기이고;X 1 and X 2 are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C1 및 C2는 서로 동일하거나 상이하고, 각각 독립적으로 하기 화학식 2a, 화학식 2b, 화학식 2c, 또는 화학식 2d 중 하나로 표시되고, 단, C1 및 C2 중 하나 이상은 화학식 2a로 표시되며;C 1 And C 2 are the same or different from each other, and each independently represents one of the following formulas (2a), (2b), (2c), or (2d), provided that at least one of C 1 and C 2 is represented by formula (2a);
[화학식 2a](2a)
[화학식 2b](2b)
[화학식 2c][Chemical Formula 2c]
[화학식 2d](2d)
상기 화학식 2a, 2b, 2c, 및 2d에서, In the above formulas (2a), (2b), (2c) and (2d)
R1 내지 R28은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 실릴알킬기, C1 내지 C20의 알콕시실릴기, C1 내지 C20의 에테르기, C1 내지 C20의 실릴에테르기, C1 내지 C20의 알콕시기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이고,R 1 to R 28 are the same or different from each other and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, A C1 to C20 silyl ether group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, ,
R'1 내지 R'3은 서로 동일하거나 상이하고, 각각 독립적으로, 수소, 할로겐, C1 내지 C20의 알킬기, C2내지 C20의 알케닐기, C6 내지 C20의 아릴기이며,R'1 to R'3 are the same or different from each other and each independently represent hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group,
상기 R1 내지 R28 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있다.The R 1 to R 28 Two or more of which are adjacent to each other may be connected to form a substituted or unsubstituted aliphatic or aromatic ring.
본 발명에 따른 메탈로센 화합물에 있어서, 상기 화학식 1의 치환기들을 보다 구체적으로 설명하면 하기와 같다.In the metallocene compound according to the present invention, the substituents of the above formula (1) will be more specifically described below.
상기 C1 내지 C20의 알킬기로는 직쇄 또는 분지쇄의 알킬기를 포함하고, 구체적으로 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기, tert-부틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.Examples of the C1 to C20 alkyl group include a linear or branched alkyl group and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, An octyl group, and the like, but are not limited thereto.
상기 C2 내지 C20의 알케닐기로는 직쇄 또는 분지쇄의 알케닐기를 포함하고, 구체적으로 알릴기, 에테닐기, 프로페닐기, 부테닐기, 펜테닐기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.The C2 to C20 alkenyl group includes a straight chain or branched alkenyl group, and specific examples include, but are not limited to, an allyl group, an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group.
상기 C6 내지 C20의 아릴기로는 단환 또는 축합환의 아릴기를 포함하고, 구체적으로 페닐기, 비페닐기, 나프틸기, 페난트레닐기, 플루오레닐기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.The C6 to C20 aryl group includes an aryl group of a monocyclic or condensed ring, and specifically includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group and a fluorenyl group.
상기 C5 내지 C20의 헤테로아릴기로는 단환 또는 축합환의 헤테로아릴기를 포함하고, 카바졸릴기, 피리딜기, 퀴놀린기, 이소퀴놀린기, 티오페닐기, 퓨라닐기, 이미다졸기, 옥사졸릴기, 티아졸릴기, 트리아진기, 테트라하이드로피라닐기, 테트라하이드로퓨라닐기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.The C5 to C20 heteroaryl group includes a heteroaryl group of a monocyclic or condensed ring and includes a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.
상기 C1 내지 C20의 알콕시기로는 메톡시기, 에톡시기, 페닐옥시기, 시클로헥실옥시기, tert-부톡시헥실기 등을 들 수 있으나, 이에만 한정되는 것은 아니다.Examples of the C1 to C20 alkoxy groups include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, and a tert-butoxyhexyl group.
상기 C1 내지 C20의 알킬실릴기로는 메틸실릴기, 디메틸실릴기, 트리메틸실릴기 등을 들 수 있으나, 이에만 한정되는 것은 아니다. Examples of the C1 to C20 alkylsilyl group include methylsilyl group, dimethylsilyl group, trimethylsilyl group and the like, but are not limited thereto.
상기 C1 내지 C20의 실릴알킬기로는 실릴메틸기, 디메틸실릴메틸기(-CH2-Si(CH3)2H), 트리메틸실릴메틸기(-CH2-Si(CH3)3) 등을 들 수 있으나, 이에만 한정되는 것은 아니다. A silyl group of the C1 to C20 is a silyl group, dimethylsilyl group (-CH 2 -Si (CH 3) 2 H), trimethyl silyl methyl group (-CH 2 -Si (CH 3) 3) , and the like. However, But is not limited thereto.
상기 4족 전이금속으로는 티타늄(Ti), 지르코늄(Zr), 하프늄(Hf) 등을 들 수 있으나, 이에만 한정되는 것은 아니다.
Examples of the Group 4 transition metal include titanium (Ti), zirconium (Zr), hafnium (Hf), and the like.
본 발명에 따른 메탈로센 화합물에 있어서, 상기 화학식 2a, 2b, 2c, 및 2d의 R1 내지 R28은 각각 독립적으로 수소, 할로겐, 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기, tert-부틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 에틸렌기, 프로필렌기, 부틸렌기, 페닐기, 벤질기, 나프틸기, 할로겐기, 에테르기, 트리메틸실릴기, 트리에틸실릴기, 트리프로필실릴기, 트리부틸실릴기, 트리이소프로필실릴기, 트리메틸실릴메틸기, 디메틸에테르기, tert-부틸디메틸실릴에테르기, 메톡시기, 에톡시기, 또는 tert-부톡시헥실기인 것이 바람직하나, 이에만 한정되는 것은 아니다. In the metallocene compound according to the present invention, each of R 1 to R 28 in the above formulas (2a), (2b), (2c) and (2d) is independently selected from the group consisting of hydrogen, halogen, a methyl group, an ethyl group, a propyl group, a halogen atom, an ether group, a trimethylsilyl group, a triethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, It is preferably a silyl group such as tripropylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethylsilylmethyl group, dimethyl ether group, tert-butyldimethylsilylether group, methoxy group, ethoxy group, or tert- But is not limited thereto.
본 발명에 따른 메탈로센 화합물에 있어서, 상기 화학식 1의 Q1 및 Q2는 수소, 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기, tert-부틸기, 메톡시메틸기, tert-부톡시메틸기, 1-에톡시에틸기, 1-메틸-1-메톡시에틸기, tert-부톡시헥실기, 테트라하이드로피라닐기, 또는 테트라하이드로퓨라닐기인 것이 바람직하나, 이에만 한정되는 것은 아니다.In the metallocene compound according to the present invention, Q 1 and Q 2 in the general formula (1) are each independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, Butoxymethyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tert-butoxyhexyl group, tetrahydropyranyl group or tetrahydrofuranyl group, but is not limited thereto.
본 발명에 따른 메탈로센 화합물에 있어서, 상기 화학식 1의 B는 실리콘(Si)인 것이 바람직하나, 이에만 한정되는 것은 아니다.In the metallocene compound according to the present invention, B of Formula 1 is preferably silicon (Si), but is not limited thereto.
상기 화학식 1의 메탈로센 화합물은 특히, 상기 화학식 2a의 치환기에서 트리메틸실릴 메틸기(trimethylsilyl methyl)와 같은 C1 내지 C20의 실릴알킬기를 적어도 하나 이상 포함하는 것을 특징으로 한다. The metallocene compound of Formula 1 is characterized in that at least one C1 to C20 silylalkyl group such as trimethylsilyl methyl is included in the substituent of Formula 2a.
보다 구체적으로, 상기 화학식 2a의 인덴 유도체는 인데노인돌 유도체나 플루오레닐 유도체에 비해 상대적으로 전자 밀도가 낮으며, 입체 장애가 큰 실릴알킬기를 포함함에 따라 입체 장애 효과 및 전자 밀도적 요인에 의하여 유사한 구조의 메탈로센 화합물에 비해 상대적으로 낮은 분자량의 올레핀 중합체를 고활성으로 중합할 수 있다. More specifically, the indene derivative of the above formula (2a) has a relatively low electron density compared to the indanediol derivative or the fluorenyl derivative, and the silylalkyl group having a large steric hindrance has a similar steric hindrance effect and electron density factor An olefin polymer having a relatively low molecular weight as compared with the metallocene compound having a structure can be polymerized with high activity.
