KR20230023196A - Transition Metal Compound, Catalyst Comprising the Same, and Processes for Preparing the Same - Google Patents
Transition Metal Compound, Catalyst Comprising the Same, and Processes for Preparing the Same Download PDFInfo
- Publication number
- KR20230023196A KR20230023196A KR1020210105076A KR20210105076A KR20230023196A KR 20230023196 A KR20230023196 A KR 20230023196A KR 1020210105076 A KR1020210105076 A KR 1020210105076A KR 20210105076 A KR20210105076 A KR 20210105076A KR 20230023196 A KR20230023196 A KR 20230023196A
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- substituted
- compound represented
- aluminum
- unsubstituted
- Prior art date
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- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 25
- -1 2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene] Chemical compound 0.000 claims abstract description 44
- 150000001336 alkenes Chemical class 0.000 claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims description 209
- 239000000126 substance Substances 0.000 claims description 97
- 239000002904 solvent Substances 0.000 claims description 79
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 229910052782 aluminium Inorganic materials 0.000 claims description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 41
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 13
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 12
- 150000002900 organolithium compounds Chemical class 0.000 claims description 11
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 claims description 6
- 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 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 3
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229910052795 boron group element Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 claims description 3
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 3
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 3
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 claims description 3
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 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 claims 1
- QGHZYTQKNCPPTK-UHFFFAOYSA-N cyclopentylalumane Chemical compound C1(CCCC1)[AlH2] QGHZYTQKNCPPTK-UHFFFAOYSA-N 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 230000000704 physical effect Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 37
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012968 metallocene catalyst Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KUGXZQNBAAJIEC-UHFFFAOYSA-N O=C(C(C(=O)OCC)C=1C(C2(CCC=1)CCCCC2)=O)C Chemical compound O=C(C(C(=O)OCC)C=1C(C2(CCC=1)CCCCC2)=O)C KUGXZQNBAAJIEC-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ISUXBNXLVOPNBA-UHFFFAOYSA-N spiro[5.5]undecan-5-one Chemical compound O=C1CCCCC11CCCCC1 ISUXBNXLVOPNBA-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- GEPLRUHKORZDGH-UHFFFAOYSA-N 4-bromospiro[5.5]undecan-5-one Chemical compound O=C1C(Br)CCCC11CCCCC1 GEPLRUHKORZDGH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GEJRSRKNYBUPGB-UHFFFAOYSA-N O=C(CC1C(C2(CCC1)CCCCC2)=O)C Chemical compound O=C(CC1C(C2(CCC1)CCCCC2)=O)C GEJRSRKNYBUPGB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- JDPRRECMRPCSIF-UHFFFAOYSA-N ethyl 3-oxobutanoate;sodium Chemical compound [Na].CCOC(=O)CC(C)=O JDPRRECMRPCSIF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- C08F4/00—Polymerisation catalysts
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Abstract
Description
본 발명은 전이금속 화합물, 이를 포함하는 올레핀 중합용 촉매 및 이들을 제조하는 방법에 관한 것이다. 구체적으로, 본 발명은 2'-메틸-1',5',6',7'- 테트라하이드로스피로[사이클로헥산-1,4'-인덴](2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene]) 골격을 갖는 전이금속 화합물, 이를 포함하는 올레핀 중합용 촉매 및 해당 전이금속 화합물 및 촉매를 제조하는 방법에 관한 것이다.The present invention relates to a transition metal compound, a catalyst for olefin polymerization comprising the same, and a method for preparing the same. Specifically, the present invention is 2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene] (2'-methyl-1',5',6 It relates to a transition metal compound having a ',7'-tetrahydrospiro[cyclohexane-1,4'-indene]) skeleton, a catalyst for olefin polymerization including the same, and a method for preparing the transition metal compound and catalyst.
폴리올레핀계 중합체는 실생활에서 쇼핑백, 비닐하우스, 어망, 담배 포장지, 라면 봉지, 요구르트 병, 배터리 케이스, 자동차 범퍼, 내장재, 신발 밑창, 세탁기 등의 소재로 다양하게 사용되고 있다.Polyolefin-based polymers are widely used in real life as materials such as shopping bags, vinyl houses, fishing nets, cigarette wrappers, ramen bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, and washing machines.
종래 폴리에틸렌, 폴리프로필렌 및 에틸렌-알파올레핀 공중합체와 같은 폴리올레핀계 중합체와 이들의 공중합체는 티타늄 화합물과 알킬 알루미늄 화합물로 이루어진 지글러-나타(Ziegler-Natta) 촉매와 같은 불균일계 촉매에 의하여 제조되었다.Conventional polyolefin polymers such as polyethylene, polypropylene, and ethylene-alpha olefin copolymers and copolymers thereof are prepared by a heterogeneous catalyst such as a Ziegler-Natta catalyst composed of a titanium compound and an alkyl aluminum compound.
최근에는 촉매 활성이 매우 높은 균일계 촉매인 메탈로센 촉매를 이용한 폴리올레핀의 제조방법이 연구되고 있다. 메탈로센 촉매는 전이금속 또는 전이금속 할로겐 화합물에 사이클로펜타디에닐(cyclopentadienyl), 인데닐(indenyl), 사이클로헵타디에닐(cycloheptadienyl) 등의 리간드가 배위 결합된 화합물로서 샌드위치 구조를 기본적인 형태로 갖는다. 이때, 리간드의 형태와 중심 금속의 종류에 따라 다양한 분자 구조를 갖는다.Recently, a method for producing polyolefin using a metallocene catalyst, which is a homogeneous catalyst having very high catalytic activity, has been studied. A metallocene catalyst is a compound in which a ligand such as cyclopentadienyl, indenyl, or cycloheptadienyl is coordinated with a transition metal or transition metal halide compound, and has a sandwich structure as a basic form. . At this time, it has various molecular structures depending on the shape of the ligand and the type of the central metal.
불균일계 촉매인 지글러-나타(Ziegler-Natta) 촉매가 활성점인 금속 성분이 불활성인 고체 표면에 분산되어 활성점의 성질이 균일하지 않은데 반해, 메탈로센 촉매는 일정한 구조를 갖는 하나의 화합물이기 때문에 모든 활성점이 동일한 중합 특성을 갖는 단일 활성점 촉매(single-site catalyst)로 알려져 있다.Whereas the Ziegler-Natta catalyst, which is a heterogeneous catalyst, has a non-uniform nature of the active site because the metal component, which is the active site, is dispersed on an inert solid surface, the metallocene catalyst is a compound with a certain structure. Therefore, it is known as a single-site catalyst having the same polymerization characteristics at all active sites.
일반적으로, 메탈로센 촉매는 그 자체만으로는 중합 촉매로서의 활성이 없기 때문에, 메틸 알루미녹산 등의 조촉매와 함께 사용된다. 조촉매의 작용에 의하여 메탈로센 촉매가 양이온으로 활성화되고, 동시에 조촉매는 메탈로센 촉매에 배위하지 않은 음이온으로서 불포화된 양이온 활성종을 안정화시켜 각종 올레핀 중합에 활성을 갖는 촉매계를 형성한다.In general, since a metallocene catalyst is inactive as a polymerization catalyst by itself, it is used together with a cocatalyst such as methyl aluminoxane. The metallocene catalyst is activated as a cation by the action of the cocatalyst, and at the same time, the cocatalyst stabilizes the unsaturated cationic active species as an anion that is not coordinated to the metallocene catalyst to form a catalyst system having activity in various olefin polymerizations.
이러한 메탈로센 촉매는 공중합이 용이하고 촉매의 대칭성에 따라 중합체의 입체 구조를 조절할 수 있으며, 이로부터 제조된 고분자는 분자량 분포가 좁고 공단량체의 분포가 균일하다는 장점을 갖는다.Such a metallocene catalyst is easy to copolymerize and can control the three-dimensional structure of the polymer according to the symmetry of the catalyst, and the polymer prepared therefrom has the advantage of having a narrow molecular weight distribution and a uniform distribution of comonomers.
그러나, 활성이 높고, 공중합성이 더욱 향상되며, 물성이 향상된 수지를 제조할 수 있는 올레핀 중합용 메탈로센 촉매가 여전히 요구되고 있다.However, there is still a need for a metallocene catalyst for olefin polymerization capable of preparing a resin having high activity, improved copolymerizability, and improved physical properties.
본 발명의 목적은 활성이 높고, 우수한 물성을 가지는 수지를 제조할 수 있으며, 신규한 구조를 갖는 올레핀 중합 촉매용 전이금속 화합물 및 이를 포함하는 올레핀 중합용 촉매를 제공하는 것이다.An object of the present invention is to provide a transition metal compound for olefin polymerization catalyst having a novel structure and a catalyst for olefin polymerization including the same, which can prepare a resin having high activity and excellent physical properties.
본 발명의 다른 목적은 위 전이금속 화합물 및 이를 포함하는 올레핀 중합용 촉매를 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing the above transition metal compound and a catalyst for olefin polymerization comprising the same.
본 발명의 목적을 달성하기 위한 일 구현예에 따라서, 아래 화학식 1로 표시되는 전이금속 화합물이 제공된다.According to one embodiment for achieving the object of the present invention, a transition metal compound represented by Formula 1 below is provided.
[화학식 1][Formula 1]
위 화학식 1에서, l은 0 내지 2의 정수, m은 0 내지 3의 정수, n은 0 내지 5의 정수이고,In Formula 1 above, l is an integer from 0 to 2, m is an integer from 0 to 3, n is an integer from 0 to 5,
M은 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이고,M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도 또는 C6-20 아릴아미도이고,X is each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido or C 6-20 arylamido;
R1 내지 R3는 각각 독립적으로 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이되, R1 내지 R3는 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있고,R 1 to R 3 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted substituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl, wherein R One to R 3 may each independently form a substituted or unsubstituted saturated or unsaturated C 4-20 ring by connecting adjacent groups;
R4는 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴 또는 치환 또는 비치환된 C1-20 알킬리덴이다.R 4 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6- 20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl or substituted or unsubstituted C 1 -20 It is an alkylidene.
구체적으로, 위 화학식 1에서, l은 1 또는 2이고, m과 n은 각각 0 또는 1이고, M은 지르코늄이고, X는 각각 할로겐 또는 치환 또는 비치환된 C1-20 알킬이고, R1 내지 R3는 각각 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴이고, R4는 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴 또는 치환 또는 비치환된 C1-20 알킬리덴일 수 있다.Specifically, in Formula 1 above, l is 1 or 2, m and n are each 0 or 1, M is zirconium, X is each halogen or substituted or unsubstituted C 1-20 alkyl, R 1 to R 3 are each substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-20 aryl, and R 4 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, or substituted or unsubstituted C 1-20 alkylidene.
바람직하게는, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-1 내지 1-21로 표시되는 전이금속 화합물 중 적어도 하나이다.Preferably, the transition metal compound represented by Formula 1 above is at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below.
