WO2022139317A1 - 혼성 촉매 조성물, 이를 포함하는 촉매 및 이를 이용한 올레핀계 중합체의 제조방법 - Google Patents
혼성 촉매 조성물, 이를 포함하는 촉매 및 이를 이용한 올레핀계 중합체의 제조방법 Download PDFInfo
- Publication number
- WO2022139317A1 WO2022139317A1 PCT/KR2021/019133 KR2021019133W WO2022139317A1 WO 2022139317 A1 WO2022139317 A1 WO 2022139317A1 KR 2021019133 W KR2021019133 W KR 2021019133W WO 2022139317 A1 WO2022139317 A1 WO 2022139317A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- aluminum
- boron
- olefin
- transition metal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 71
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 81
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims description 71
- -1 cationic Lewis base Chemical class 0.000 claims description 47
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 38
- 229910052796 boron Inorganic materials 0.000 claims description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- 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
- 239000002879 Lewis base Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [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
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052795 boron group element Inorganic materials 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
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 claims description 3
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 3
- 229940069096 dodecene Drugs 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
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 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
- 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 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
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 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 2
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000499 gel Substances 0.000 description 16
- 239000012968 metallocene catalyst Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000009826 distribution Methods 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 7
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 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
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 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
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- DBQOUEWUAIHCNY-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)alumane Chemical compound Fc1c(F)c(F)c([AlH2])c(F)c1F DBQOUEWUAIHCNY-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- FLFNHHSXSLXYQB-UHFFFAOYSA-L CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 FLFNHHSXSLXYQB-UHFFFAOYSA-L 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
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- SSLYIXHGTXGSJZ-UHFFFAOYSA-L cyclopentane;dichlorozirconium;indene Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.C1=CC=C[C]2[CH][CH][CH][C]21 SSLYIXHGTXGSJZ-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- MWSOLOKEHHPOBC-UHFFFAOYSA-N pentylaluminum Chemical compound CCCCC[Al] MWSOLOKEHHPOBC-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/025—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Definitions
- the present invention relates to a hybrid catalyst composition, a catalyst comprising the same, and a method for preparing an olefin-based polymer using the same.
- the present invention relates to a hybrid catalyst composition comprising a heterogeneous transition metal compound, a catalyst for olefin polymerization comprising the same, and a method for preparing an olefin-based polymer in which gel formation is suppressed using the catalyst.
- Polyolefin-based polymers are widely used in real life as materials for shopping bags, plastic houses, fishing nets, cigarette wrappers, ramen bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, washing machines, and the like.
- polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-alpha olefin copolymers and copolymers thereof have been prepared using a heterogeneous catalyst such as a Ziegler-Natta catalyst made of a titanium compound and an alkyl aluminum compound.
- a heterogeneous catalyst such as a Ziegler-Natta catalyst made of a titanium compound and an alkyl aluminum compound.
- a metallocene catalyst is a compound in which ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl are coordinated to a transition metal or transition metal halide compound, and has a sandwich structure in a basic form. . In this case, it has various molecular structures according to the type of ligand and the type of the central metal.
- the active site metal component is dispersed on an inactive solid surface and thus the properties of the active site are not uniform, the metallocene catalyst has a uniform structure. Since it is a compound with The polymer polymerized with such a metallocene catalyst has a narrow molecular weight distribution and a uniform distribution of comonomers.
- a metallocene catalyst since a metallocene catalyst has no activity 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 co-catalyst, and at the same time, the co-catalyst is an anion that is not coordinated with the metallocene catalyst and stabilizes the unsaturated cationic active species to form a catalyst system having activity in various olefin polymerizations.
- 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 uniform distribution of comonomers.
- the polymer prepared by the metallocene catalyst has a problem in that it has excellent mechanical strength but low processability due to a narrow molecular weight distribution.
- various methods such as changing the molecular structure of the polymer or widening the molecular weight distribution have been proposed.