또한 상기 화학식 2b와 같이 표시될 수 있는 인데노 인돌(Indeno indole) 유도체, 상기 화학식 2c와 같이 표시될 수 있는 플루오레닐(Fluorenyl) 유도체, 상기 화학식 2d와 같이 표시될 수 있는 인덴(Indene) 유도체가 브릿지에 의해 가교된 구조를 형성하며, 리간드 구조에 루이스 염기로 작용할 수 있는 비공유 전자쌍을 가짐으로써 높은 중합 활성을 나타낸다.The indenoindole derivative represented by Formula 2b, the fluorenyl derivative which may be represented by Formula 2c, the indene derivative represented by Formula 2d, Forms a structure bridged by a bridge and exhibits a high polymerization activity by having a non-covalent electron pair capable of acting as a Lewis base in the ligand structure.
본 발명의 일 실시예에 따르면, 상기 화학식 2a로 표시되는 작용기의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나, 본 발명이 이에만 한정되는 것은 아니다.According to an embodiment of the present invention, specific examples of the functional group represented by the formula (2a) include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 화학식 2b로 표시되는 작용기의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나, 본 발명이 이에만 한정되는 것은 아니다.According to an embodiment of the present invention, specific examples of the functional group represented by Formula 2b include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 화학식 2c로 표시되는 작용기의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나, 본 발명이 이에만 한정되는 것은 아니다.According to one embodiment of the present invention, specific examples of the functional group represented by Formula 2c include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 화학식 2d로 표시되는 작용기의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나, 본 발명이 이에만 한정되는 것은 아니다.According to one embodiment of the present invention, specific examples of the functional group represented by Formula 2d include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 본 발명의 메탈로센 화합물의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나, 이에만 한정되는 것은 아니다.According to one embodiment of the present invention, the metallocene compound of the present invention represented by Formula 1 may be a compound represented by one of the following structural formulas, but is not limited thereto.
본 발명에 따른 메탈로센 화합물은 활성이 우수하고 저분자량의 올레핀계 중합체를 중합할 수 있다. The metallocene compound according to the present invention can polymerize an olefin polymer having excellent activity and a low molecular weight.
또한, 저분자량과 동시에 넓은 분자량 분포를 갖는 올레핀계 중합체를 제조하기 위해 수소를 포함하여 중합 반응을 진행하는 경우에도, 본 발명에 따른 메탈로센 화합물은 낮은 수소 반응성을 나타내어 여전히 높은 활성으로 저분자량의 올레핀계 중합체의 중합이 가능하다. 따라서, 다른 특성을 갖는 촉매와 혼성으로 사용하는 경우에도 활성의 저하없이 저분자량의 특성을 만족시키는 올레핀계 중합체를 제조할 수 있어, 저분자의 올레핀계 중합체를 포함하면서 넓은 분자량 분포를 갖는 올레핀계 중합체를 용이하게 제조할 수 있다. In addition, when the polymerization reaction is carried out in the presence of hydrogen to produce an olefin polymer having a low molecular weight and a broad molecular weight distribution, the metallocene compound of the present invention exhibits low hydrogen reactivity, Of the olefinic polymer. Accordingly, even when used in combination with a catalyst having other properties, it is possible to produce an olefin-based polymer that satisfies the characteristics of a low molecular weight without deteriorating its activity, and can provide an olefin polymer containing a low molecular weight olefin- Can be easily produced.
본 발명의 일 실시예에 따르면, 상기 화학식 1의 메탈로센 화합물은 인덴 유도체와, 사이클로펜타디엔 유도체를 브릿지 화합물로 연결하여 리간드 화합물로 제조한 다음, 금속 전구체 화합물을 투입하여 메탈레이션(metallation)을 수행함으로써 수득될 수 있으나, 이에 제한되는 것은 아니다.According to an embodiment of the present invention, the metallocene compound of Formula 1 is prepared by ligating an indene derivative and a cyclopentadiene derivative with a bridge compound to prepare a ligand compound, and then adding a metal precursor compound to perform metallation. , But is not limited thereto.
보다 구체적으로 예를 들어, 인덴 유도체를 n-BuLi와 같은 유기 리튬 화합물과 반응시켜 리튬염을 제조하고, 브릿지 화합물의 할로겐화 화합물을 혼합한 후, 이들 혼합물을 반응시켜 리간드 화합물을 제조한다. 상기 리간드 화합물 또는 이의 리튬염과 금속 전구체 화합물을 혼합하고 반응이 완결될 때까지 약 12시간 내지 약 24시간 전후로 반응시킨 후 반응물을 여과 및 감압 하에서 건조함으로써 상기 화학식 1로 표시되는 메탈로센 화합물을 수득할 수 있다. More specifically, for example, a lithium salt is prepared by reacting an indene derivative with an organolithium compound such as n-BuLi, and a halogenated compound of the bridging compound is mixed and then reacted to prepare a ligand compound. The ligand compound or a lithium salt thereof and a metal precursor compound are mixed and reacted for about 12 hours to about 24 hours until the reaction is completed. The reaction product is then filtered and dried under reduced pressure to obtain the metallocene compound represented by Formula 1 .
본 발명의 메탈로센 화합물의 제조방법은 후술하는 실시예에 구체화하여 설명한다. The method for producing the metallocene compound of the present invention will be described in the following Examples.
상기 화학식 1의 메탈로센 화합물은 단독으로 또는 조촉매와 함께 촉매 조성물로써 올레핀 중합체를 제조하는데 사용할 수 있다. 예를 들어, 상기 화학식 1의 메탈로센 화합물을 포함하는 촉매 조성물과 올레핀계 단량체를 접촉시켜 중합 공정을 수행함으로써 올레핀 단일 중합체 또는 올레핀 공중합체를 제공할 수 있다. The metallocene compound of Formula 1 may be used alone or in combination with a cocatalyst to prepare an olefin polymer as a catalyst composition. For example, an olefin homopolymer or an olefin copolymer may be provided by contacting a catalytic composition comprising the metallocene compound of Formula 1 and an olefin monomer to perform a polymerization process.
상기 촉매 조성물은 상기 메탈로센 화합물 이외에 하기 화학식 3, 화학식 4 또는 화학식 5로 표시되는 조촉매 화합물 중 1종 이상을 추가로 포함할 수 있다.In addition to the metallocene compound, the catalyst composition may further include at least one of the following promoter compounds represented by the following formulas (3), (4), and (5)
[화학식 3](3)
-[Al(R30)-O]m- - [Al (R 30) -O ] m -
상기 화학식 3에서,In Formula 3,
R30은 서로 동일하거나 다를 수 있으며, 각각 독립적으로 할로겐; 탄소수 1 내지 20의 탄화수소; 또는 할로겐으로 치환된 탄소수 1 내지 20의 탄화수소이고;R 30 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
m은 2 이상의 정수이며;m is an integer of 2 or more;
[화학식 4][Chemical Formula 4]
J(R31)3 J ( R31 ) 3
상기 화학식 4에서,In Formula 4,
R31는 상기 화학식 3에서 정의된 바와 같고;R 31 is as defined in Formula 3 above;
J는 알루미늄 또는 보론이며;J is aluminum or boron;
[화학식 5][Chemical Formula 5]
[E-H]+[ZA4]- 또는 [E]+[ZA4]- [EH] + [ZA 4 ] - or [E] + [ZA 4 ] -
상기 화학식 5에서,In Formula 5,
E는 중성 또는 양이온성 루이스 염기이고;E is a neutral or cationic Lewis base;
H는 수소 원자이며;H is a hydrogen atom;
Z는 13족 원소이고;Z is a Group 13 element;
A는 서로 동일하거나 다를 수 있으며, 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 탄화수소, 알콕시 또는 페녹시로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 탄소수 1 내지 20의 알킬기이다.A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
상기 화학식 3으로 표시되는 화합물의 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등이 있으며, 더욱 바람직한 화합물은 메틸알루미녹산이다.Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.
상기 화학식 4로 표시되는 화합물의 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등이 포함되며, 더욱 바람직한 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄 중에서 선택된다.Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
상기 화학식 5로 표시되는 화합물의 예로는 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리부틸암모니움테트라펜타플로로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플로로페닐보론, 디에틸암모니움테트라펜타플로로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리부틸암모니움테트라펜타플로로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플로로페닐알루미늄, 디에틸암모니움테트라펜타테트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라펜타플로로페닐보론 등이 있다.Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.