[화학식 1-1] [화학식 1-2] [화학식 1-3][Formula 1-1] [Formula 1-2] [Formula 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6][Formula 1-4] [Formula 1-5] [Formula 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9][Formula 1-7] [Formula 1-8] [Formula 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12][Formula 1-10] [Formula 1-11] [Formula 1-12]
[화학식 1-13] [화학식 1-14] [화학식 1-15][Formula 1-13] [Formula 1-14] [Formula 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18][Formula 1-16] [Formula 1-17] [Formula 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21][Formula 1-19] [Formula 1-20] [Formula 1-21]
본 발명의 일 구현예에 따라서, (1) 아래 화학식 2로 표시되는 화합물과 아래 화학식 3으로 표시되는 화합물을 반응시켜 아래 화학식 4로 표시되는 화합물을 얻는 단계; (2) 화학식 4로 표시되는 화합물과 아래 화학식 5로 표시되는 화합물을 반응시켜 아래 화학식 6으로 표시되는 화합물을 얻는 단계; (3) 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 반응시켜 아래 화학식 7로 표시되는 화합물을 얻는 단계; 및 (4) 화학식 7로 표시되는 화합물과 아래 화학식 8로 표시되는 화합물을 반응시켜 위 화학식 1로 표시되는 전이금속 화합물을 얻는 단계를 포함하는 전이금속 화합물의 제조방법이 제공된다.According to one embodiment of the present invention, (1) reacting the compound represented by the formula (2) and the compound represented by the formula (3) to obtain a compound represented by the formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 below to obtain a transition metal compound represented by Chemical Formula 1 above.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
Me2Si(Xa)2 Me 2 Si(X a ) 2
[화학식 4][Formula 4]
[화학식 5][Formula 5]
R4NH2 R 4 NH 2
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
MX4 MX4
위 화학식에서, l, m, n, M, X, R1 내지 R4는 위 전이금속 화합물의 항목에서 설명한 바와 같고, Me는 메틸, Xa는 할로겐이다.In the above formula, l, m, n, M, X, R 1 to R 4 are as described in the above transition metal compound, Me is methyl, and X a is halogen.
바람직하게는, 위 화학식 2로 표시되는 화합물이 아래 화학식 2-1 내지 2-16으로 표시되는 화합물 중 적어도 하나이다.Preferably, the compound represented by Formula 2 above is at least one of the compounds represented by Formulas 2-1 to 2-16 below.
[화학식 2-1][화학식 2-2][화학식 2-3][Formula 2-1] [Formula 2-2] [Formula 2-3]
[화학식 2-4][화학식 2-5][화학식 2-6][Formula 2-4] [Formula 2-5] [Formula 2-6]
[화학식 2-7][화학식 2-8][화학식 2-9][Formula 2-7] [Formula 2-8] [Formula 2-9]
[화학식 2-10][화학식 2-11][화학식 2-12][Formula 2-10] [Formula 2-11] [Formula 2-12]
[화학식 2-13][화학식 2-14][화학식 2-15][Formula 2-13] [Formula 2-14] [Formula 2-15]
[화학식 2-16][Formula 2-16]
본 발명의 구체예에서, 위 단계 (1) 내지 단계 (4)의 반응이 각각 독립적으로 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라하이드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종의 용매의 존재하에 수행될 수 있다.In an embodiment of the present invention, the reactions of the above steps (1) to (4) are independently selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate. It may be performed in the presence of at least one solvent selected from.
본 발명의 구체예에서, 단계 (4)의 반응이 아민계 화합물의 존재하에 수행될 수 있다.In an embodiment of the present invention, the reaction of step (4) may be carried out in the presence of an amine-based compound.
본 발명의 다른 목적을 달성하기 위한 일 구현예에 따라서, 위 화학식 1로 표시되는 전이금속 화합물; 및 조촉매 화합물을 포함하는 올레핀 중합용 촉매가 제공된다.According to one embodiment for achieving another object of the present invention, the transition metal compound represented by Formula 1 above; And a catalyst for olefin polymerization comprising a cocatalyst compound is provided.
여기서, 조촉매 화합물은 아래 화학식 9로 표시되는 화합물, 화학식 10으로 표시되는 화합물 및 화학식 11로 표시되는 화합물로 구성되는 군으로부터 선택되는 하나 이상일 수 있다.Here, the cocatalyst compound may be at least one selected from the group consisting of a compound represented by Formula 9, a compound represented by Formula 10, and a compound represented by Formula 11 below.
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]- [LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
위 화학식 9에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소기 또는 할로겐으로 치환된 C1-20 탄화수소기이고,In Formula 9 above, n is an integer of 2 or greater, R a is a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen,
위 화학식 10에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이며,In Formula 10, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with halogen. Or a C 1-20 alkoxy group,
위 화학식 11에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다.In Formula 11 above, L is a neutral or cationic Lewis base, [LH] + and [L] + are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group.
구체적으로, 위 화학식 9로 표시되는 화합물은 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산 및 부틸알루미녹산으로 구성되는 군으로부터 선택되는 적어도 하나이다.Specifically, the compound represented by Formula 9 is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane.
또한, 화학식 10으로 표시되는 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론 및 트리부틸보론으로 구성되는 군으로부터 선택되는 적어도 하나이다.In addition, the compound represented by Formula 10 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri- s -butyl aluminum, tricyclopentyl aluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron , At least one selected from the group consisting of triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron.
또한, 위 화학식 11로 표시되는 화합물은 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 및 트리페닐카보니움테트라펜타플로로페닐보론으로 구성되는 군으로부터 선택되는 적어도 하나이다.In addition, the compound represented by Formula 11 above is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra ( p -tolyl) Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra( p -tolyl) ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , Tributylammonium tetra ( p -trifluoromethylphenyl) boron, triphenylcarbonium tetra ( p -trifluoromethylphenyl) boron and triphenylcarbonium tetrapentafluorophenyl boron selected from the group consisting of at least one
본 발명의 구체예에서, 올레핀 중합용 촉매가 전이금속 화합물을 담지하는 담체를 더 포함한다. 구체적으로, 담체가 전이금속 화합물과 조촉매 화합물을 모두 담지할 수 있다.In an embodiment of the present invention, the catalyst for olefin polymerization further includes a carrier supporting a transition metal compound. Specifically, the carrier may support both the transition metal compound and the cocatalyst compound.
본 발명의 구체예에서, 위 담체는 실리카, 알루미나 및 마그네시아로 구성되는 군으로부터 선택되는 적어도 하나를 포함할 수 있다.In an embodiment of the present invention, the carrier may include at least one selected from the group consisting of silica, alumina and magnesia.
여기서, 담체에 담지되는 전이금속 화합물의 총량이 담체 1 g을 기준으로 0.001~1 mmole이며, 담체에 담지되는 조촉매 화합물의 총량이 담체 1 g을 기준으로 2~15 mmole이다.Here, the total amount of the transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier.
본 발명의 다른 구현예에 따라서, (1) 위 화학식 2로 표시되는 화합물과 위 화학식 3으로 표시되는 화합물을 반응시켜 위 화학식 4로 표시되는 화합물을 얻는 단계; (2) 화학식 4로 표시되는 화합물과 위 화학식 5로 표시되는 화합물을 반응시켜 위 화학식 6으로 표시되는 화합물을 얻는 단계; (3) 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 반응시켜 위 화학식 7로 표시되는 화합물을 얻는 단계; 및 (4) 화학식 7로 표시되는 화합물과 위 화학식 8로 표시되는 화합물을 반응시켜 위 화학식 1로 표시되는 전이금속 화합물을 얻는 단계; 및 (5) 단계 (4)에서 얻어진 전이금속 화합물, 조촉매 화합물 또는 둘 다를 담체에 담지시키는 단계를 포함하는 올레핀 중합용 촉매의 제조방법이 제공된다.According to another embodiment of the present invention, (1) reacting the compound represented by the above formula (2) and the compound represented by the above formula (3) to obtain a compound represented by the above formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 to obtain a compound represented by Chemical Formula 6; (3) obtaining a compound represented by Chemical Formula 7 by reacting a compound represented by Chemical Formula 6 with an organic lithium compound; and (4) reacting the compound represented by Chemical Formula 7 with the compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 above; and (5) supporting the transition metal compound, cocatalyst compound, or both obtained in step (4) on a carrier.
본 발명의 구체예에 따른 전이금속 화합물 및 이를 포함하는 올레핀 중합용 촉매는 특이한 입체 구조를 가지기 때문에 중합체의 물성 조절이 가능하다.Since the transition metal compound and the catalyst for olefin polymerization including the same according to an embodiment of the present invention have a unique three-dimensional structure, physical properties of the polymer can be controlled.
이하, 본 발명에 관하여 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
전이금속 화합물transition metal compound
본 발명의 일 구현예에 따라서, 아래 화학식 1로 표시되는 전이금속 화합물이 제공된다.According to one embodiment of the present invention, a transition metal compound represented by Formula 1 below is provided.
[화학식 1][Formula 1]
위 화학식 1에서, l은 0 내지 2의 정수, m은 0 내지 3의 정수, n은 0 내지 5의 정수이다. 구체적으로, l은 1 또는 2이고, m과 n은 각각 0 또는 1일 수 있다.In Formula 1 above, l is an integer from 0 to 2, m is an integer from 0 to 3, and n is an integer from 0 to 5. Specifically, l may be 1 or 2, and m and n may be 0 or 1, respectively.
M은 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이다. 구체적으로, M은 하프늄 또는 지르코늄일 수 있으며, 바람직하게는 지르코늄일 수 있다.M is titanium (Ti), zirconium (Zr) or hafnium (Hf). Specifically, M may be hafnium or zirconium, preferably zirconium.
X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도 또는 C6-20 아릴아미도이다. 구체적으로, X는 각각 할로겐 또는 치환 또는 비치환된 C1-20 알킬일 수 있다. 더 구체적으로, X는 각각 할로겐일 수 있으며, 바람직하게는 염소(Cl)일 수 있다.X is each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido or C 6-20 arylamido. Specifically, each X may be a halogen or a substituted or unsubstituted C 1-20 alkyl. More specifically, each X may be a halogen, preferably chlorine (Cl).
R1 내지 R3는 각각 독립적으로 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이다. 여기서, R1 내지 R3는 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있다. 구체적으로, R1 내지 R3는 각각 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴일 수 있다.R 1 to R 3 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted substituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl. Here, R 1 to R 3 may each independently form a substituted or unsubstituted saturated or unsaturated C 4-20 ring by connecting adjacent groups. Specifically, R 1 to R 3 may each be substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
R4는 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴 또는 치환 또는 비치환된 C1-20 알킬리덴이다. 구체적으로, R4는 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴 또는 치환 또는 비치환된 C1-20 알킬리덴일 수 있다.R 4 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6- 20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl or substituted or unsubstituted C 1 -20 It is an alkylidene. Specifically, R 4 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6-20 aryl or substituted or unsubstituted C 1-20 alkylidene.
본 발명의 구체예에서, 위 화학식 1에서, l은 1 또는 2이고, m과 n은 각각 0 또는 1이며, M은 지르코늄이고, X는 각각 할로겐 또는 치환 또는 비치환된 C1-20 알킬이고, R1 내지 R3는 각각 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴이고, R4는 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴 또는 치환 또는 비치환된 C1-20 알킬리덴일 수 있다.In an embodiment of the present invention, in Formula 1 above, l is 1 or 2, m and n are each 0 or 1, M is zirconium, X is each halogen or substituted or unsubstituted C 1-20 alkyl, and , R 1 to R 3 are each substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-20 aryl, and R 4 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, or substituted or unsubstituted C 1-20 alkylidene.
본 발명의 바람직한 구체예서, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-1 내지 1-21로 표시되는 전이금속 화합물 중 적어도 하나일 수 있다.In a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above may be at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below.