- a catalyst for introducing a long chain branch (LCB) as a side branch to the main chain of the polymer is used to improve the processability of the polymer, but in the case of a supported catalyst, the activity is low. do.
- LCB long chain branch
- polyolefin having a bimodal molecular weight distribution prepared in this way has improved processability, but may exhibit non-uniformity of the polyolefin resin due to having different molecular weight distributions.
- polyolefin may contain a plurality of gels, or a product may have poor appearance or a sudden change in physical properties due to processing.
- It is an object of the present invention to provide a hybrid catalyst composition comprising a heterogeneous transition metal compound, a catalyst for olefin polymerization comprising the same, and a method for preparing an olefin-based polymer in which non-uniformity, particularly gel formation, is suppressed using the catalyst.
- l, n, p and q are each independently an integer of 0 to 4
- m is each independently an integer of 0 to 2
- o is an integer of 0 to 5;
- each M is independently titanium (Ti), zirconium (Zr) or hafnium (Hf);
- each X is independently halogen, nitro, 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;
- each Q is independently carbon (C), silicon (Si), germanium (Ge) or tin (Sn);
- R 1 to R 8 are each independently hydrogen, 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 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 , R 1 to R 6 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.
- the first transition metal compound, the second transition metal compound, and the third transition metal compound are each represented by a compound represented by Formula 1-1 below, a compound represented by Formula 2-1, and a compound represented by Formula 3-1 It may be the indicated compound.
- Bu is a butyl group and Ph is a phenyl group.
- the hybrid catalyst composition and the cocatalyst compound according to the embodiment of the present invention including the hybrid catalyst composition and the cocatalyst compound according to the embodiment of the present invention, wherein the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 1:100 to 100:1 and the content of the third transition metal compound is 10 to 90 mol% based on the total number of moles of the hybrid catalyst composition.
- a catalyst for olefin polymerization is provided.
- the cocatalyst compound may include at least one selected from a compound represented by Formula 4 below, a compound represented by Formula 5 below, and a compound represented by Formula 6 below.
- n is an integer of 2 or more
- R a is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen
- D is aluminum (Al) or boron (B)
- R b , R c and R d are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen substituted C 1 to 20 carbon atom It is a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms,
- L is a neutral or cationic Lewis base
- [LH] + and [L] + are a Bronsted acid
- Z is a group 13 element
- A is each independently a substituted or unsubstituted carbon number of 6 It is an aryl group of ⁇ 20 or a substituted or unsubstituted alkyl group of 1 ⁇ 20 carbon atoms.
- the compound represented by Formula 4 above is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane.
- the compound represented by Formula 5 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclopentylaluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron , at least one selected from the group consisting of triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron.
- the compound represented by the above formula (6) is triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra ( p -tolyl) Boron, trimethylammonium tetra( o , p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, trimethylammonium tetra( p -trifluoromethylphenyl)boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophen
- the catalyst for olefin polymerization may further include a carrier supporting the above hybrid catalyst composition, the above cocatalyst compound, or both.
- the carrier may include at least one selected from the group consisting of silica, alumina and magnesia.
- the total amount of the hybrid catalyst composition 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 may be 2 to 15 mmole based on 1 g of the carrier.
- a method for producing an olefin-based polymer comprising the step of polymerizing an olefin-based monomer in the presence of the olefin polymerization catalyst.
- the olefinic monomer is ethylene and the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1 It may be at least one selected from the group consisting of -decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene.
- the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene, and the olefinic polymer may be a linear low density polyethylene.
- the polymerization of the olefinic monomer may be carried out by slurry polymerization, and specifically, the polymerization of the olefinic monomer may be carried out in a slurry batch reactor.
- an olefin-based polymer which is prepared by the above method for preparing an olefin-based polymer and has a gel index of 1 or less when molded into a film having a thickness of 50 ⁇ m.