바람직하게는 알룸옥산을 사용할 수 있으며, 더 바람직하게는 알킬알룸옥산인 메틸알룸옥산(MAO)이다.Preferably, alumoxane can be used, more preferably methylalumoxane (MAO), which is alkylalumoxane.
상기 촉매 조성물은, 첫 번째 방법으로서 1) 상기 화학식 1로 표시되는 메탈로센 화합물과 상기 화학식 3 또는 화학식 4로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 2) 상기 혼합물에 상기 화학식 5로 표시되는 화합물을 첨가하는 단계를 포함하는 방법으로 제조될 수 있다.The catalyst composition comprises, as a first method, 1) contacting the metallocene compound represented by Formula 1 and the compound represented by Formula 3 or 4 to obtain a mixture; And 2) adding the compound represented by Formula 5 to the mixture.
또한, 상기 촉매 조성물은, 두 번째 방법으로서 상기 화학식 1로 표시되는 메탈로센 화합물과 상기 화학식 3으로 표시되는 화합물을 접촉시키는 방법으로 제조될 수 있다.The catalyst composition may be prepared by a method of contacting the metallocene compound represented by Formula 1 and the compound represented by Formula 3 as a second method.
상기 촉매 조성물의 제조시에 반응 용매로서 펜탄, 헥산, 헵탄 등과 같은 탄화수소계 용매, 또는 벤젠, 톨루엔 등과 같은 방향족계 용매가 사용될 수 있다.In the preparation of the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent.
상기 메탈로센 화합물을 포함하는 촉매 조성물의 존재 하에 올레핀계 단량체를 중합함으로써 올레핀계 중합체를 제조할 수 있다. The olefinic polymer can be prepared by polymerizing the olefinic monomer in the presence of the catalyst composition comprising the metallocene compound.
상기 중합 반응은 하나의 연속식 슬러리 중합 반응기, 루프 슬러리 반응기, 기상 반응기 또는 용액 반응기 등을 이용하여, 용액 중합 공정, 슬러리 공정 또는 기상 공정에 의해 수행될 수 있다. 또한 하나의 올레핀 단량체로 호모중합하거나 또는 2종 이상의 단량체로 공중합하여 진행할 수 있다.The polymerization reaction may be carried out by a solution polymerization process, a slurry process or a gas phase process using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, and the like. Further, homopolymerization with one olefin monomer or copolymerization with two or more kinds of monomers can be carried out.
상기 올레핀계 단량체의 중합은 약 25 내지 약 500℃의 온도 및 약 1 내지 약 100 kgf/cm2에서 약 1 내지 약 24시간 동안 반응시켜 수행할 수 있다. 구체적으로, 상기 올레핀계 단량체의 중합은 약 25 내지 약 500℃, 바람직하게는 약 25 내지 약 200℃, 보다 바람직하게는 약 50 내지 약 100℃ 의 온도에서 수행할 수 있다. 또한 반응 압력은 약 1 내지 약 100 kgf/cm2, 바람직하게는 약 1 내지 약 50 kgf/cm2, 보다 바람직하게는 약 5 내지 약 40 kgf/cm2에서 수행할 수 있다. The polymerization of the olefinic monomer can be carried out by reacting at a temperature of from about 25 to about 500 DEG C and from about 1 to about 100 kgf / cm < 2 > for about 1 to about 24 hours. In particular, the polymerization of the olefinic monomer may be carried out at a temperature of from about 25 ° C to about 500 ° C, preferably from about 25 ° C to about 200 ° C, more preferably from about 50 ° C to about 100 ° C. The reaction pressure can also be carried out at from about 1 to about 100 kgf / cm 2 , preferably from about 1 to about 50 kgf / cm 2 , and more preferably from about 5 to about 40 kgf / cm 2 .
상기 올레핀계 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 등이 있으며, 이들을 2종 이상 혼합하여 공중합한 공중합체일 수 있다.Specific examples of the olefinic monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, -Dodecene, 1-tetradecene, 1-hexadecene, 1-icocene and the like, and copolymers obtained by copolymerizing two or more of them.
상기 올레핀계 중합체는 폴리에틸렌 중합체일 수 있으나, 이에만 한정되는 것은 아니다.The olefin-based polymer may be a polyethylene polymer, but is not limited thereto.
상기 올레핀계 중합체가 에틸렌/알파올레핀 공중합체인 경우에 있어서, 상기 공단량체인 알파올레핀의 함량은 특별히 제한되는 것은 아니며, 올레핀계 중합체의 용도, 목적 등에 따라 적절하게 선택할 수 있다. 보다 구체적으로는 0 초과 99 몰% 이하일 수 있다.In the case where the olefin-based polymer is an ethylene / alpha olefin copolymer, the content of the alpha-olefin as the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose and the like of the olefin-based polymer. More specifically, it may be more than 0 and 99 mol% or less.
상기 제조되는 올레핀계 중합체는 유사 구조의 유기 금속 화합물을 촉매로 사용하여 제조되는 경우 보다 상대적으로 낮은 분자량을 나타낼 수 있다.The olefin-based polymer may exhibit a relatively low molecular weight as compared with the olefin-based polymer prepared by using an organometallic compound having a similar structure as a catalyst.
본 발명의 일 실시예에 따르면, 상기 올레핀계 중합체의 중량 평균 분자량(Mw)은 약 10,000 내지 약 500,000 g/mol 일 수 있고, 바람직하게는 약 10,000 내지 약 200,000 g/mol 일 수 있다. According to one embodiment of the present invention, the olefinic polymer may have a weight average molecular weight (Mw) of about 10,000 to about 500,000 g / mol, and preferably about 10,000 to about 200,000 g / mol.
또한, 상기 올레핀계 중합체의 분자량 분포(Mw/Mn)는 약 1 내지 약 10, 바람직하게는 약 3 내지 약 6일 수 있다. The molecular weight distribution (Mw / Mn) of the olefin-based polymer may be about 1 to about 10, preferably about 3 to about 6.
따라서, 본 발명에 따른 올레핀계 중합체는 저분자량을 나타내어 사용되는 그 용도에 따라 다양하게 적용될 수 있다.Accordingly, the olefin-based polymer according to the present invention exhibits a low molecular weight and can be applied variously according to the use thereof.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.
<< 실시예Example >>
<< 메탈로센Metallocene 화합물의 제조 Preparation of compounds 실시예Example >>
제조 Produce 실시예Example 1 One
1-1 1-1 리간드Ligand 화합물의 제조 Preparation of compounds
건조된 250 mL Schlenk flask에 2.3 g (20 mmol)의 인덴(indene)을 채우고 아르곤 기체 하에서 40 mL의 디에틸에테르(Diethylether)에 녹였다. 이 용액을 0℃까지 냉각한 후, 헥산(hexane)에 녹인 2.5 M의 n-BuLi(hexane solution) 9.6 mL (24 mmol)를 천천히 적가하였다. 반응 혼합물을 천천히 상온으로 승온시킨 후, 24시간 동안 교반하였다. 이 혼합물에 디메틸디클로로규소(dimethyldichlorosilicone)을 인덴에 대하여 0.5당량이 되도록 적가한 후 하룻동안 교반하였다. 여기에 50 mL의 물을 넣고 유기층을 50 mL의 ether 로 3회 추출하였다. 모아진 유기층에 적당량의 MgSO4를 넣어 잠시 교반시킨 후, 필터하여 감압 하에 용매를 건조시켰다.The dried 250 mL Schlenk flask was filled with 2.3 g (20 mmol) of indene and dissolved in 40 mL of diethylether under argon gas. After cooling the solution to 0 ° C, 9.6 mL (24 mmol) of 2.5 M n-BuLi (hexane solution) dissolved in hexane was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 hours. To this mixture was added dropwise dimethyldichlorosilicone in an amount of 0.5 equivalent based on indene, and the mixture was stirred for one day. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO 4 was added to the collected organic layer, stirred for a while, filtered, and the solvent was dried under reduced pressure.