[화학식 1-1] [화학식 1-2] [화학식 1-3][Formula 1-1] [Formula 1-2] [Formula 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6][Formula 1-4] [Formula 1-5] [Formula 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9][Formula 1-7] [Formula 1-8] [Formula 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12][Formula 1-10] [Formula 1-11] [Formula 1-12]
[화학식 1-13] [화학식 1-14] [화학식 1-15][Formula 1-13] [Formula 1-14] [Formula 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18][Formula 1-16] [Formula 1-17] [Formula 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21][Formula 1-19] [Formula 1-20] [Formula 1-21]
전이금속 화합물의 제조방법Method for preparing transition metal compound
본 발명의 다른 구현예에 따라서, (1) 아래 화학식 2로 표시되는 화합물과 아래 화학식 3으로 표시되는 화합물을 반응시켜 아래 화학식 4로 표시되는 화합물을 얻는 단계; (2) 화학식 4로 표시되는 화합물과 아래 화학식 5로 표시되는 화합물을 반응시켜 아래 화학식 6으로 표시되는 화합물을 얻는 단계; (3) 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 반응시켜 아래 화학식 7로 표시되는 화합물을 얻는 단계; 및 (4) 화학식 7로 표시되는 화합물과 아래 화학식 8로 표시되는 화합물을 반응시켜 아래 화학식 1로 표시되는 전이금속 화합물을 얻는 단계를 포함하는 전이금속 화합물의 제조방법이 제공된다.According to another embodiment of the present invention, (1) reacting the compound represented by the formula (2) and the compound represented by the formula (3) to obtain a compound represented by the formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 below to obtain a transition metal compound represented by Chemical Formula 1 below.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
Me2Si(Xa)2 Me 2 Si(X a ) 2
[화학식 4][Formula 4]
[화학식 5][Formula 5]
R4NH2 R 4 NH 2
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
MX4 MX4
위 화학식에서, l, m, n, M, X, R1 내지 R4는 위 전이금속 화합물의 항목에서 설명한 바와 같고, Me는 메틸, Xa는 할로겐이다.In the above formula, l, m, n, M, X, R 1 to R 4 are as described in the above transition metal compound, Me is methyl, and X a is halogen.
바람직하게는, 위 화학식 2로 표시되는 화합물이 아래 화학식 2-1 내지 2-16으로 표시되는 화합물 중 적어도 하나일 수 있다.Preferably, the compound represented by Formula 2 above may be at least one of the compounds represented by Formulas 2-1 to 2-16 below.
[화학식 2-1][화학식 2-2][화학식 2-3][Formula 2-1] [Formula 2-2] [Formula 2-3]
[화학식 2-4][화학식 2-5][화학식 2-6][Formula 2-4] [Formula 2-5] [Formula 2-6]
[화학식 2-7][화학식 2-8][화학식 2-9][Formula 2-7] [Formula 2-8] [Formula 2-9]
[화학식 2-10][화학식 2-11][화학식 2-12][Formula 2-10] [Formula 2-11] [Formula 2-12]
[화학식 2-13][화학식 2-14][화학식 2-15][Formula 2-13] [Formula 2-14] [Formula 2-15]
[화학식 2-16][Formula 2-16]
바람직하게는, 위 화학식 8로 표시되는 화합물이 ZrCl4일 수 있다.Preferably, the compound represented by Formula 8 above may be ZrCl 4 .
본 발명의 구체예에서, 위 단계 (1) 내지 단계 (4)의 반응이 각각 독립적으로 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라하이드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종의 용매의 존재하에 수행될 수 있으나, 용매가 이들로 특별히 제한되는 것은 아니다.In an embodiment of the present invention, the reactions of the above steps (1) to (4) are independently selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate. It may be performed in the presence of at least one solvent selected from, but the solvent is not particularly limited thereto.
단계 (1)step (1)
위 단계 (1)에서, 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 4로 표시되는 화합물을 얻는다. 바람직하게는, 화학식 3으로 표시되는 화합물이 Me2SiCl2일 수 있다.In step (1) above, the compound represented by Chemical Formula 2 is reacted with the compound represented by Chemical Formula 3 to obtain the compound represented by Chemical Formula 4. Preferably, the compound represented by Formula 3 may be Me 2 SiCl 2 .
단계 (1)의 반응은 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라하이드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종의 용매의 존재하에 수행될 수 있으나, 용매가 이들로 특별히 제한되는 것은 아니다. 바람직하게는, 용매가 톨루엔일 수 있다.The reaction of step (1) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be toluene.
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 용매에 용해시킬 때, 각 화합물의 투입 순서는 특별히 제한되지 않는다. 즉, 화학식 2로 표시되는 화합물을 먼저 용매에 첨가하여 용해시킨 후 화학식 3으로 표시되는 화합물을 용매에 첨가하여 용해시켜도 좋고, 그 반대의 순서로 용해시켜도 좋다. 또한, 이 두 화합물을 각각 용매에 용해시킨 후 천천히 혼합하여도 좋다.When the compound represented by Formula 2 and the compound represented by Formula 3 are dissolved in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 2 may be first added to a solvent to be dissolved, and then the compound represented by Chemical Formula 3 may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed.
용매에 각각 용해시킨 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 혼합할 때, 온도는 특별히 제한되지 않는다. 예를 들어, 용매에 각각 용해시킨 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 -78~30℃의 온도, 바람직하게는 -78~-30℃의 온도, 더 바람직하게는 약 -30℃의 온도에서 천천히 혼합할 수 있다.When mixing the compound represented by Formula 2 and the compound represented by Formula 3 respectively dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Formula 2 and the compound represented by Formula 3 dissolved in a solvent, respectively, are dissolved at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at about -30 ° C. It can be mixed slowly at a temperature of °C.
용매에 각각 용해시킨 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 혼합한 후, 생성된 용액을 교반하여 화학식 4로 표시되는 화합물을 얻는다.After mixing the compound represented by the formula (2) and the compound represented by the formula (3) respectively dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by the formula (4).
이때, 교반 시 온도와 시간은 특별히 제한되지 않는다. 예를 들어, 25~150℃의 온도, 바람직하게는 80~110℃의 온도, 더 바람직하게는 약 90℃의 온도에서 1 내지 24시간, 바람직하게는 5 내지 20시간, 더 바람직하게는 약 16시간 동안 교반하여 반응시킬 수 있다.At this time, the temperature and time during stirring are not particularly limited. For example, at a temperature of 25 to 150 ° C, preferably at a temperature of 80 to 110 ° C, more preferably at a temperature of about 90 ° C for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours. It can be reacted by stirring for a period of time.
단계 (1)의 반응 종결 후, 진공하에서 반응 용액으로부터 용매를 제거하고, 새로운 용매를 첨가하여 생성물을 추출한 후, 다시 진공하에서 용매를 제거하여 생성물을 얻을 수 있다. 이때, 생성물을 추출하기 위한 용매는 특별히 제한되지는 않으나, 펜탄(pentane)이 바람직하다.After completion of the reaction in step (1), the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.
단계 (2)step (2)
위 단계 (2)에서, 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 반응시켜 화학식 6으로 표시되는 화합물을 얻는다. 바람직하게는, 화학식 5로 표시되는 화합물이 t-부틸아민일 수 있다.In the above step (2), the compound represented by formula 6 is obtained by reacting the compound represented by formula 4 with the compound represented by formula 5. Preferably, the compound represented by Formula 5 may be t -butylamine.
단계 (2)의 반응은 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라하이드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종의 용매의 존재하에 수행될 수 있으나, 용매가 이들로 특별히 제한되는 것은 아니다. 바람직하게는, 용매가 테트라하이드로퓨란일 수 있다.The reaction of step (2) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be tetrahydrofuran.
화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 용매에 용해시킬 때, 각 화합물의 투입 순서는 특별히 제한되지 않는다. 즉, 화학식 4로 표시되는 화합물을 먼저 용매에 첨가하여 용해시킨 후 화학식 5로 표시되는 화합물을 용매에 첨가하여 용해시켜도 좋고, 그 반대의 순서로 용해시켜도 좋다. 또한, 이 두 화합물을 각각 용매에 용해시킨 후 천천히 혼합하여도 좋다.When the compound represented by Formula 4 and the compound represented by Formula 5 are dissolved in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 4 may be first added to a solvent to be dissolved, and then the compound represented by Chemical Formula 5 may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed.
용매에 각각 용해시킨 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 혼합할 때, 온도는 특별히 제한되지 않는다. 예를 들어, 용매에 각각 용해시킨 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 -78~30℃의 온도, 바람직하게는 -78~-30℃의 온도, 더 바람직하게는 약 -30℃의 온도에서 천천히 혼합할 수 있다.When mixing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 respectively dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 respectively dissolved in a solvent at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at about -30 ° C. It can be mixed slowly at a temperature of °C.
용매에 각각 용해시킨 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 혼합한 후, 생성된 용액을 교반하여 화학식 6으로 표시되는 화합물을 얻는다.After mixing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 respectively dissolved in a solvent, the resulting solution is stirred to obtain the compound represented by Chemical Formula 6.
이때, 교반 시 온도와 시간은 특별히 제한되지 않는다. 예를 들어, -30~100℃의 온도, 바람직하게는 0~50℃의 온도, 더 바람직하게는 상온에서 1 내지 24시간, 바람직하게는 5 내지 20시간, 더 바람직하게는 약 16시간 동안 교반하여 반응시킬 수 있다.At this time, the temperature and time during stirring are not particularly limited. For example, stirring at a temperature of -30 to 100 ° C, preferably at a temperature of 0 to 50 ° C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours can react.
단계 (2)의 반응 종결 후, 진공하에서 반응 용액으로부터 용매를 제거하고, 새로운 용매를 첨가하여 생성물을 추출한 후, 다시 진공하에서 용매를 제거하여 생성물을 얻을 수 있다. 이때, 생성물을 추출하기 위한 용매는 특별히 제한되지는 않으나, 펜탄(pentane)이 바람직하다.After completion of the reaction in step (2), the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.
단계 (3)step (3)
위 단계 (3)에서, 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 반응시켜 화학식 7로 표시되는 화합물을 얻는다. 바람직하게는, 유기 리튬 화합물이 n-부틸리튬일 수 있다.In the above step (3), the compound represented by Chemical Formula 6 is reacted with an organolithium compound to obtain a compound represented by Chemical Formula 7. Preferably, the organolithium compound may be n -butyllithium.
단계 (3)의 반응은 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라하이드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종의 용매의 존재하에 수행될 수 있으나, 용매가 이들로 특별히 제한되는 것은 아니다. 바람직하게는, 용매가 헥산일 수 있다.The reaction of step (3) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be hexane.
화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 용매에 용해시킬 때, 각 화합물의 투입 순서는 특별히 제한되지 않는다. 즉, 화학식 6으로 표시되는 화합물을 먼저 용매에 첨가하여 용해시킨 후 유기 리튬 화합물을 용매에 첨가하여 용해시켜도 좋고, 그 반대의 순서로 용해시켜도 좋다. 또한, 이 두 화합물을 각각 용매에 용해시킨 후 천천히 혼합하여도 좋다. 구체적으로, 화학식 6으로 표시되는 화합물이 용매에 용해된 용액에 유기 리튬 화합물이 용매에 용해된 용액을 천천히 첨가하는 것이 바람직하다.When dissolving the compound represented by Formula 6 and the organolithium compound in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Formula 6 may be first added to a solvent to be dissolved, and then the organolithium compound may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed. Specifically, it is preferable to slowly add a solution in which the organolithium compound is dissolved in a solvent to a solution in which the compound represented by Formula 6 is dissolved in a solvent.
용매에 각각 용해시킨 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 혼합할 때, 온도는 특별히 제한되지 않는다. 예를 들어, 용매에 각각 용해시킨 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 -78~30℃의 온도, 바람직하게는 -78~-30℃의 온도, 더 바람직하게는 약 -30℃의 온도에서 천천히 혼합할 수 있다.When mixing the compound represented by Formula 6 and the organolithium compound each dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Formula 6 and the organic lithium compound respectively dissolved in a solvent at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at a temperature of about -30 ° C can be mixed slowly.
용매에 각각 용해시킨 화학식 6으로 표시되는 화합물과 리튬 화합물을 혼합한 후, 생성된 용액을 교반하여 화학식 7로 표시되는 화합물을 얻는다.After mixing the compound represented by Chemical Formula 6 and the lithium compound respectively dissolved in a solvent, the resulting solution is stirred to obtain a compound represented by Chemical Formula 7.