- the method for producing an olefin-based polymer according to an embodiment of the present invention can provide an olefin-based polymer in which non-uniformity of the olefin-based polymer, in particular, the generation of a gel is suppressed.
- the hybrid catalyst composition according to an embodiment of the present invention comprises a first transition metal compound represented by Formula 1 below, a second transition metal compound represented by Formula 2 below, and a third transition metal compound represented by Formula 3 below,
- the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 1:100 to 100:1, and the content of the third transition metal compound is 10 to 90 mol% based on the total number of moles of the hybrid catalyst composition.
- l, n, p and q are each independently an integer of 0 to 4
- m is each independently an integer of 0 to 2
- o is an integer of 0 to 5.
- l, m, p, and q may each be 1, and n and o may each be 0.
- M is each independently titanium (Ti), zirconium (Zr) or hafnium (Hf). Specifically, each M may be zirconium.
- each X is independently halogen, nitro, 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.
- each X may be a halogen. More specifically, X may be chlorine.
- each Q is each independently carbon (C), silicon (Si), germanium (Ge), or tin (Sn). Specifically, each Q may be carbon or silicon.
- R 1 to R 8 are each independently hydrogen, 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 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.
- R 1 to R 6 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.
- R 1 to R 8 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, or substituted or unsubstituted C 6-20 aryl.
- the first transition metal compound, the second transition metal compound, and the third transition metal compound are each represented by a compound represented by Formula 1-1 below, a compound represented by Formula 2-1, and a compound represented by Formula 3-1 It may be the indicated compound.
- Bu is a butyl group and Ph is a phenyl group.
- the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 1:100 to 100:1.
- the molar ratio of these two compounds may be 1:50-50:1. More preferably, the molar ratio of the two compounds may be 1:10 to 10:1.
- an appropriate supported catalyst activity may be exhibited, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.
- the olefin-based polymer prepared in the presence of a catalyst for olefin polymerization satisfying the above range exhibits excellent processability, and a film prepared therefrom may exhibit excellent mechanical and optical properties.
- the content of the third transition metal compound is 10 to 90 mol% based on the total number of moles of the hybrid catalyst composition.
- the content of the third transition metal compound may be 10 to 80 mol% or 10 to 60 mol%.
- the catalyst for olefin polymerization comprises a first transition metal compound represented by Formula 1 below, a second transition metal compound represented by Formula 2 below, and a third transition metal compound represented by Formula 3 below.
- a hybrid catalyst composition and a cocatalyst compound wherein the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 1:100 to 100:1, and the third transition metal based on the total number of moles of the hybrid catalyst composition
- the content of the compound is 10 to 90 mol%.
- the first transition metal compound, the second transition metal compound, and the third transition metal compound are each represented by a compound represented by Formula 1-1 below, a compound represented by Formula 2-1, and a compound represented by Formula 3-1 It may be the indicated compound.
- Bu is a butyl group and Ph is a phenyl group.
- the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 1:100 to 100:1.
- the molar ratio of these two compounds may be 1:50-50:1. More preferably, the molar ratio of the two compounds may be 1:10 to 10:1.
- an appropriate supported catalyst activity may be exhibited, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.
- the olefin-based polymer prepared in the presence of a catalyst for olefin polymerization satisfying the above range exhibits excellent processability, and a film prepared therefrom may exhibit excellent mechanical and optical properties.
- the content of the third transition metal compound is 10 to 90 mol% based on the total number of moles of the hybrid catalyst composition.
- the content of the third transition metal compound may be 10 to 80 mol% or 10 to 60 mol%.
- the cocatalyst compound may include at least one selected from a compound represented by Formula 4 below, a compound represented by Formula 5 below, and a compound represented by Formula 6 below.
- n is an integer of 2 or more
- R a may be a halogen atom, a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms substituted with a halogen.
- R a may be methyl, ethyl, n -butyl or isobutyl.
- D is aluminum (Al) or boron (B)
- R b , R c and R d are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen substituted C 1 to 20 carbon atom It is a hydrocarbon group or a C1-C20 alkoxy group.