이러게 얻은 결과물을 Schlenk flask에서 잘 건조시킨 후, 아르곤 기체 하에서 증류된 THF 40ml를 가하고 -78℃까지 냉각하였다. 여기에 요오드화메틸트리메틸실란((iodomethyl)trimethylsilane)을 인덴에 대하여 2.1당량 주입하고, 상온으로 천천히 승온한 후, 24시간동안 교반하였다. 여기에 50 mL의 물을 넣고 유기층을 50 mL의 ether 로 3회 추출하였다. 모아진 유기층에 적당량의 MgSO4를 넣어 잠시 교반시킨 후, 필터하여 감압 하에 용매를 건조시킨 결과, 4.2 g (분자량: 460.87, 9.2mmol)의 짙은 갈색의 오일 형태의 리간드 화합물을 수득하였다. 얻어진 리간드 화합물은 별도의 분리 과정없이 메탈로센 화합물의 제조에 사용하였다. The resultant was dried well in a Schlenk flask, and 40 ml of distilled THF was added under argon gas and cooled to -78 ° C. To the solution, 2.1 equivalents of iodomethyl trimethylsilane was added to indene, and the temperature was slowly raised to room temperature, followed by stirring for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO 4 was added to the collected organic layer, stirred for a while, filtered, and the solvent was dried under reduced pressure to obtain 4.2 g (molecular weight: 460.87, 9.2 mmol) of a dark brown oily ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.
1H NMR (500MHz, CDCl3): -0.47, -0.34. -0.11(6H, t), 0.06(18H, d), 2.06 (2H, s), 2.10 (2H, s), 3.52 (1H, s), 3.55(1H, s), 5.97 (1H, s), 6.17 (1H, s), 7.14 (2H, m), 7.24 (2H, m), 7.36 (3H, m), 7.44 (1H, m)
1 H NMR (500MHz, CDCl 3 ): -0.47, -0.34. (2H, s), 3.52 (1H, s), 3.55 (1H, s), 5.97 (2H, m), 7.36 (3H, m), 7.44 (1H, m)
1-2 1-2 메탈로센Metallocene 화합물의 제조 Preparation of compounds
오븐에 건조한 250 mL Schlenk flask에 1-1에서 합성한 리간드 화합물을 넣고 4당량의 메틸터셔리부틸에테르(methyl tert-butyl ether)와 50ml의 톨루엔에 녹인 다음, 2 당량의 n-BuLi hexane solution 을 가해 lithiation시켰다. 하루가 지난 후 진공 조건에서 플라스크 내부의 용매를 모두 제거하고 동량의 톨루엔에 용해시켰다. Glove box 내에서 1 당량의 ZrCl4(THF)2을 취해 250 mL Schlenk flask에 담고 톨루엔을 넣은 서스펜션(suspension)을 준비하였다. 위의 두 개의 플라스크 모두 -78℃까지 냉각시킨 후 lithiation된 리간드 화합물을 천천히 ZrCl4(THF)2 의 톨루엔 서스펜션에 가하였다. 주입이 끝난 후, 반응 혼합물은 천천히 상온까지 올려 하룻동안 교반하여 반응을 진행시킨 후 혼합물 내의 톨루엔을 약 1/5 부피까지 진공 감압을 통해 제거하고 남은 톨루엔의 5배 정도 부피의 헥산을 가해 재결정시켰다. 외부 공기와 닿지 않게 혼합물을 여과하여 메탈로센 화합물을 수득하였으며, 약간의 헥산을 사용하여 필터 윗 부분에 얻어진 필터 케?(filter cake)을 씻어준 다음, glove box 내에서 계량하여 합성 여부, 수율, 순도를 확인하였다. The ligand compound synthesized in 1-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 50 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was subjected to lithiation. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl 4 (THF) 2 was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl 4 (THF) 2 . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.
Meso 화합물이 우세한 2.68g(4.32mmol)의 주황색 고체(filtrate)와 Racemic 화합물이 우세한 1.89g(3.04mmol)의 주황색 고체(filter cake)을 확인할 수 있었으며. Meso 화합물이 우세한 경우는 racemic 과 meso의 비율이 13.08 : 86.92였고, racemic화합물이 우세한 경우는 racemic 과 meso의 비율이 90.32 : 9.68 이었다. 2.68 g (4.32 mmol) of an orange solid (filtrate) dominated by the Meso compound and 1.89 g (3.04 mmol) of an orange solid (filter cake) dominated by racemic compounds were identified. The ratio of racemic to meso was found to be 13.08: 86.92 when the Meso compound was dominant, and the ratio of racemic to meso was 90.32: 9.68 when the racemic compound was dominant.
1H NMR (500MHz, CDCl3): -0.12 (18H, m), 0.82, 1.07, 1.36 (6H, t), 2.31 (4H, s), 5.23 (2H, s), 6.83 (2H, m), 7.10 (2H, m), 7.30 (2H, d), 7.48 (2H, d).
1 H NMR (500MHz, CDCl 3 ): -0.12 (18H, m), 0.82, 1.07, 1.36 (6H, t), 2.31 (4H, s), 5.23 (2H, s), 6.83 (2H, m), 7.10 (2 H, m), 7.30 (2 H, d), 7.48 (2 H, d).
제조 Produce 실시예Example 2 2
2-1 2-1 리간드Ligand 화합물의 제조 Preparation of compounds
건조된 250 mL Schlenk flask에 4.05 g (20 mmol)의 ((1H-inden-3-yl)methyl)trimethylsilane을 채우고 아르곤 기체 하에서 40 mL의 디에틸에테르(Diethylether)에 녹였다. 이 용액을 0℃까지 냉각한 후, 헥산(hexane)에 녹인 1.2 당량의 2.5 M의 n-BuLi(hexane solution) 9.6 mL (24 mmol)를 천천히 적가하였다. 반응 혼합물을 천천히 상온으로 승온시킨 후, 24시간 동안 교반하였다. 다른 250ml Schlenk flask에 silicone tether 2.713g(10mmol)을 헥산 30ml에 녹인 용액을 준비하고, 이를 -78℃까지 냉각한 뒤, 여기에 위에서 준비된 혼합물을 천천히 적가하였다. 적가한 후 혼합물을 상온으로 천천히 승온하고, 24시간 동안 교반시켰다. 여기에 50 mL의 물을 넣고 유기층을 50 mL의 ether 로 3회 추출하였다. 모아진 유기층에 적당량의 MgSO4를 넣어 잠시 교반시킨 후, 필터하여 감압 하에 용매를 건조시킨 결과, 6.1 g (분자량: 603.11, 10.05 mmol, 100.5 % 수율)의 노란색 오일 형태의 리간드 화합물을 수득하였다. 얻어진 리간드 화합물은 별도의 분리 과정없이 메탈로센 화합물의 제조에 사용하였다. 4.05 g (20 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was charged into a dried 250 mL Schlenk flask and dissolved in 40 mL of diethylether under argon gas. After cooling the solution to 0 ° C, 1.2 equivalents of 2.5 M n-BuLi (hexane solution) dissolved in hexane was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 hours. A solution of 2.713 g (10 mmol) of a silicone tether in 30 ml of hexane was prepared in another 250 ml Schlenk flask, cooled to -78 ° C, and the above prepared mixture was slowly added dropwise thereto. After the dropwise addition, the mixture was slowly warmed to room temperature and stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO 4 was added to the collected organic layer, stirred for a while, filtered and the solvent was dried under reduced pressure to obtain 6.1 g (molecular weight: 603.11, 10.05 mmol, 100.5% yield) of a yellow oil-like ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.
1H NMR (500MHz, CDCl3): 0.02 (18H, m), 0.82 (3H, m), 1.15 (3H, m), 1.17 (9H, m), 1.42 (H, m), 1.96 (2H, m), 2.02 (2H, m), 3.21 (2H, m), 3.31 (1H, s), 5.86 (1H, m), 6.10 (1H, m), 7.14 (3H, m), 7.14 (2H, m) 7.32 (3H, m).
1 H NMR (500 MHz, CDCl 3 ): 0.02 (18 H, m), 0.82 (3 H, m), 1.15 (3 H, m), 1.17 ), 2.02 (2H, m), 3.21 (2H, m), 3.31 (1H, s), 5.86 (1H, m), 6.10 7.32 (3 H, m).