이때, 교반 시 온도와 시간은 특별히 제한되지 않는다. 예를 들어, -30~100℃의 온도, 바람직하게는 0~50℃의 온도, 더 바람직하게는 상온에서 1 내지 24시간, 바람직하게는 5 내지 20시간, 더 바람직하게는 약 16시간 동안 교반하여 반응시킬 수 있다.At this time, the temperature and time during stirring are not particularly limited. For example, stirring at a temperature of -30 to 100 ° C, preferably at a temperature of 0 to 50 ° C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours can react.
단계 (3)의 반응 종결 후, 진공하에서 반응 용액으로부터 용매를 제거하고, 새로운 용매를 첨가하여 생성물을 추출한 후, 다시 진공하에서 용매를 제거하여 생성물을 얻을 수 있다. 이때, 생성물을 추출하기 위한 용매는 특별히 제한되지는 않으나, 펜탄(pentane)이 바람직하다.After completion of the reaction in step (3), the solvent is removed from the reaction solution under vacuum, a new solvent is added to extract the product, and then the solvent is removed again under vacuum to obtain the product. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.
단계 (4)step (4)
위 단계 (4)에서, 화학식 7로 표시되는 화합물과 화학식 8로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 전이금속 화합물을 얻는다. 바람직하게는, 화학식 8로 표시되는 화합물이 염화지르코늄(ZrCl4)일 수 있다.In the above step (4), the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 are reacted to obtain a transition metal compound represented by Chemical Formula 1. Preferably, the compound represented by Chemical Formula 8 may be zirconium chloride (ZrCl 4 ).
단계 (4)의 반응은 헥산, 펜탄, 톨루엔, 벤젠, 디클로로메탄, 디에틸에테르, 테트라하이드로퓨란, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종의 용매의 존재하에 수행될 수 있으나, 용매가 이들로 특별히 제한되는 것은 아니다. 바람직하게는, 용매가 톨루엔일 수 있다.The reaction of step (4) may be carried out in the presence of at least one solvent selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate, The solvent is not particularly limited to these. Preferably, the solvent may be toluene.
단계 (4)의 반응은 아민계 화합물의 존재하에 수행될 수 있다. 아민계 화합물은 반응 환경을 염기성으로 유지시켜 화학식 7로 표시되는 불안정한 화합물을 안정시키고 이 화합물이 양성자화(protonation)되는 것을 방지한다. 바람직하게는, 아민계 화합물이 트리에틸아민(trimethylamine)일 수 있으나, 이것으로 특별히 제한되는 것은 아니다.The reaction of step (4) may be carried out in the presence of an amine-based compound. The amine-based compound stabilizes the unstable compound represented by Chemical Formula 7 by maintaining a basic reaction environment and prevents the compound from being protonated. Preferably, the amine compound may be triethylamine, but is not particularly limited thereto.
화학식 7로 표시되는 화합물과 화학식 8로 표시되는 화합물을 용매에 용해시킬 때, 각 화합물의 투입 순서는 특별히 제한되지 않는다. 즉, 화학식 7로 표시되는 화합물을 먼저 용매에 첨가하여 용해시킨 후 화학식 8로 표시되는 화합물을 용매에 첨가하여 용해시켜도 좋고, 그 반대의 순서로 용해시켜도 좋다. 또한, 이 두 화합물을 각각 용매에 용해시킨 후 천천히 혼합하여도 좋다.When the compound represented by Formula 7 and the compound represented by Formula 8 are dissolved in a solvent, the order of adding each compound is not particularly limited. That is, the compound represented by Chemical Formula 7 may be first added to a solvent to be dissolved, and then the compound represented by Chemical Formula 8 may be added to a solvent to be dissolved, or may be dissolved in the reverse order. Alternatively, these two compounds may be dissolved in a solvent and then slowly mixed.
여기서, 아민계 화합물의 투입 순서 도한 특별히 제한되지 않는다. 바람직하게는, 화학식 7로 표시되는 화합물이 용해된 용액에 아민계 화합물을 투입한 후 충분히 교반시켜 용해시킬 수 있다.Here, the order of adding the amine-based compound is not particularly limited. Preferably, after adding the amine-based compound to a solution in which the compound represented by Formula 7 is dissolved, it can be dissolved by sufficiently stirring.
용매에 각각 용해시킨 화학식 7로 표시되는 화합물과 화학식 8로 표시되는 화합물을 혼합할 때, 온도는 특별히 제한되지 않는다. 예를 들어, 용매에 각각 용해시킨 화학식 7로 표시되는 화합물과 화학식 8로 표시되는 화합물을 -78~30℃의 온도, 바람직하게는 -78~-30℃의 온도, 더 바람직하게는 약 -30℃의 온도에서 천천히 혼합할 수 있다.When mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 respectively dissolved in a solvent, the temperature is not particularly limited. For example, the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 respectively dissolved in a solvent at a temperature of -78 to 30 ° C, preferably at a temperature of -78 to -30 ° C, more preferably at about -30 ° C. It can be mixed slowly at a temperature of °C.
용매에 각각 용해시킨 화학식 7로 표시되는 화합물과 화학식 8로 표시되는 화합물을 혼합한 후, 생성된 용액을 교반하여 화학식 1로 표시되는 전이금속 화합물을 얻는다.After mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 respectively dissolved in a solvent, the resulting solution is stirred to obtain a transition metal compound represented by Chemical Formula 1.
이때, 교반 시 온도와 시간은 특별히 제한되지 않는다. 예를 들어, -30~100℃의 온도, 바람직하게는 0~50℃의 온도, 더 바람직하게는 상온에서 1 내지 24시간, 바람직하게는 5 내지 20시간, 더 바람직하게는 약 16시간 동안 교반하여 반응시킬 수 있다.At this time, the temperature and time during stirring are not particularly limited. For example, stirring at a temperature of -30 to 100 ° C, preferably at a temperature of 0 to 50 ° C, more preferably at room temperature for 1 to 24 hours, preferably 5 to 20 hours, more preferably about 16 hours can react.
단계 (4)의 반응 종결 후, 반응 용액을 필터에 통과시켜 불순물을 제거한다. 진공하에서 반응 용액으로부터 용매를 제거하고, 새로운 용매를 첨가하여 생성물을 추출한 후, 다시 진공하에서 용매를 제거하여 생성물을 얻을 수 있다. 이때, 생성물을 추출하기 위한 용매는 특별히 제한되지는 않으나, 펜탄(pentane)이 바람직하다.After completion of the reaction in step (4), the reaction solution is passed through a filter to remove impurities. The product can be obtained by removing the solvent from the reaction solution under vacuum, adding a new solvent to extract the product, and then removing the solvent under vacuum again. At this time, the solvent for extracting the product is not particularly limited, but pentane is preferred.
올레핀 중합용 촉매Catalyst for olefin polymerization
본 발명의 다른 구현예에 따라서, 아래 화학식 1로 표시되는 전이금속 화합물; 및 조촉매 화합물을 포함하는 올레핀 중합용 촉매가 제공된다.According to another embodiment of the present invention, a transition metal compound represented by Formula 1 below; And a catalyst for olefin polymerization comprising a cocatalyst compound is provided.
[화학식 1][Formula 1]
위 화학식 1에서, l, m, n, M, X, R1 내지 R4는 위 전이금속 화합물 항목에서 설명한 바와 같다.In Formula 1 above, l, m, n, M, X, R 1 to R 4 are as described in the transition metal compound section above.
본 발명의 바람직한 구체예에 있어서, 위 화학식 1로 표시되는 전이금속 화합물이 아래 화학식 1-1 내지 1-21로 표시되는 전이금속 화합물 중 적어도 하나일 수 있다.In a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above may be at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below.
[화학식 1-1] [화학식 1-2] [화학식 1-3][Formula 1-1] [Formula 1-2] [Formula 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6][Formula 1-4] [Formula 1-5] [Formula 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9][Formula 1-7] [Formula 1-8] [Formula 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12][Formula 1-10] [Formula 1-11] [Formula 1-12]
[화학식 1-13] [화학식 1-14] [화학식 1-15][Formula 1-13] [Formula 1-14] [Formula 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18][Formula 1-16] [Formula 1-17] [Formula 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21][Formula 1-19] [Formula 1-20] [Formula 1-21]
한편, 조촉매 화합물은 아래 화학식 9로 표시되는 화합물, 화학식 10으로 표시되는 화합물 및 화학식 11로 표시되는 화합물 중 하나 이상을 포함할 수 있다.Meanwhile, the cocatalyst compound may include at least one of a compound represented by Formula 9, a compound represented by Formula 10, and a compound represented by Formula 11 below.
[화학식 9][Formula 9]
위 화학식 9에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소 또는 할로겐으로 치환된 C1-20 탄화수소일 수 있다. 구체적으로, Ra는 메틸, 에틸, n-부틸 또는 이소부틸일 수 있다.In Formula 9, n is an integer of 2 or greater, and R a may be a halogen atom, a C 1-20 hydrocarbon, or a C 1-20 hydrocarbon substituted with a halogen. Specifically, R a can be methyl, ethyl, n -butyl or isobutyl.
[화학식 10][Formula 10]
위 화학식 10에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이다. 구체적으로, D가 알루미늄(Al)일 때, Rb, Rc 및 Rd는 각각 독립적으로 메틸 또는 이소부틸일 수 있고, D가 보론(B)일 때, Rb, Rc 및 Rd는 각각 펜타플루오로페닐일 수 있다.In Formula 10, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with halogen. or a C 1-20 alkoxy group. Specifically, when D is aluminum (Al), R b , R c and R d may each independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d are Each may be pentafluorophenyl.
[화학식 11][Formula 11]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]- [LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
위 화학식 11에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다. 구체적으로, [L-H]+는 디메틸아닐리늄 양이온일 수 있고, [Z(A)4]-는 [B(C6F5)4]-일 수 있으며, [L]+는 [(C6H5)3C]+일 수 있다.In Formula 11 above, L is a neutral or cationic Lewis base, [LH] + and [L] + are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group. Specifically, [LH] + may be a dimethylanilinium cation, [Z(A) 4 ] - may be [B(C 6 F 5 ) 4 ] - , and [L] + may be [(C 6 H 5 ) 3 C] + .
구체적으로, 위 화학식 9로 표시되는 화합물의 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등을 들 수 있으며, 메틸알루미녹산이 바람직하나, 이들로 제한되는 것은 아니다.Specifically, examples of the compound represented by Formula 9 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and methyl aluminoxane is preferable, but is not limited thereto.
위 화학식 10으로 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 등을 들 수 있으며, 트리메틸알루미늄, 트리에틸알루미늄 및 트리이소부틸알루미늄이 바람직하나, 이들로 제한되는 것은 아니다.Examples of the compound represented by Formula 10 above are trimethylaluminum, triethylaluminium, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminium, tri- s -butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and trimethylaluminum, triethylaluminum and triisobutylaluminum are preferred, but not limited thereto.
위 화학식 11로 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 등을 들 수 있다.Examples of the compound represented by Formula 11 above are triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra ( p -tolyl) Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra( p -tolyl) ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , tributylammonium tetra( p -trifluoromethylphenyl) boron, triphenylcarbonium tetra( p -trifluoromethylphenyl)boron, triphenylcarbonium tetrapentafluorophenylboron, and the like.
본 발명의 바람직한 구체예에 있어서, 올레핀 중합용 촉매가 전이금속 화합물을 담지하는 담체를 더 포함할 수 있다. 구체적으로, 담체가 전이금속 화합물과 조촉매 화합물을 모두 담지할 수 있다.In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound. Specifically, the carrier may support both the transition metal compound and the cocatalyst compound.
이때, 담체는 표면에 히드록시기를 함유하는 물질을 포함할 수 있으며, 바람직하게는 건조되어 표면에 수분이 제거된, 반응성이 큰 히드록시기와 실록산기를 갖는 물질이 사용될 수 있다. 예컨대, 담체는 실리카, 알루미나 및 마그네시아로 구성되는 군으로부터 선택되는 적어도 하나를 포함할 수 있다. 구체적으로, 고온에서 건조된 실리카, 실리카-알루미나, 및 실리카-마그네시아 등이 담체로서 사용될 수 있고, 이들은 통상적으로 Na2O, K2CO3, BaSO4, 및 Mg(NO3)2 등의 산화물, 탄산염, 황산염, 및 질산염 성분을 함유할 수 있다. 또한, 이들은 탄소, 제올라이트, 염화 마그네슘 등을 포함할 수도 있다. 다만, 담체가 이들로 제한되는 것은 아니며, 전이금속 화합물과 조촉매 화합물을 담지할 수 있는 것이면 특별히 제한되지 않는다.At this time, the carrier may include a material containing a hydroxyl group on the surface, and preferably, a material having a highly reactive hydroxyl group and a siloxane group, from which moisture is removed from the surface by drying, may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica dried at high temperature, silica-alumina, silica-magnesia, and the like can be used as carriers, which are usually oxides such as Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) 2 . , carbonate, sulfate, and nitrate components. In addition, they may contain carbon, zeolites, magnesium chloride, and the like. However, the carrier is not limited thereto, and is not particularly limited as long as it can support the transition metal compound and the cocatalyst compound.
담체는 평균 입도가 10~250 ㎛일 수 있으며, 바람직하게는 평균 입도가 10~150 ㎛일 수 있고, 보다 바람직하게는 20~100 ㎛일 수 있다.The carrier may have an average particle size of 10 to 250 μm, preferably 10 to 150 μm, and more preferably 20 to 100 μm.
담체의 미세기공 부피는 0.1~10 cc/g일 수 있으며, 바람직하게는 0.5~5 cc/g일 수 있고, 보다 바람직하게는 1.0~3.0 cc/g일 수 있다.The micropore volume of the carrier may be 0.1 to 10 cc/g, preferably 0.5 to 5 cc/g, and more preferably 1.0 to 3.0 cc/g.
담체의 비표면적은 1~1,000 ㎡/g일 수 있으며, 바람직하게는 100~800 ㎡/g일 수 있고, 보다 바람직하게는 200~600 ㎡/g일 수 있다.The specific surface area of the carrier may be 1 to 1,000 m2/g, preferably 100 to 800 m2/g, and more preferably 200 to 600 m2/g.
바람직한 일 실시예에서, 담체가 실리카일 경우, 실리카는 건조 온도는 상온~900℃일 수 있다. 건조 온도는 바람직하게는 상온~800℃, 보다 바람직하게는 상온~700℃일 수 있다. 건조 온도가 상온보다 낮을 경우에는 수분이 너무 많아서 표면의 수분과 조촉매가 반응하게 되고, 900℃를 초과하게 되면 담체의 구조가 붕괴될 수 있다.In a preferred embodiment, when the carrier is silica, the drying temperature of the silica may be from room temperature to 900°C. The drying temperature may be preferably from room temperature to 800°C, more preferably from room temperature to 700°C. When the drying temperature is lower than room temperature, too much moisture causes the surface moisture to react with the cocatalyst, and when the drying temperature exceeds 900° C., the structure of the carrier may collapse.
건조된 실리카 내의 히드록시기의 농도는 0.1~5 mmole/g일 수 있으며, 바람직하게는 0.7~4 mmole/g일 수 있고, 보다 바람직하게는 1.0~2 mmole/g일 수 있다. 히드록시기의 농도가 0.1 mmole/g 미만이면 조촉매의 담지량이 낮아지며, 5 mmole/g을 초과하면 촉매 성분이 불활성화되는 문제점이 발생할 수 있다.The concentration of the hydroxy group in the dried silica may be 0.1 to 5 mmole/g, preferably 0.7 to 4 mmole/g, and more preferably 1.0 to 2 mmole/g. If the concentration of the hydroxy group is less than 0.1 mmole/g, the supported amount of the cocatalyst is low, and if it exceeds 5 mmole/g, a problem of inactivation of the catalyst component may occur.
담체에 담지되는 전이금속 화합물의 총량은 담체 1 g을 기준으로 0.001~1 mmole일 수 있다. 전이금속 화합물과 담체의 비가 위 범위를 만족하면, 적절한 담지 촉매 활성을 나타내어 촉매의 활성 유지 및 경제성 측면에서 유리하다.The total amount of the transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier. When the ratio of the transition metal compound and the carrier satisfies the above range, it exhibits appropriate supported catalyst activity, which is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.
담체에 담지되는 조촉매 화합물의 총량은 담체 1 g을 기준으로 2~15 mmole일 수 있다. 조촉매 화합물과 담체의 비가 위 범위를 만족하면, 촉매의 활성 유지 및 경제성 측면에서 유리하다.The total amount of the cocatalyst compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier. When the ratio of the cocatalyst compound and the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.
담체는 1종 또는 2종 이상이 사용될 수 있다. 예를 들어, 1종의 담체에 전이금속 화합물과 조촉매 화합물이 모두 담지될 수도 있고, 2종 이상의 담체에 전이금속 화합물과 조촉매 화합물이 각각 담지될 수도 있다. 또한, 전이금속 화합물과 조촉매 화합물 중 하나만이 담체에 담지될 수도 있다.One or two or more carriers may be used. For example, both the transition metal compound and the cocatalyst compound may be supported on one carrier, or the transition metal compound and the cocatalyst compound may be supported on two or more carriers, respectively. In addition, only one of the transition metal compound and the cocatalyst compound may be supported on the carrier.
올레핀 중합용 촉매의 제조방법Method for preparing a catalyst for olefin polymerization
본 발명의 다른 구현예에 따라서, (1) 아래 화학식 2로 표시되는 화합물과 아래 화학식 3으로 표시되는 화합물을 반응시켜 아래 화학식 4로 표시되는 화합물을 얻는 단계; (2) 화학식 4로 표시되는 화합물과 아래 화학식 5로 표시되는 화합물을 반응시켜 아래 화학식 6으로 표시되는 화합물을 얻는 단계; (3) 화학식 6으로 표시되는 화합물과 유기 리튬 화합물을 반응시켜 아래 화학식 7로 표시되는 화합물을 얻는 단계; 및 (4) 화학식 7로 표시되는 화합물과 아래 화학식 8로 표시되는 화합물을 반응시켜 아래 화학식 1로 표시되는 전이금속 화합물을 얻는 단계; 및 (5) 단계 (4)에서 얻어진 전이금속 화합물, 조촉매 화합물 또는 둘 다를 담체에 담지시키는 단계를 포함하는 올레핀 중합용 촉매의 제조방법이 제공된다.According to another embodiment of the present invention, (1) reacting the compound represented by the formula (2) and the compound represented by the formula (3) to obtain a compound represented by the formula (4); (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 below; and (5) supporting the transition metal compound, cocatalyst compound, or both obtained in step (4) on a carrier.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
Me2Si(Xa)2 Me 2 Si(X a ) 2
[화학식 4][Formula 4]
[화학식 5][Formula 5]
R4NH2 R 4 NH 2
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
MX4 MX4
위 화학식에서, l, m, n, M, X, R1 내지 R4는 위 전이금속 화합물의 항목에서 설명한 바와 같고, Me는 메틸, Xa는 할로겐이다.In the above formula, l, m, n, M, X, R 1 to R 4 are as described in the above transition metal compound, Me is methyl, and X a is halogen.
위 단계 (1) 내지 단계 (4)의 구체적인 내용은 위 전이금속 화합물의 제조방법의 단계 (1) 내지 단계 (4)와 실질적으로 동일하다.Details of the above steps (1) to (4) are substantially the same as steps (1) to (4) of the above transition metal compound preparation method.
단계 (5)step (5)
위 단계 (5)에서, 전이금속 화합물, 조촉매 화합물 또는 둘 다를 담체에 담지시킨다.In the above step (5), the transition metal compound, the cocatalyst compound or both are supported on the carrier.
전이금속 화합물 및/또는 조촉매 화합물을 담지하는 방법으로서, 물리적 흡착 방법 또는 화학적 흡착 방법이 사용될 수 있다.As a method for supporting the transition metal compound and/or cocatalyst compound, a physical adsorption method or a chemical adsorption method may be used.
예를 들어, 물리적 흡착 방법은 전이금속 화합물이 용해된 용액을 담체에 접촉시킨 후 건조하는 방법, 전이금속 화합물과 조촉매 화합물이 용해된 용액을 담체에 접촉시킨 후 건조하는 방법, 또는 전이금속 화합물이 용해된 용액을 담체에 접촉시킨 후 건조하여 전이금속 화합물이 담지된 담체를 제조하고, 이와 별개로 조촉매 화합물이 용해된 용액을 담체에 접촉시킨 후 건조하여 조촉매 화합물이 담지된 담체를 제조한 후, 이들을 혼합하는 방법 등일 수 있다.For example, the physical adsorption method is a method of contacting a solution in which a transition metal compound is dissolved with a carrier and then drying it, a method of bringing a solution in which a transition metal compound and a cocatalyst compound are dissolved into contact with a carrier, and drying the solution, or a transition metal compound The dissolved solution is brought into contact with a carrier and dried to prepare a carrier supported with a transition metal compound, and separately, the solution in which the cocatalyst compound is dissolved is brought into contact with a carrier and then dried to prepare a carrier supported with a cocatalyst compound. After that, it may be a method of mixing them.
화학적 흡착 방법은 담체의 표면에 조촉매 화합물을 먼저 담지시킨 후, 조촉매 화합물에 전이금속 화합물을 담지시키는 방법, 또는 담체의 표면의 작용기(예를 들어, 실리카의 경우 실리카 표면의 히드록시기(-OH))와 전이금속 화합물을 공유결합시키는 방법 등일 수 있다.The chemical adsorption method is a method in which a cocatalyst compound is first supported on the surface of a carrier and then a transition metal compound is supported on the cocatalyst compound, or a functional group on the surface of the carrier (for example, in the case of silica, a hydroxyl group on the silica surface (-OH) )) and a method of covalently bonding a transition metal compound.
여기서, 전이금속 화합물 및/또는 조촉매 화합물을 담지시킬 때 사용되는 용매는 특별히 제한되지 않는다. 예를 들어, 용매는 헥산, 펜탄과 같은 지방족 탄화수소 용매, 톨루엔, 벤젠과 같은 방향족 탄화 수소 용매, 디클로로메탄과 같은 염소 원자로 치환된 탄화수소 용매, 디에틸에테르, 테트라하이드로퓨란과 같은 에테르계 용매, 아세톤 및 에틸아세테이트로 구성되는 군으로부터 선택되는 적어도 1종을 포함할 수 있다.Here, the solvent used for supporting the transition metal compound and/or the cocatalyst compound is not particularly limited. For example, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether or tetrahydrofuran, or acetone. And it may include at least one selected from the group consisting of ethyl acetate.
바람직한 일 실시예에서, 위 단계 (5)에서 담체에 전이금속 화합물 및/또는 조촉매 화합물을 담지시키는 과정은 0~100℃의 온도, 바람직하게는 실온~90℃의 온도에서 수행될 수 있다.In a preferred embodiment, the process of supporting the transition metal compound and/or cocatalyst compound on the support in step (5) may be performed at a temperature of 0 to 100°C, preferably from room temperature to 90°C.
또한, 단계 (5)에서 담체에 전이금속 화합물 및/또는 조촉매 화합물을 담지시키는 과정은 전이금속 화합물 및/또는 조촉매 화합물과 담체의 혼합물을 1분~24시간, 바람직하게는 5분~15시간 동안 충분히 교반함으로써 수행될 수 있다.In addition, in the process of supporting the transition metal compound and/or cocatalyst compound on the carrier in step (5), the mixture of the transition metal compound and/or cocatalyst compound and the carrier is maintained for 1 minute to 24 hours, preferably 5 minutes to 15 hours. It can be performed by sufficiently stirring for a period of time.