2-2 2-2 메탈로센Metallocene 화합물의 제조 Preparation of compounds
오븐에 건조한 250 mL Schlenk flask에 2-1에서 합성한 리간드 화합물을 넣고 4당량의 메틸터셔리부틸에테르(methyl tert-butyl ether)와 60ml의 톨루엔에 녹인 다음, 2 당량의 n-BuLi hexane solution 을 가해 lithiation시켰다. 하루가 지난 후 진공 조건에서 플라스크 내부의 용매를 모두 제거하고 동량의 톨루엔에 용해시켰다. Glove box 내에서 1 당량의 ZrCl4(THF)2을 취해 250 mL Schlenk flask에 담고 톨루엔을 넣은 서스펜션(suspension)을 준비하였다. 위의 두 개의 플라스크 모두 -78℃까지 냉각시킨 후 lithiation된 리간드 화합물을 천천히 ZrCl4(THF)2 의 톨루엔 서스펜션에 가하였다. 주입이 끝난 후, 반응 혼합물은 천천히 상온까지 올려 하룻동안 교반하여 반응을 진행시킨 후 혼합물 내의 톨루엔을 약 1/5 부피까지 진공 감압을 통해 제거하고 남은 톨루엔의 5배 정도 부피의 헥산을 가해 재결정시켰다. 외부 공기와 닿지 않게 혼합물을 여과하여 메탈로센 화합물을 수득하였으며, 약간의 헥산을 사용하여 필터 윗 부분에 얻어진 필터 케?(filter cake)을 씻어준 다음, glove box 내에서 계량하여 합성 여부, 수율, 순도를 확인하였다. The ligand compound synthesized in 2-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 60 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was subjected to lithiation. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl 4 (THF) 2 was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl 4 (THF) 2 . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.
6.1g (10mmol)의 리간드 화합물로부터 7.3g (9.56mmol, 95.6%)의 자주색 오일을 얻어 톨루엔 용액으로 보관하였다. (순도: 100%, 분자량: 763.23)7.3 g (9.56 mmol, 95.6%) of a purple oil were obtained from 6.1 g (10 mmol) of the ligand compound and stored in toluene solution. (Purity: 100%, molecular weight: 763.23)
1H NMR (500MHz, CDCl3): 0.03 (18H, m), 0.98, 1.28 (3H, d), 1.40 (9H, m), 1.45 (4H, m), 1.66 (6H, m), 2.43 (4H, s), 3.47 (2H, m), 5.34 (1H, m), 5.56 (1H, m), 6.95 (1H, m), 6.97 (1H, m), 6.98(1H, m), 7.22 (1H, m), 7.36 (2H, m), 7.43 (1H, m), 7.57 (1H, m)
1 H NMR (500 MHz, CDCl 3 ): 0.03 (18H, m), 0.98, 1.28 (3H, d), 1.40 (9H, m), 1.45 (1H, m), 6.47 (1H, m), 6.47 (1H, m) m), 7.36 (2H, m), 7.43 (IH, m), 7.57
제조 Produce 실시예Example 3 3
3-1 3-1 리간드Ligand 화합물의 제조 Preparation of compounds
건조된 250 mL Schlenk flask에 1.66 g (10 mmol)의 fluorene을 채우고 아르곤 상태를 만든 후, 감압 하에서 50 mL의 ether를 주입하였다. ether 용액을 0℃까지 냉각한 후 플라스크 내부를 아르곤으로 치환하고 4.8 mL (12 mmol)의 2.5 M n-BuLi hexane solution을 천천히 적가하였다. 반응 혼합물을 천천히 상온까지 올린 후 하루동안 교반하였다. 다른 250 mL Schlenk flask에 헥산 40 mL를 채운 후, 2.713g (10mmol)의 silicone tether을 주입하였다. 주입 후, -78℃까지 냉각하고, 여기에 위에서 준비한 혼합물을 천천히 적가하였다. 주입 후 상온까지 천천히 승온시키고 12시간 동안 교반하였다. The dried 250 mL Schlenk flask was filled with 1.66 g (10 mmol) of fluorene and placed in an argon atmosphere. 50 mL of ether was then added under reduced pressure. The ether solution was cooled to 0 ° C, the inside of the flask was replaced with argon, and 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for one day. Another 250 mL Schlenk flask was filled with 40 mL of hexane and then 2.713 g (10 mmol) of silicone tether was injected. After the injection, the mixture was cooled to -78 deg. C, and the mixture prepared above was slowly added dropwise thereto. After the injection, the temperature was slowly raised to room temperature and stirred for 12 hours.
다른 건조된 250 mL Schlenk flask에 2.02g (10mmol)의 ((1H-inden-3-yl)methyl)trimethylsilane을 넣고 50ml의 THF를 가하여 용해시켰다. 이 용액을 0℃로 냉각시키고, 4.8ml (12mmol)의 2.5M n-BuLi(hexane solution)을 적가하고, 상온으로 승온시킨 후 12시간 동안 교반하였다. To another dried 250 mL Schlenk flask, 2.02 g (10 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was added and dissolved in 50 mL of THF. The solution was cooled to 0 占 폚, and 4.8 ml (12 mmol) of 2.5M n-BuLi (hexane solution) was added dropwise, and the mixture was warmed to room temperature and stirred for 12 hours.
앞에서 준비한 fluorene 혼합물을 -78℃로 냉각하고, 여기에 lithiated ((1H-inden-3-yl)methyl)trimethylsilane을 적가한 후, 상온으로 천천히 승온하고, 24시간동안 교반하였다. 여기에 50 mL의 물을 넣고 유기층을 50 mL의 ether 로 3회 추출하였다. 모아진 유기층에 적당량의 MgSO4를 넣어 잠시 교반시킨 후, 필터하여 감압 하에 용매를 건조시킨 결과, 5.8g(분자량 566.96, 10.3 mmol, 수율: 103%)의 노란색 오일 형태의 리간드 화합물을 수득하였다. 얻어진 리간드 화합물은 별도의 분리 과정없이 메탈로센 화합물의 제조에 사용하였다. The fluorene mixture prepared above was cooled to -78 ° C, lithiated ((1H-inden-3-yl) methyl) trimethylsilane was added dropwise thereto, the temperature was slowly raised to room temperature, and the mixture was stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO 4 was added to the collected organic layer, stirred for a while, filtered and the solvent was dried under reduced pressure to obtain 5.8 g (molecular weight 566.96, 10.3 mmol, yield: 103%) of a yellow oil-type ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.
1H NMR (500MHz, CDCl3): 0.00, 0.26 (3H, d), 0.46 (9H, m), 0.67 (1H, m), 0.83 (1H, m), 1.01 (1H, m), 1.25 (2H, m), 1.42 (2H, m), 1.49 (2H, m), 1.60 (9H, m), 1.72 (2H, m), 2.41 (2H, m), 3.66 (2H, m), 3.70, 3.77 (1H, s), 4.52 (1H, m), 6.01, 6.26, 6.37 (1H, s), 7.50 (1H, m), 7.59 - 7.80 (7H, m), 7.81 (1H, q), 7.97 (1H, d), 8.29 (2H, m). 1 H NMR (500 MHz, CDCl 3 ): 0.00, 0.26 (3H, d), 0.46 (9H, m), 0.67 (1H, m), 0.83 m), 1.42 (2H, m), 1.49 (2H, m), 1.60 (9H, m), 1.72 1H, s), 4.52 (1H, m), 6.01, 6.26, 6.37 (1H, s), 7.50 (1H, m), 7.59-7.80 d), 8.29 (2 H, m).
3-2 3-2 메탈로센Metallocene 화합물의 제조 Preparation of compounds
오븐에 건조한 250 mL Schlenk flask에 3-1에서 합성한 리간드 화합물을 넣고 4당량의 메틸터셔리부틸에테르(methyl tert-butyl ether)와 60ml의 톨루엔에 녹인 다음, 2 당량의 n-BuLi hexane solution 을 가해 lithiation시켰다. 하루가 지난 후 진공 조건에서 플라스크 내부의 용매를 모두 제거하고 동량의 톨루엔에 용해시켰다. Glove box 내에서 1 당량의 ZrCl4(THF)2을 취해 250 mL Schlenk flask에 담고 톨루엔을 넣은 서스펜션(suspension)을 준비하였다. 위의 두 개의 플라스크 모두 -78℃까지 냉각시킨 후 lithiation된 리간드 화합물을 천천히 ZrCl4(THF)2 의 톨루엔 서스펜션에 가하였다. 주입이 끝난 후, 반응 혼합물은 천천히 상온까지 올려 하룻동안 교반하여 반응을 진행시킨 후 혼합물 내의 톨루엔을 약 1/5 부피까지 진공 감압을 통해 제거하고 남은 톨루엔의 5배 정도 부피의 헥산을 가해 재결정시켰다. 외부 공기와 닿지 않게 혼합물을 여과하여 메탈로센 화합물을 수득하였으며, 약간의 헥산을 사용하여 필터 윗 부분에 얻어진 필터 케?(filter cake)을 씻어준 다음, glove box 내에서 계량하여 합성 여부, 수율, 순도를 확인하였다. The ligand compound synthesized in 3-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 60 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was subjected to lithiation. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl 4 (THF) 2 was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl 4 (THF) 2 . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.