올레핀의 중합polymerization of olefins
본 발명의 구현예에 따른 올레핀 중합용 촉매의 존재하에 올레핀계 단량체를 중합하여 올레핀계 중합체를 제조할 수 있다.An olefin-based polymer may be prepared by polymerizing an olefin-based monomer in the presence of a catalyst for olefin polymerization according to an embodiment of the present invention.
여기서, 올레핀계 중합체는 올레핀계 단량체의 단독 중합체(homopolymer) 또는 올레핀계 단량체와 공단량체의 공중합체(copolymer)일 수 있다.Here, the olefin-based polymer may be a homopolymer of olefin-based monomers or a copolymer of olefin-based monomers and comonomers.
올레핀계 단량체는 C2-20 알파-올레핀(α-olefin), C1-20 디올레핀(diolefin), C3-20 사이클로올레핀(cycloolefin) 및 C3-20 사이클로디올레핀(cyclodiolefin)으로 구성되는 군으로부터 선택되는 적어도 하나이다.The olefinic monomer is composed of C 2-20 alpha-olefin, C 1-20 diolefin, C 3-20 cycloolefin and C 3-20 cyclodiolefin. It is at least one selected from the group.
예를 들어, 올레핀계 단량체는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센 또는 1-헥사데센 등일 수 있고, 올레핀계 중합체는 위에서 예시된 올레핀계 단량체를 1종만 포함하는 단독 중합체이거나 2종 이상 포함하는 공중합체일 수 있다.For example, olefinic monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 It may be dodecene, 1-tetradecene or 1-hexadecene, etc., and the olefinic polymer may be a homopolymer containing only one olefinic monomer or a copolymer containing two or more of the olefinic monomers exemplified above.
예시적인 구체예에서, 올레핀계 중합체는 에틸렌과 C3-20 알파-올레핀이 공중합된 공중합체일 수 있으며, 에틸렌과 1-헥센이 공중합된 공중합체가 바람직하나, 이들로 제한되는 것은 아니다.In an exemplary embodiment, the olefin-based polymer may be a copolymer of ethylene and C 3-20 alpha-olefin, preferably a copolymer of ethylene and 1-hexene, but is not limited thereto.
이 경우, 에틸렌의 함량은 55~99.9 중량%인 것이 바람직하고, 90~99.9 중량%인 것이 더욱 바람직하다. 알파-올레핀계 공단량체의 함량은 0.1~45 중량%가 바람 직하고, 0.1~10 중량%인 것이 더욱 바람직하다.In this case, the content of ethylene is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight. The content of the alpha-olefin comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.
예시적인 구체예에서, 올레핀계 중합체는 자유 라디칼(free radical), 양이온(cationic), 배위(coordination), 축합(condensation), 첨가(addition) 등의 중합반응에 의해 중합될 수 있으나, 이들로 제한되는 것은 아니다.In an exemplary embodiment, the olefin-based polymer may be polymerized by a polymerization reaction such as free radical, cationic, coordination, condensation, or addition, but is limited to these it is not going to be
바람직한 구체예로서, 올레핀계 중합체는 기상 중합법, 용액 중합법 또는 슬러리 중합법 등으로 제조될 수 있다. 올레핀계 중합체가 용액 중합법 또는 슬러리 중합법으로 제조되는 경우, 사용될 수 있는 용매의 예로서, 펜탄, 헥산, 헵탄, 노난, 데칸 및 이들의 이성질체와 같은 C5-12 지방족 탄화수소 용매; 톨루엔, 벤젠과 같은 방향족 탄화수소 용매; 디클로로메탄, 클로로벤젠과 같은 염소 원자로 치환된 탄화수소 용매; 및 이들의 혼합물 등을 들 수 있으나, 이들로 제한되는 것은 아니다.As a preferred embodiment, the olefin-based polymer may be prepared by gas phase polymerization, solution polymerization or slurry polymerization. When the olefinic polymer is produced by solution polymerization or slurry polymerization, examples of solvents that can be used include C 5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; aromatic hydrocarbon solvents such as toluene and benzene; hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; and mixtures thereof, but are not limited thereto.
실시예Example
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 단, 아래의 실시예는 본 발명을 예시하기 위한 것일 뿐이며, 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for exemplifying the present invention, and the scope of the present invention is not limited only to these.
실시예Example 1: N- 1:N- terttert -부틸-1,1-디메틸-1-(2'--Butyl-1,1-dimethyl-1-(2'- 메틸methyl -1',5',6',7'--1',5',6',7'- 테트라하이드로스피로tetrahydrospiro [사이클로헥산-1,4'-인데닐])실란아민 지르코늄 디클로라이드(N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; 화학식 1-[Cyclohexane-1,4'-indenyl]) Silanamine Zirconium dichloride (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7' -tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; 1)의1) of 제조 manufacturing
아래 반응식 1에 정리된 합성 절차에 따라서 화학식 1-1의 전이금속 화합물을 제조하였다.A transition metal compound of Chemical Formula 1-1 was prepared according to the synthesis procedure outlined in Reaction Scheme 1 below.
[반응식 1][Scheme 1]
단계 1: Step 1: 스피로[5.5]운데칸Spiro[5.5]undecane -1-온(-1-one ( spiro[5.5]undecanspiro[5.5]undecan -1-one; 화학식 -1-one; chemical formula bb )의 합성) synthesis of
칼륨 t-부톡사이드(potassium tert-butoxide)(11.43 g, 102 mmole)를 톨루엔(80 ㎖)에 분산시킨 용액에 사이클로헥사논(cyclohexanone; 화학식 a)(5.0 g, 51 mmole)을 톨루엔(50 ㎖)에 희석한 용액과 1,5-디브로모펜탄(1,5-dibromopentane)(11.71 g, 51 mmole)을 톨루엔(70 ㎖)에 희석한 용액을 천천히 첨가하였다. 그후, 110℃에서 12시간 교반하였다. 반응을 종결시키기 위해 0℃에서 1 M 염산을 첨가하여 중화한 후, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘(MgSO4)으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거한 후, 컬럼 크로마토그래피(헥산:에틸아세테이트 = 20/1, v/v)로 분리하여 흰색 고체 화합물 5.59 g(66%)을 얻었다.To a solution in which potassium tert-butoxide (11.43 g, 102 mmole) was dispersed in toluene (80 ml), cyclohexanone (Formula a ) (5.0 g, 51 mmole) was added to toluene (50 ml). ) and a diluted solution of 1,5-dibromopentane (11.71 g, 51 mmole) in toluene (70 ml) were slowly added. After that, the mixture was stirred at 110°C for 12 hours. After neutralization by adding 1 M hydrochloric acid at 0 °C to terminate the reaction, the organic layer was separated using a separatory funnel. After removing the remaining water with magnesium sulfate (MgSO 4 ) and removing the solvent under vacuum, it was separated by column chromatography (hexane: ethyl acetate = 20/1, v/v) to give 5.59 g (66%) of a white solid compound. got
1H NMR (300 MHz, CDCl3): δ 2.40 (t, 2 H), 1.80-1.93 (m, 4 H), 1.66-1.75 (m, 4 H), 1.45-1.53 (m, 4 H), 1.30-1.45 (m, 4 H). 1 H NMR (300 MHz, CDCl 3 ): δ 2.40 (t, 2 H), 1.80-1.93 (m, 4 H), 1.66-1.75 (m, 4 H), 1.45-1.53 (m, 4 H), 1.30-1.45 (m, 4 H).
단계 step 2: 22:2 -- 브로모스피로[5,5]운데칸bromospiro[5,5]undecane -1-온(2--1-one (2- bromospiro[5,5]undecanbromospiro[5,5]undecan -1-one; 화학식 -1-one; chemical formula cc )의 합성) synthesis of
화학식 b의 화합물(5.59 g, 34 mmole)을 디에틸에테르(50 ㎖)에 희석한 용액에 브롬(5.37 g, 34 mmole)을 디에틸에테르(50 ㎖)에 희석한 용액을 0℃에서 천천히 첨가한 후, 온도를 서서히 상온으로 올려 12시간 동안 교반하였다. 반응을 종결시키기 위해 티오황산나트륨(Na2S2O3) 포화 용액을 첨가하여 반응 후 남아 있는 브롬을 제거하고, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거한 후, 컬럼 크로마토그래피(헥산:에틸아세테이트 = 20/1, v/v)로 분리하여 노란색 액체 화합물 9.23 g(당량적인 수율)을 얻었다.To a solution of the compound of Formula b (5.59 g, 34 mmole) diluted in diethyl ether (50 mL), a solution of bromine (5.37 g, 34 mmole) diluted in diethyl ether (50 mL) was slowly added at 0 ° C. After that, the temperature was gradually raised to room temperature and stirred for 12 hours. To terminate the reaction, a saturated solution of sodium thiosulfate (Na 2 S 2 O 3 ) was added to remove bromine remaining after the reaction, and the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum, followed by column chromatography (hexane:ethyl acetate = 20/1, v/v) to obtain 9.23 g (equivalent yield) of a yellow liquid compound.
1H NMR (300 MHz, CDCl3): δ 4.94 (dd, 1 H), 2.57-2.66 (m, 1 H), 2.09 (dd, 1 H), 1.85-2.01 (m, 4 H), 1.64-1.78 (m, 4 H), 1.37-1.61 (m, 6 H), 1.20-1.34 (m, 2 H). 1 H NMR (300 MHz, CDCl 3 ): δ 4.94 (dd, 1 H), 2.57-2.66 (m, 1 H), 2.09 (dd, 1 H), 1.85-2.01 (m, 4 H), 1.64- 1.78 (m, 4 H), 1.37–1.61 (m, 6 H), 1.20–1.34 (m, 2 H).
단계 3: 에틸 3-옥소-2-Step 3: Ethyl 3-oxo-2- (1-옥소스피로[5,5]운데켄-2-일)부티레이트(ethyl 3-oxo-2-(1-oxospiro[5,5]undecen-2-yl)butyrate (ethyl 3-oxo-2- (1-oxospiro[5.5]undecen-2-yl)butyrate; 화학식 (1-oxospiro[5.5]undecen-2-yl)butyrate; chemical formula dd )의 합성) synthesis of
에틸아세토아세테이트 나트륨 염(ethyl acetoacetate sodium salt)(11.45 g, 75 mmole)을 톨루엔(70 ㎖)에 분산시킨 용액에 화학식 c의 화합물(9.23 g, 38 mmole)을 톨루엔(30 ㎖)에 희석한 용액을 첨가하였다. 그후 110℃에서 12시간 동안 교반하였다. 반응을 종결시키기 위해 0℃에서 1 M 염산을 첨가하여 중화한 후, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거하여, 화학식 d의 화합물과 에틸아세토아세테이트가 혼합된 노란색 액체 혼합물 12.30 g(당량적인 수율)를 얻었다.A solution obtained by dispersing ethyl acetoacetate sodium salt (11.45 g, 75 mmole) in toluene (70 ml) and diluting the compound of formula c (9.23 g, 38 mmole) in toluene (30 ml). was added. It was then stirred at 110° C. for 12 hours. After neutralization by adding 1 M hydrochloric acid at 0 °C to terminate the reaction, the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum to obtain 12.30 g (equivalent yield) of a yellow liquid mixture of the compound of formula d and ethylacetoacetate.