4.05g (5.56mmol, 55.6%)의 주황색 고체를 수득하였다. (순도: 100%, 분자량: 727.08)4.05 g (5.56 mmol, 55.6%) of orange solid was obtained. (Purity: 100%, molecular weight: 727.08)
1H NMR (500MHz, CDCl3): -0.13 (9H, m), -0.13(3H, m), 0.53 (2H, m), 0.87 (2H, m), 1.25 (9H, m), 1.29 (4H, m), 1.51 (2H, s), 1.64 (2H, m), 3.34 (2H, m), 5.26 (1H, s), 6.81 (1H, m), 7.07 (2H, m), 7.18 (1H, m), 7.38 (1H, m), 7.46 - 7.56 (4H, m), 7.72 (1H, q), 7.95 (1H, d), 8.03 (1H, d)
1 H NMR (500 MHz, CDCl 3 ): -0.13 (9H, m), -0.13 (3H, m), 0.53 (2H, m), 0.87 (1H, m), 1.51 (2H, s), 1.64 (2H, m), 3.34 (2H, m), 5.26 m), 7.38 (1H, m), 7.46-7.56 (4H, m), 7.72
제조 Produce 실시예Example 4 4
4-1 4-1 리간드Ligand 화합물의 제조 Preparation of compounds
건조된 250 mL Schlenk flask에 2.33 g (10 mmol)의 indenoindole을 채우고 아르곤 상태를 만든 후, 감압 하에서 50 mL의 ether를 주입하였다. ether 용액을 0℃까지 냉각한 후 플라스크 내부를 아르곤으로 치환하고 4.8 mL (12 mmol)의 2.5 M n-BuLi hexane solution을 천천히 적가하였다. 반응 혼합물을 천천히 상온까지 올린 후 하루동안 교반하였다. 다른 250 mL Schlenk flask에 헥산 40 mL를 채운 후, 2.713g (10mmol)의 silicone tether을 주입하였다. 주입 후, -78℃까지 냉각하고, 여기에 위에서 준비한 혼합물을 천천히 적가하였다. 주입 후 상온까지 천천히 승온시키고 12시간 동안 교반하였다. The dried 250 mL Schlenk flask was filled with 2.33 g (10 mmol) of indenoindole and placed in an argon atmosphere. 50 mL of ether was then added under reduced pressure. The ether solution was cooled to 0 ° C, the inside of the flask was replaced with argon, and 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for one day. Another 250 mL Schlenk flask was filled with 40 mL of hexane and then 2.713 g (10 mmol) of silicone tether was injected. After the injection, the mixture was cooled to -78 deg. C, and the mixture prepared above was slowly added dropwise thereto. After the injection, the temperature was slowly raised to room temperature and stirred for 12 hours.
Indenoindole 화합물의 합성을 확인한 후, 다른 건조된 250 mL Schlenk flask에 2.02g (10mmol)의 ((1H-inden-3-yl)methyl)trimethylsilane을 넣고 50ml의 THF를 가하여 용해시켰다. 이 용액을 0℃로 냉각시키고, 4.8ml (12mmol)의 2.5M n-BuLi(hexane solution)을 적가하고, 상온으로 승온시킨 후 12시간 동안 교반하였다. After confirming the synthesis of the indenoindole compound, 2.02 g (10 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was added to another 250 mL Schlenk flask and dissolved in 50 mL of THF. The solution was cooled to 0 占 폚, and 4.8 ml (12 mmol) of 2.5M n-BuLi (hexane solution) was added dropwise, and the mixture was warmed to room temperature and stirred for 12 hours.
앞에서 준비한 indenoindole 혼합물을 -78℃로 냉각하고, 여기에 lithiated ((1H-inden-3-yl)methyl)trimethylsilane을 적가한 후, 상온으로 천천히 승온하고, 24시간동안 교반하였다. 여기에 50 mL의 물을 넣고 유기층을 50 mL의 ether 로 3회 추출하였다. 모아진 유기층에 적당량의 MgSO4를 넣어 잠시 교반시킨 후, 필터하여 감압 하에 용매를 건조시킨 결과, 6.5g(분자량 634.05, 10.3 mmol, 수율: 103%)의 노란색 오일 형태의 리간드 화합물을 수득하였다. 얻어진 리간드 화합물은 별도의 분리 과정없이 메탈로센 화합물의 제조에 사용하였다. The indenoindole mixture prepared above was cooled to -78 ° C., lithiated ((1H-inden-3-yl) methyl) trimethylsilane was added dropwise thereto, the temperature was slowly raised to room temperature, and the mixture was stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with 50 mL of ether. An appropriate amount of MgSO 4 was added to the collected organic layer, stirred for a while, filtered, and the solvent was dried under reduced pressure to give 6.5 g (molecular weight 634.05, 10.3 mmol, yield: 103%) of a yellow oil-like ligand compound. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.
1H NMR (500MHz, CDCl3): -0.40, -0.37 (3H, d), 0.017 (9H, m), 1.10 (H, m), 1.18 (9H, s), 1.34 (6H, m), 2.41 (3H, m), 3.25 (2H, m), 3.25 (1H, m), 3.53 (1H, m), 4.09 (3H, s), 5.62, 5.95, 5.95, 6.11, (1H, s), 7.04-7.32 (9H, m), 7.54 (1H, m), 7.75 (1H, m).
1 H NMR (500 MHz, CDCl 3 ): -0.40, -0.37 (3H, d), 0.017 (9H, m), 1.10 (3H, m), 3.25 (2H, m), 3.25 (1H, m), 3.53 (1H, m), 4.09 (3H, s), 5.62, 5.95, 7.32 (9 H, m), 7.54 (1 H, m), 7.75 (1 H, m).
4-2 4-2 메탈로센Metallocene 화합물의 제조 Preparation of compounds
오븐에 건조한 250 mL Schlenk flask에 4-1에서 합성한 리간드 화합물을 넣고 4당량의 메틸터셔리부틸에테르(methyl tert-butyl ether)와 60ml의 톨루엔에 녹인 다음, 2 당량의 n-BuLi hexane solution 을 가해 lithiation시켰다. 하루가 지난 후 진공 조건에서 플라스크 내부의 용매를 모두 제거하고 동량의 톨루엔에 용해시켰다. Glove box 내에서 1 당량의 ZrCl4(THF)2을 취해 250 mL Schlenk flask에 담고 톨루엔을 넣은 서스펜션(suspension)을 준비하였다. 위의 두 개의 플라스크 모두 -78℃까지 냉각시킨 후 lithiation된 리간드 화합물을 천천히 ZrCl4(THF)2 의 톨루엔 서스펜션에 가하였다. 주입이 끝난 후, 반응 혼합물은 천천히 상온까지 올려 하룻동안 교반하여 반응을 진행시킨 후 혼합물 내의 톨루엔을 약 1/5 부피까지 진공 감압을 통해 제거하고 남은 톨루엔의 5배 정도 부피의 헥산을 가해 재결정시켰다. 외부 공기와 닿지 않게 혼합물을 여과하여 메탈로센 화합물을 수득하였으며, 약간의 헥산을 사용하여 필터 윗 부분에 얻어진 필터 케?(filter cake)을 씻어준 다음, glove box 내에서 계량하여 합성 여부, 수율, 순도를 확인하였다. The ligand compound synthesized in 4-1 was added to a 250 mL Schlenk flask dried in an oven, dissolved in 4 equivalents of methyl tert-butyl ether and 60 mL of toluene, and 2 equivalents of n-BuLi hexane solution Was subjected to lithiation. After one day, all of the solvent in the flask was removed under vacuum and dissolved in the same amount of toluene. In the glove box, one equivalent of ZrCl 4 (THF) 2 was taken in a 250 mL Schlenk flask and toluene was added to prepare a suspension. Both of the above flasks were cooled to -78 ° C. and the lithiated ligand compound was slowly added to the toluene suspension of ZrCl 4 (THF) 2 . After the completion of the pouring, the reaction mixture was slowly warmed to room temperature and stirred for one day to conduct the reaction. Toluene in the mixture was removed through vacuum decompression to about 1/5 volume, recrystallized by adding hexane of about 5 times the amount of toluene remaining . The mixture was filtered to avoid contact with the outside air to obtain a metallocene compound. The filter cake was washed on the top of the filter using a little hexane and then weighed in a glove box, , And purity.