단계 step 4: 24:2 -- (2-옥소프로필)스피로[5,5]운데칸(2-oxopropyl)spiro[5,5]undecane -1-온(2--1-one (2- (2-oxopropyl)spiro[5.5](2-oxopropyl)spiro[5.5] undecan-1-one; 화학식 undecan-1-one; chemical formula ee )의 합성) synthesis of
화학식 d의 화합물과 에틸아세토아세테이트의 혼합물을 메탄올(120 ㎖)에 희석한 용액에 3.0 M 수산화칼륨 수용액(120 ㎖)를 첨가하고, 65℃에서 12시간 동안 교반하였다. 반응을 종결시키기 위해 0℃에서 1 M 염산을 첨가하여 중화한 후, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거한 후, 컬럼 크로마토그래피(헥산:에틸아세테이트 = 20/1, v/v)로 분리하여 노란색 액체 화합물 3.46 g(31%)을 얻었다.A 3.0 M aqueous solution of potassium hydroxide (120 ml) was added to a solution of a mixture of the compound of formula d and ethyl acetoacetate diluted in methanol (120 ml), and the mixture was stirred at 65° C. for 12 hours. After neutralization by adding 1 M hydrochloric acid at 0 °C to terminate the reaction, the organic layer was separated using a separatory funnel. The remaining water was removed with magnesium sulfate, and the solvent was removed under vacuum, followed by column chromatography (hexane:ethyl acetate = 20/1, v/v) to obtain 3.46 g (31%) of a yellow liquid compound.
1H NMR (300 MHz, CDCl3): δ 3.25-3.36 (m, 1 H), 2.94 (dd, 1 H), 2.22 (s, 3 H), 2.12 (dd, 1 H), 1.85-2.04 (m, 4 H), 1.55-1.70 (m, 4 H), 1.24-1.52 (m, 7 H), 1.01-1.10 (m, 1 H). 1 H NMR (300 MHz, CDCl 3 ): δ 3.25-3.36 (m, 1 H), 2.94 (dd, 1 H), 2.22 (s, 3 H), 2.12 (dd, 1 H), 1.85-2.04 ( m, 4 H), 1.55–1.70 (m, 4 H), 1.24–1.52 (m, 7 H), 1.01–1.10 (m, 1 H).
단계 step 5: 55:5 ',6',7',7a'-',6',7',7a'- 테트라하이드로스피로tetrahydrospiro [[ 사이클로헥산cyclohexane -1,4'--1,4'- 인덴inden ]2' (1'H)-온(5',6',7',7a'-tetrahydrospiro[cyclohexane-1,4'-inden]2' (] 2' (1'H) -one (5', 6', 7', 7a'-tetrahydrospiro [cyclohexane-1,4'-inden] 2' ( 1'H1'H )-one; 화학식 ) - one; chemical formula ff )의 합성) synthesis of
화학식 e의 화합물(3.46 g, 16 mmole)을 톨루엔(35 ㎖)에 희석한 용액에 칼륨 t-부톡사이드(2.10 g, 19 mmole)를 첨가하고, 상온에서 4시간 동안 교반하였다. 증류수를 첨가하여 반응을 종결시키고, 에틸아세테이트로 추출하여, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거한 후, 컬럼 크로마토그래피(헥산:에틸아세테이트 = 20/1, v/v)로 분리하여 노란색 바늘형 고체와 노란색 액체가 혼합된 화합물 1.65 g(52%)을 얻었다.Potassium t -butoxide (2.10 g, 19 mmole) was added to a solution of the compound of formula e (3.46 g, 16 mmole) diluted in toluene (35 ml), and the mixture was stirred at room temperature for 4 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. After removing the remaining water with magnesium sulfate, removing the solvent under vacuum, and separating by column chromatography (hexane: ethyl acetate = 20/1, v/v), 1.65 g of a compound obtained as a mixture of a yellow needle-like solid and a yellow liquid was obtained. (52%).
1H NMR (300 MHz, CDCl3): δ 5.90 and 5.81 (s, 1 H), 2.85-2.93 and 2.75-2,81 (m, 1 H), 2.59 and 2.75 (d, 1 H), 2.15-2.38 (m, 3 H), 0.92-2.02 (m, 14 H). 1 H NMR (300 MHz, CDCl 3 ): δ 5.90 and 5.81 (s, 1 H), 2.85-2.93 and 2.75-2,81 (m, 1 H), 2.59 and 2.75 (d, 1 H), 2.15- 2.38 (m, 3 H), 0.92–2.02 (m, 14 H).
단계 6: 2'-메틸-1',2',5',6',7',7a'-헥사하이드로스피로[사이클로헥산-1,4'-인덴]-2'-올(2'-methyl-1',2',5',6',7',7a'-hexahydrospiro[cyclohexane-1,4'-inden]-2'-ol; 화학식 Step 6: 2'-methyl-1', 2', 5', 6', 7', 7a'-hexahydrospiro [cyclohexane-1,4'-indene] -2'-ol (2'-methyl -1',2',5',6',7',7a'-hexahydrospiro[cyclohexane-1,4'-inden]-2'-ol; gg )의 합성) synthesis of
화학식 f의 화합물(1.0 g, 4.89 mmole)을 테트라하이드로퓨란(20 ㎖)에 녹인 용액을 -30℃까지 냉각한 후, 1.6 M의 메틸리튬 용액(4.6 ㎖, 7.34 mmole)을 천천히 주입한 후, 상온에서 16시간 교반하였다. 증류수를 첨가하여 반응을 종결시키고, 에틸아세테이트로 추출하여, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거한 후, 얻은 화학식 g의 화합물을 그대로 다음 반응에 사용하였다.After cooling the solution of the compound of formula f (1.0 g, 4.89 mmole) in tetrahydrofuran (20 ml) to -30 ° C, a 1.6 M methyllithium solution (4.6 ml, 7.34 mmole) was slowly injected, The mixture was stirred at room temperature for 16 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was separated using a separatory funnel. After removing remaining water with magnesium sulfate and removing the solvent under vacuum, the obtained compound of formula g was used in the next reaction as it is.
단계 step 7: 27:2 '-'- 메틸methyl -5',6',7',7a'--5',6',7',7a'- 테트라하이드로스피로tetrahydrospiro [[ 사이클로헥산cyclohexane -1,4'--1,4'- 인덴inden ](2'-methyl-5',6',7',7a'-tetrahydrospiro[cyclohexane-1,4'-indene; 화학식 ](2'-methyl-5',6',7',7a'-tetrahydrospiro[cyclohexane-1,4'-indene; chemical formula hh )의 합성) synthesis of
화학식 g의 화합물을 디에틸에테르(10 ㎖)에 녹인 용액을 0℃까지 냉각한 후, 1 M 염산(6 ㎖)를 주입하고, 온도를 유지하면서 2시간 교반하였다. 그후, 증류수(10 ㎖)로 희석하고, 에틸아세테이트로 추출하여, 분별 깔때기로 유기 층을 분리하였다. 황산마그네슘으로 남아 있는 물을 제거하고, 진공하에서 용매를 제거한 후, 컬럼 크로마토그래피(헥산)로 분리하여, 무색 액체인 깨끗한 화학식 h의 화합물 466 ㎎(47%)을 얻었다.A solution of the compound of Formula g dissolved in diethyl ether (10 ml) was cooled to 0°C, then 1 M hydrochloric acid (6 ml) was added thereto, and the mixture was stirred for 2 hours while maintaining the temperature. Then, it was diluted with distilled water (10 ml), extracted with ethyl acetate, and the organic layer was separated with a separatory funnel. The remaining water was removed with magnesium sulfate, the solvent was removed under vacuum, and then separated by column chromatography (hexane) to give 466 mg (47%) of compound h as a clear colorless liquid.
1H NMR (300 MHz, CDCl3): δ 6.10 and 5.85 (s, 1 H), 2.83 and 2.77 (s, 2 H), 2.23-2.10 (m, 2 H), 2.00 (s, 3 H), 1.71-1.54 (m, 4 H), 1.54-1.41 (m, 10 H). 1 H NMR (300 MHz, CDCl 3 ): δ 6.10 and 5.85 (s, 1 H), 2.83 and 2.77 (s, 2 H), 2.23-2.10 (m, 2 H), 2.00 (s, 3 H), 1.71-1.54 (m, 4 H), 1.54-1.41 (m, 10 H).
단계 step 8: 28:2 '-'- 메틸methyl -5',6',7',7a'--5',6',7',7a'- 테트라하이드로스피로tetrahydrospiro [[ 사이클로헥산cyclohexane -1,4'--1,4'- 인데닐indenyl ] 리튬(2'-methyl-5',6',7',7a'-] Lithium (2'-methyl-5',6',7',7a'- tetrahydrospirotetrahydrospiro [[ cyclohexanecyclohexane -1,4'--1,4'- indenylindenyl ] lithium; 화학식 ] lithium; chemical formula ii )의 합성) synthesis of
화학식 h의 화합물(51 ㎎, 0.25 mmole)을 테트라하이드로퓨란(5 ㎖)에 녹인 용액을 -30℃까지 냉각한 후, 1.6 M의 n-부틸리튬 용액(0.2 ㎖, 0.31 mmole)을 천천히 주입한 후, 상온에서 16시간 동안 교반하였다. 진공하에서 테트라하이드로퓨란 용매를 제거한 후, 헥산을 첨가하여 분별 깔때기로 생성된 리튬 염 화합물(화학식 i)을 걸러낸 후, 헥산으로 여러 번 씻어 깨끗하게 정제하여 42 ㎎(79%)을 얻었다.A solution of the compound of formula h (51 mg, 0.25 mmole) in tetrahydrofuran (5 ml) was cooled to -30 ° C, and then a 1.6 M n- butyllithium solution (0.2 ml, 0.31 mmole) was slowly injected. Then, the mixture was stirred at room temperature for 16 hours. After removing the tetrahydrofuran solvent under vacuum, hexane was added to filter out the lithium salt compound (Formula i ) produced through a separatory funnel, and then washed several times with hexane to obtain 42 mg (79%).
단계 9: 클로로디메틸(2'-메틸-1',5',6',7'-테트라하이드로스피로[사이클로헥산-1,4'-인덴]-1'-일)실란(chlorodimethyl(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silane; 화학식 Step 9: Chlorodimethyl(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-indene]-1'-yl)silane (chlorodimethyl(2'- methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silane; jj )의 합성) synthesis of
디메틸디클로로실란(Me2SiCl2)(35 ㎎, 0.17 mmole)을 톨루엔(1 ㎖)에 녹인 용액을 -30℃까지 냉각한 후, 화학식 i의 화합물(35 ㎎, 0.17 mmole)을 톨루엔(1 ㎖)에 녹인 용액을 천천히 주입한 후, 90℃에서 16시간 동안 교반하였다. 진공하에서 톨루엔을 제거한 후, 펜탄을 첨가하여 생성물을 추출하고, 진공하에서 펜탄을 제거하여 흰색 고체 화합물 39 ㎎(78%)을 얻었다.After cooling a solution of dimethyldichlorosilane (Me 2 SiCl 2 ) (35 mg, 0.17 mmole) in toluene (1 ml) to -30 ° C, the compound of formula i (35 mg, 0.17 mmole) was added to toluene (1 ml). ) After slowly injecting the dissolved solution, the mixture was stirred at 90° C. for 16 hours. After removal of toluene under vacuum, the product was extracted by addition of pentane and removal of pentane under vacuum to give 39 mg (78%) of the compound as a white solid.
1H NMR (300 MHz, C6D6): δ 6.19 (s, 1H), 2.91 (s, 1H), 2.05 (s, 3H), 1.61-1.18 (m, 16H), 0.18-0.09 (m, 6H). 1 H NMR (300 MHz, C 6 D 6 ): δ 6.19 (s, 1H), 2.91 (s, 1H), 2.05 (s, 3H), 1.61-1.18 (m, 16H), 0.18-0.09 (m, 6H).