Metallation의 용매로는 Ether를 사용하였으며, 6.4g (10mmol)의 리간드로부터 6.08g (7.65mmol, 76.5%)의 빨강색 고체를 수득하였다. (순도: 100%, 분자량: 794.17)Ether was used as the solvent of the metallation, and 6.08 g (7.65 mmol, 76.5%) of a red solid was obtained from 6.4 g (10 mmol) of the ligand. (Purity: 100%, molecular weight: 794.17)
1H NMR (500MHz, CDCl3): -0.23, -0.16 (9H, d), 0.81 (3H, m), 1.17 (9H, m), 1.20-1.24 (3H, m), 1.31 (2H, s), 1.62-1.74 (5H, m), 1.99-2.11 (2H, m), 2.55 (3H, d), 3.33 (2H, m), 3.95, 4.13 (3H, s), 5.17, 5.21, 5.32 (1H, s), 6.89-7.07 (3H, m), 7.12-7.21 (3H, m), 7.29 (1H, m), 7.36 (1H, m), 7.44 (1H, m), 7.84 (1H, m).
1 H NMR (500MHz, CDCl 3 ): -0.23, -0.16 (9H, d), 0.81 (3H, m), 1.17 (9H, m), 1.20-1.24 (3H, m), 1.31 (2H, s) , 1.62-1.74 (5H, m), 1.99-2.11 (2H, m), 2.55 (3H, d), 3.33 m), 7.29 (1H, m), 7.36 (1H, m), 7.44 (1H, m), 7.84 (1H, m).
제조 Produce 실시예Example 5 5
5-2 5-2 메탈로센Metallocene 화합물의 제조 Preparation of compounds
제조 실시예 1-2에서 준비된 화합물 2.3 g (3.76 mmol)을 아르곤 하에서 100 ml의 THF를 주입하였다. 상기 혼합물을 -78℃까지 냉각한 후, CH3-(CH2)4-MgBr (2.0M in Diethylether, Aldrich) 용액을 5.7 ml(11.3 mmol, 3equiv.) 적가하였다. 반응 혼합물을 천천히 상온으로 승온시킨 후, 24시간 동안 교반하였다. 혼합물 내의 THF를 진공 감압을 통해 제거하여 상기 화학식으로 표시되는 화합물 1.5 g (1.52 mmol)을 얻었다. 오일 형태로 8.0 g의 Toluene Solution에 용해시켜 냉장 보관하였다 (5.968 g/ mmol). Yield는 40.3%. NMR 기준 purity (wt%) = 100%. Mw =692.36.2.3 g (3.76 mmol) of the compound prepared in Preparative Example 1-2 was introduced under argon into 100 ml of THF. The mixture was cooled to -78 ° C. and 5.7 ml (11.3 mmol, 3 equiv.) Of a solution of CH 3 - (CH 2 ) 4 -MgBr (2.0 M in Diethylether, Aldrich) was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred for 24 hours. THF in the mixture was removed under reduced pressure to obtain 1.5 g (1.52 mmol) of the compound represented by the above formula. Dissolved in 8.0 g of toluene solution in oil form and refrigerated (5.968 g / mmol). Yield is 40.3%. NMR standard purity (wt%) = 100%. Mw = 692.36.
1H NMR (500 MHz, CDCl3): -0.11 (6H, s), -0.06 (18H, m), 0.61 (2H, m), 0.84 (11H, m), 7.07 (3H, m), 1.23 (6H, m), 1.90 (4H, s), 5.37 (1H, s), 5.51 (1H, s), 6.88 (1H, m), 6.97 (2H, m), 7.00 (2H, m), 7.33 (1H, m), 7.41 (1H, m), 7.52 (1H, m), 7.54 (1H, m).
1 H NMR (500 MHz, CDCl 3): -0.11 (6H, s), -0.06 (18H, m), 0.61 (2H, m), 0.84 (11H, m), 7.07 (3H, m), 1.23 ( (2H, m), 7.00 (2H, m), 7.33 (1H, s) m), 7.41 (1H, m), 7.52 (1H, m), 7.54 (1H, m).
<올레핀<Olefin 중합 polymerization 제조예Manufacturing example >>
제조예Manufacturing example 1 내지 7 1 to 7
에틸렌 중합Ethylene polymerization
100 mL 용량의 Andrew bottle을 준비하여 impeller part와 조립한 후 glove box 내에서 내부를 아르곤으로 치환하였다. Andrew bottle 의 내부에 소량의 TMA가 처방되어 있는 70 mL의 톨루엔을 넣고 10 mL의 MAO (10 wt% in toluene) 용액을 가하였다. 상기 실시예의 메탈로센 화합물 촉매를 톨루엔에 용해시킨 1 mM의 촉매/톨루엔 용액 5 mL (촉매 5 μmol)을 Andrew bottle에 주입하였다. Andrew bottle 을 90℃로 가열된 oil bath에 담근 채 mechanical stirrer에 bottle의 상부를 고정시킨 후 반응액이 90℃에 도달할 때까지 5분간 교반하였다. Bottle 내부를 에틸렌 가스로 3회 퍼지(purge)한 후, 에틸렌 밸브(valve)를 열어 50 psig의 압력이 되도록 가압하였다. 소비된 에틸렌만큼 지속적으로 에틸렌이 공급되어 압력이 유지되도록 하면서 mechanical stirrer를 가동시켜 500 rpm에서 30분간 반응시켰다. 반응 종료 후 상온까지 온도를 내리고 에틸렌 밸브를 잠그고 교반을 중지시킨 후 반응기 내의 압력을 천천히 배기(vent)시켰다. 반응물을 400 mL의 에탄올/HCl 수용액 혼합액에 부어 넣고 1 시간 정도 교반한 후, 필터하여 얻어진 고분자를 60℃의 진공 오븐에서 20시간 동안 건조시켰다. 얻어진 고분자의 무게를 측정하여 이로부터 촉매의 활성을 산출하고, 10mg의 샘플을 취해 GPC 분석에 사용하였다.
An Andrew bottle with a volume of 100 mL was prepared, assembled with the impeller part, and replaced with argon inside the glove box. Inside the Andrew bottle, 70 mL of toluene, in which a small amount of TMA was prescribed, was added and 10 mL of MAO (10 wt% in toluene) solution was added. 5 mL of a 1 mM catalyst / toluene solution (5 μmol of the catalyst) in which the metallocene compound catalyst of the above example was dissolved in toluene was injected into an Andrew bottle. The Andrew bottle was immersed in an oil bath heated to 90 ° C, and the upper part of the bottle was fixed on a mechanical stirrer and stirred for 5 minutes until the reaction solution reached 90 ° C. The inside of the bottle was purged with ethylene gas three times, and then the ethylene valve was opened and pressurized to a pressure of 50 psig. Ethylene was supplied continuously as much as the consumed ethylene, and the mechanical stirrer was operated so that the pressure was maintained, and the reaction was carried out at 500 rpm for 30 minutes. After completion of the reaction, the temperature was lowered to room temperature, the ethylene valve was closed, stirring was stopped, and the pressure in the reactor was slowly vented. The reaction product was poured into a mixed solution of 400 mL of ethanol / HCl aqueous solution, stirred for about 1 hour, filtered, and the obtained polymer was dried in a vacuum oven at 60 DEG C for 20 hours. The weight of the obtained polymer was measured, and the activity of the catalyst was calculated therefrom. A 10 mg sample was taken and used for GPC analysis.