단계 10: N-Step 10: N- terttert -부틸-1,1-디메틸-1-(2'--Butyl-1,1-dimethyl-1-(2'- 메틸methyl -1',5',6',7'- 테트라하이드로스피로[사이클로헥산-1,4'-인덴]-1'-일)실란아민(N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine; 화학식 -1', 5', 6', 7'- tetrahydrospiro [cyclohexane-1,4'-indene] -1'-yl) silaneamine (N-tert-butyl-1,1-dimethyl-1- (2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine; kk )의 합성) synthesis of
화학식 j의 화합물(39 ㎎, 0.13 mmole)을 테트라하이드로퓨란(1 ㎖)에 녹인 용액을 -30℃까지 냉각한 후, t-부틸아민(t-butylamine)(38 ㎎, 0.53 mmole)을 테트라하이드로퓨란(1 ㎖)에 녹인 용액을 천천히 주입한 후, 상온에서 16시간 동안 교반하였다. 진공하에서 테트라하이드로퓨란을 제거한 후, 펜탄을 첨가하여 생성물을 추출하고, 진공하에서 펜탄을 제거하여 흰색 고체 화합물 43 ㎎(97%)을 얻었다.After cooling the solution of the compound of formula j (39 mg, 0.13 mmole) in tetrahydrofuran (1 ml) to -30 ° C, t -butylamine ( t -butylamine) (38 mg, 0.53 mmole) was added to tetrahydro After slowly injecting a solution dissolved in furan (1 ml), the mixture was stirred at room temperature for 16 hours. After removing tetrahydrofuran under vacuum, pentane was added to extract the product, and pentane was removed under vacuum to obtain 43 mg (97%) of the compound as a white solid.
1H NMR (300 MHz, C6D6): δ 6.24 (s, 1H), 2.75 (s, 1H), 2.11 (s, 3H), 1.91 (m, 2H), 1.70-1.58 (m, 7H), 1.51-1.45 (m, 7H), 1.07 (s, 9H), 0.13 (d, 6H). 1 H NMR (300 MHz, C 6 D 6 ): δ 6.24 (s, 1H), 2.75 (s, 1H), 2.11 (s, 3H), 1.91 (m, 2H), 1.70-1.58 (m, 7H) , 1.51–1.45 (m, 7H), 1.07 (s, 9H), 0.13 (d, 6H).
단계 11: N-Step 11: N- terttert -부틸-1,1-디메틸-1-(2'--Butyl-1,1-dimethyl-1-(2'- 메틸methyl -1',5',6',7'- -1',5',6',7'- 테트라하이드로스피로tetrahydrospiro [사이클로헥산-1,4'-인덴]-1'-일)실란아민 [Cyclohexane-1,4'-indene] -1'-yl) silaneamine 디리튬dilithium 염(N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine Salt (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl )silanamine dilithiumdilithium salt; 화학식 salt; chemical formula ll )의 합성) synthesis of
화학식 k의 화합물(43 ㎎, 0.13 mmole)을 헥산(1 ㎖)에 녹인 용액을 -30℃까지 냉각한 후, 1.6 M의 t-부틸리튬(121 ㎎, 0.28 mmole) 용액을 천천히 주입한 후, 상온에서 16시간 동안 교반하였다. 진공하에서 헥산을 제거한 후, 펜탄으로 여러 차례 세척하고 건조시켜 다음 단계에 사용하였다.After cooling a solution of the compound of formula k (43 mg, 0.13 mmole) in hexane (1 ml) to -30 ° C, a 1.6 M t -butyllithium (121 mg, 0.28 mmole) solution was slowly injected therein, It was stirred for 16 hours at room temperature. After removing the hexane under vacuum, it was washed several times with pentane and dried to be used in the next step.
단계 12: N-Step 12: N- terttert -부틸-1,1-디메틸-1-(2'--Butyl-1,1-dimethyl-1-(2'- 메틸methyl -1',5',6',7'- -1',5',6',7'- 테트라하이드로스피로tetrahydrospiro [사이클로헥산-1,4'-인덴]-1'-일)실란아민 지르코늄 디클로라이드(N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; 화학식 1-[Cyclohexane-1,4'-indene] -1'-yl) silaneamine zirconium dichloride (N-tert-butyl-1,1-dimethyl-1-(2'-methyl-1',5',6 ',7'-tetrahydrospiro[cyclohexane-1,4'-inden]-1'-yl)silanamine zirconium dichloride; 1)의1) of 합성 synthesis
화학식 l의 화합물을 톨루엔(2 ㎖)에 녹인 용액에 트리에틸아민(trimethylamine)(52 ㎎, 0.52 mmole)을 넣고 30분 동안 교반한 후, 이 용액을 -30℃까지 냉각하였다. 여기에 염화지르코늄(ZrCl4)(30 ㎎, 0.12 mmole)를 넣고 상온에서 16시간 교반하였다. 반응 혼합물을 필터에 통과시켜 불순물을 제거하고, 진공하에서 톨루엔을 제거하였다. 이어서, 펜탄을 첨가하여 생성물을 추출하고, 진공하에서 펜탄을 제거하여 화학식 1-1의 화합물 30 ㎎(47%)을 얻었다.Trimethylamine (52 mg, 0.52 mmole) was added to a solution of the compound of Formula 1 in toluene (2 ml), stirred for 30 minutes, and then the solution was cooled to -30 °C. Zirconium chloride (ZrCl 4 ) (30 mg, 0.12 mmole) was added thereto, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was passed through a filter to remove impurities and toluene was removed under vacuum. Then, pentane was added to extract the product, and pentane was removed under vacuum to give 30 mg (47%) of the compound of Formula 1-1.
1H NMR (300 MHz, C6D6): δ 6.39 (s, 1H), 2.08 (s, 3H), 1.71-1.09 (m, 16H), 1.34 (s, 9H), 0.39 (s, 3H), 0.34 (s, 3H). 1 H NMR (300 MHz, C 6 D 6 ): δ 6.39 (s, 1H), 2.08 (s, 3H), 1.71-1.09 (m, 16H), 1.34 (s, 9H), 0.39 (s, 3H) , 0.34 (s, 3H).
본 발명의 구체예에 따른 전이금속 화합물 및 이를 포함하는 올레핀 중합용 촉매는 특이한 입체 구조를 가지기 때문에 중합체의 물성 조절이 가능하다.Since the transition metal compound and the catalyst for olefin polymerization containing the same according to an embodiment of the present invention have a unique three-dimensional structure, the physical properties of the polymer can be controlled.
Claims (16)
[화학식 1]
위 화학식 1에서, l은 0 내지 2의 정수, m은 0 내지 3의 정수, n은 0 내지 5의 정수이고,
M은 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이고,
X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도 또는 C6-20 아릴아미도이고,
R1 내지 R3는 각각 독립적으로 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이되, R1 내지 R3는 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있고,
R4는 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴 또는 치환 또는 비치환된 C1-20 알킬리덴이다.A transition metal compound represented by Formula 1 below:
[Formula 1]
In Formula 1 above, l is an integer from 0 to 2, m is an integer from 0 to 3, n is an integer from 0 to 5,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
X is each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido or C 6-20 arylamido;
R 1 to R 3 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted substituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl, wherein R One to R 3 may each independently form a substituted or unsubstituted saturated or unsaturated C 4-20 ring by connecting adjacent groups;
R 4 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl C 6- 20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl or substituted or unsubstituted C 1 -20 It is an alkylidene.
[화학식 1-1] [화학식 1-2] [화학식 1-3]
[화학식 1-4] [화학식 1-5] [화학식 1-6]
[화학식 1-7] [화학식 1-8] [화학식 1-9]
[화학식 1-10] [화학식 1-11] [화학식 1-12]
[화학식 1-13] [화학식 1-14] [화학식 1-15]
[화학식 1-16] [화학식 1-17] [화학식 1-18]
[화학식 1-19] [화학식 1-20] [화학식 1-21]
.The transition metal compound according to claim 1, wherein the transition metal compound represented by Formula 1 is at least one of transition metal compounds represented by Formulas 1-1 to 1-21 below:
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
[Formula 1-7] [Formula 1-8] [Formula 1-9]
[Formula 1-10] [Formula 1-11] [Formula 1-12]
[Formula 1-13] [Formula 1-14] [Formula 1-15]
[Formula 1-16] [Formula 1-17] [Formula 1-18]
[Formula 1-19] [Formula 1-20] [Formula 1-21]
.
[화학식 1]
[화학식 2]
[화학식 3]
Me2Si(Xa)2
[화학식 4]
[화학식 5]
R4NH2
[화학식 6]
[화학식 7]
[화학식 8]
MX4
위 화학식에서, l, m, n, M, X, R1 내지 R4는 위 전이금속 화합물의 항목에서 설명한 바와 같고, Me는 메틸, Xa는 할로겐이다.(1) reacting a compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3 below to obtain a compound represented by Chemical Formula 4; (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; and (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 below:
[Formula 1]
[Formula 2]
[Formula 3]
Me 2 Si(X a ) 2
[Formula 4]
[Formula 5]
R 4 NH 2
[Formula 6]
[Formula 7]
[Formula 8]
MX4
In the above formula, l, m, n, M, X, R 1 to R 4 are as described in the above transition metal compound, Me is methyl, and X a is halogen.
[화학식 2-1][화학식 2-2][화학식 2-3]
[화학식 2-4][화학식 2-5][화학식 2-6]
[화학식 2-7][화학식 2-8][화학식 2-9]
[화학식 2-10][화학식 2-11][화학식 2-12]
[화학식 2-13][화학식 2-14][화학식 2-15]
[화학식 2-16]
.The method of claim 4, wherein the compound represented by Formula 2 is at least one of the compounds represented by Formulas 2-1 to 2-16 below:
[Formula 2-1] [Formula 2-2] [Formula 2-3]
[Formula 2-4] [Formula 2-5] [Formula 2-6]
[Formula 2-7] [Formula 2-8] [Formula 2-9]
[Formula 2-10] [Formula 2-11] [Formula 2-12]
[Formula 2-13] [Formula 2-14] [Formula 2-15]
[Formula 2-16]
.
[화학식 9]
[화학식 10]
[화학식 11]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]-
위 화학식 9에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소기 또는 할로겐으로 치환된 C1-20 탄화수소기이고,
위 화학식 10에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이며,
위 화학식 11에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다.The catalyst for olefin polymerization according to claim 8, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by Formula 9, a compound represented by Formula 10, and a compound represented by Formula 11:
[Formula 9]
[Formula 10]
[Formula 11]
[LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
In Formula 9 above, n is an integer of 2 or greater, R a is a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen,
In Formula 10, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with halogen. Or a C 1-20 alkoxy group,
In Formula 11 above, L is a neutral or cationic Lewis base, [LH] + and [L] + are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group.
[화학식 1]
[화학식 2]
[화학식 3]
Me2Si(Xa)2
[화학식 4]
[화학식 5]
R4NH2
[화학식 6]
[화학식 7]
[화학식 8]
MX4
위 화학식에서, l, m, n, M, X, R1 내지 R4는 위 전이금속 화합물의 항목에서 설명한 바와 같고, Me는 메틸, Xa는 할로겐이다.(1) reacting a compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3 below to obtain a compound represented by Chemical Formula 4; (2) reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below to obtain a compound represented by Chemical Formula 6; (3) reacting the compound represented by Chemical Formula 6 with an organolithium compound to obtain a compound represented by Chemical Formula 7 below; (4) reacting a compound represented by Chemical Formula 7 with a compound represented by Chemical Formula 8 to obtain a transition metal compound represented by Chemical Formula 1 below; and (5) supporting a transition metal compound, a cocatalyst compound, or both obtained in step (4) on a carrier.
[Formula 1]
[Formula 2]
[Formula 3]
Me 2 Si(X a ) 2
[Formula 4]
[Formula 5]
R 4 NH 2
[Formula 6]
[Formula 7]
[Formula 8]
MX4
In the above formula, l, m, n, M, X, R 1 to R 4 are as described in the above transition metal compound, Me is methyl, and X a is halogen.
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