에틸렌-1-Ethylene-1- 헥센Hexen 공중합 Copolymerization
100 mL 용량의 Andrew bottle을 준비하여 impeller part와 조립한 후 glove box 내에서 내부를 아르곤으로 치환하였다. Andrew bottle 의 내부에 소량의 TMA가 처방되어 있는 70 mL의 톨루엔을 넣고 10 mL의 MAO (10 wt% in toluene) 용액을 가하였다. 상기 실시예의 메탈로센 화합물 촉매를 톨루엔에 용해시킨 1 mM의 촉매/톨루엔 용액 5 mL (촉매 5 μmol)을 Andrew bottle에 주입하였다. Andrew bottle 을 90℃로 가열된 oil bath에 담근 채 mechanical stirrer에 bottle의 상부를 고정시킨 후 반응액이 90℃에 도달할 때까지 5분간 교반하였다. 공단량체인 1-헥센(1-hexen) 5 mL를 주입하고, Bottle 내부를 에틸렌 가스로 3회 퍼지(purge)한 후, 에틸렌 밸브(valve)를 열어 천천히 가압하였다. 소비된 에틸렌만큼 지속적으로 에틸렌이 공급되어 압력이 유지되도록 하면서 mechanical stirrer를 가동시켜 500 rpm에서 30분간 반응시켰다. 반응 종료 후 상온까지 온도를 내리고 에틸렌 밸브를 잠그고 교반을 중지시킨 후 반응기 내의 압력을 천천히 배기(vent)시켰다. 반응물을 400 mL의 에탄올/HCl 수용액 혼합액에 부어 넣고 1 시간 정도 교반한 후, 필터하여 얻어진 고분자를 60℃의 진공 오븐에서 20시간 동안 건조시켰다. 얻어진 고분자의 무게를 측정하여 이로부터 촉매의 활성을 산출하고, 10mg의 샘플을 취해 GPC 분석에 사용하였다.
An Andrew bottle with a volume of 100 mL was prepared, assembled with the impeller part, and replaced with argon inside the glove box. Inside the Andrew bottle, 70 mL of toluene, in which a small amount of TMA was prescribed, was added and 10 mL of MAO (10 wt% in toluene) solution was added. 5 mL of a 1 mM catalyst / toluene solution (5 μmol of the catalyst) in which the metallocene compound catalyst of the above example was dissolved in toluene was injected into an Andrew bottle. The Andrew bottle was immersed in an oil bath heated to 90 ° C, and the upper part of the bottle was fixed on a mechanical stirrer and stirred for 5 minutes until the reaction solution reached 90 ° C. 5 mL of a comonomer, 1-hexene, was injected, and the inside of the bottle was purged with ethylene gas three times, and then an ethylene valve was opened and slowly pressurized. Ethylene was supplied continuously as much as the consumed ethylene, and the mechanical stirrer was operated so that the pressure was maintained, and the reaction was carried out at 500 rpm for 30 minutes. After completion of the reaction, the temperature was lowered to room temperature, the ethylene valve was closed, stirring was stopped, and the pressure in the reactor was slowly vented. The reaction product was poured into a mixed solution of 400 mL of ethanol / HCl aqueous solution, stirred for about 1 hour, filtered, and the obtained polymer was dried in a vacuum oven at 60 DEG C for 20 hours. The weight of the obtained polymer was measured, and the activity of the catalyst was calculated therefrom. A 10 mg sample was taken and used for GPC analysis.
각 제조예의 반응 조건 및 결과를 정리하면 다음 표 1과 같다. Table 1 summarizes the reaction conditions and results of each production example.
(mL)1-Hex
(mL)
(Χ106)Activity b
(Χ10 6 )
(g/mol)Mw c
(g / mol)
(1-Hx mol%)Branch
(1-Hx mol%)
실시예 1
(Meso)Produce
Example 1
(Meso)
실시예 1
(Rac)Produce
Example 1
(Rac)
실시예 1
(Mix)Produce
Example 1
(Mix)
실시예 2Produce
Example 2
실시예 3Produce
Example 3
실시예 4Produce
Example 4
실시예 5Produce
Example 5
b g/mol·hr
c GPC a Conditions: Catalytic amount (5 탆 ol), ethylene pressure (PE = 50 psig), Al / Zr = 3000, temperature: 90 캜, reaction time 30 min.
b g / mol · hr
c GPC
Claims (8)
[화학식 1]
상기 화학식 1에서,
M은 4족 전이금속이고;
B는 탄소, 실리콘 또는 게르마늄이고;
Q1 및 Q2는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, C7 내지 C20의 아릴알킬기, C1 내지 C20의 알콕시기, C2 내지 C20의 알콕시알킬기, C3 내지 C20의 헤테로시클로알킬기, 또는 C5 내지 C20의 헤테로아릴기이고;
X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C6 내지 C20의 아릴기, 니트로기, 아미도기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 알콕시기, 또는 C1 내지 C20의 술폰네이트기이고;
C1 및 C2는 서로 동일하거나 상이하고, 각각 독립적으로 하기 화학식 2a, 화학식 2b, 화학식 2c, 또는 화학식 2d 중 하나로 표시되고, 단, C1 및 C2 중 하나 이상은 화학식 2a로 표시되며;
[화학식 2a]
[화학식 2b]
[화학식 2c]
[화학식 2d]
상기 화학식 2a, 2b, 2c, 및 2d에서,
R1 내지 R28은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C1 내지 C20의 알킬실릴기, C1 내지 C20의 실릴알킬기, C1 내지 C20의 알콕시실릴기, C1 내지 C20의 에테르기, C1 내지 C20의 실릴에테르기, C1 내지 C20의 알콕시기, C6 내지 C20의 아릴기, C7 내지 C20의 알킬아릴기, 또는 C7 내지 C20의 아릴알킬기이고,
R'1 내지 R'3은 서로 동일하거나 상이하고, 각각 독립적으로, 수소, 할로겐, C1 내지 C20의 알킬기, C2내지 C20의 알케닐기, C6 내지 C20의 아릴기이며,
상기 R1 내지 R28 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있다.
A metallocene compound represented by the following formula (1):
[Chemical Formula 1]
In Formula 1,
M is a Group 4 transition metal;
B is carbon, silicon or germanium;
Q 1 and Q 2 are the same or different and are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, A C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
X 1 and X 2 are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C 1 and C 2 are the same or different and each independently represents one of the following structural formulas (2a), (2b), (2c), or (2d) with the proviso that at least one of C 1 and C 2 is represented by formula (2a);
(2a)
(2b)
[Chemical Formula 2c]
(2d)
In the above formulas (2a), (2b), (2c) and (2d)
R 1 to R 28 are the same or different from each other and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, A C1 to C20 silyl ether group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, ,
R'1 to R'3 are the same or different from each other and each independently represent hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group,
The R 1 to R 28 Two or more of which are adjacent to each other may be connected to form a substituted or unsubstituted aliphatic or aromatic ring.
상기 화학식 2a, 2b, 2c, 및 2d의 R1 내지 R28은 각각 독립적으로 수소, 할로겐, 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기, tert-부틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 에틸렌기, 프로필렌기, 부틸렌기, 페닐기, 벤질기, 나프틸기, 할로겐기, 에테르기, 트리메틸실릴기, 트리에틸실릴기, 트리프로필실릴기, 트리부틸실릴기, 트리이소프로필실릴기, 트리메틸실릴메틸기, 디메틸에테르기, tert-부틸디메틸실릴에테르기, 메톡시기, 에톡시기, 또는 tert-부톡시헥실기인 메탈로센 화합물.
The method according to claim 1,
R 1 to R 28 in formulas (2a), (2b), (2c) and (2d) are each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, A halogen atom, an ether group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triethylsilyl group, a tributylsilyl group, a tributylsilyl group, a tributylsilyl group, An isopropylsilyl group, a trimethylsilylmethyl group, a dimethyl ether group, a tert-butyldimethylsilyl ether group, a methoxy group, an ethoxy group, or a tert-butoxyhexyl group.
상기 화학식 1의 Q1 및 Q2는 수소, 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기, tert-부틸기, 메톡시메틸기, tert-부톡시메틸기, 1-에톡시에틸기, 1-메틸-1-메톡시에틸기, tert-부톡시헥실기, 테트라하이드로피라닐기, 또는 테트라하이드로퓨라닐기인 메탈로센 화합물.
The method according to claim 1,
Q 1 and Q 2 in the general formula (1) are each independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, A methyl-1-methoxyethyl group, a tert-butoxyhexyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group.
The method of claim 1, wherein the functional group represented by Formula 2a is a metallocene compound having one of the following formulas:
The method of claim 1, wherein the functional group represented by Formula 2b is a metallocene compound having one of the following formulas:
The method according to claim 1, wherein the functional group represented by Formula 2c is a metallocene compound having one of the following formulas:
The method of claim 1, wherein the functional group represented by Formula 2d is a metallocene compound having one of the following formulas:
The compound according to claim 1, wherein the compound represented by Formula 1 is a metallocene compound having one of the following formulas:
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