- R b , R c and R d may each independently be methyl or isobutyl
- D is boron (B)
- R b , R c and R d are each may be pentafluorophenyl.
- L is a neutral or cationic Lewis base
- [LH] + and [L] + are a Bronsted acid
- Z is a group 13 element
- A is each independently a substituted or unsubstituted carbon number of 6 It is an aryl group of ⁇ 20 or a substituted or unsubstituted alkyl group of 1 ⁇ 20 carbon atoms.
- [LH] + may be a dimethylanilinium cation
- [Z(A) 4 ] - may be [B(C 6 F 5 ) 4 ] -
- [L] + may be [(C 6 H) 5 ) 3 C] + .
- examples of the compound represented by the above formula (4) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferred, but limited thereto it is not
- examples of the compound represented by Formula 5 above include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide , trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are preferred, but not limited thereto.
- examples of the compound represented by Formula 6 above include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammoniumtetraphenylboron, and trimethylammonium Umtetra( p -tolyl)boron, trimethylammonium tetra( o , p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, trimethylammonium tetra( p -trifluoromethylphenyl) Boron, tributylammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophen
- the catalyst for olefin polymerization may further include a carrier supporting the hybrid catalyst composition.
- the carrier may support both the transition metal compound and the promoter compound.
- the carrier may include a material containing a hydroxyl group on the surface, preferably dried to remove moisture on the surface, a material having a high reactivity hydroxyl group and siloxane group may be used.
- the carrier may include at least one selected from the group consisting of silica, alumina and magnesia.
- silica dried at high temperature, silica-alumina, silica-magnesia, and the like may be used as the carrier, and these are typically oxides such as Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) 2 .
- carbonate, sulfate, and nitrate components may also contain carbon, zeolites, magnesium chloride, and the like.
- the carrier is not particularly limited to these.
- the carrier may have an average particle size of 10-250 ⁇ m, preferably an average particle size of 10-150 ⁇ m, and more preferably 20-100 ⁇ m.
- the micropore volume of the carrier may be 0.1-10 cc/g, preferably 0.5-5 cc/g, and more preferably 1.0-3.0 cc/g.
- 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.
- the silica drying temperature when the carrier is silica, may be 200 ⁇ 900 °C.
- the drying temperature may be preferably 300 to 800°C, more preferably 400 to 700°C. If the drying temperature is less than 200 °C, there is too much moisture, the surface moisture and the cocatalyst compound react, and if it exceeds 900 °C, the structure of the carrier may be collapsed.
- the concentration of hydroxyl groups in the dried silica may be 0.1-5 mmole/g, preferably 0.7-4 mmole/g, and more preferably 1.0-2 mmole/g.
- concentration of the hydroxyl group is less than 0.1 mmole/g, the supported amount of the promoter compound is lowered, and when it exceeds 5 mmole/g, a problem in that the catalyst component is deactivated may occur.
- the total amount of the hybrid catalyst composition supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier.
- the total amount of the promoter compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier.
- One type or two or more types of carriers may be used.
- both the hybrid catalyst composition and the promoter compound may be supported on one type of support, or the hybrid catalyst composition and the promoter compound may be supported on two or more types of support, respectively.
- only one of the hybrid catalyst composition and the cocatalyst compound may be supported on the carrier.
- the method for producing an olefin-based polymer according to an embodiment of the present invention includes polymerizing an olefin-based monomer in the presence of a catalyst for olefin polymerization according to an embodiment of the present invention.
- the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.
- the olefinic monomer is a C 2-20 alpha-olefin, a C 1-20 diolefin, a C 3-20 cycloolefin and a C 3-20 cyclodiolefin . At least one selected from the group consisting of olefins (cyclodiolefin).
- the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 - may be dodecene, 1-tetradecene, 1-hexadecene, etc.
- the olefinic polymer may be a homopolymer including only one type of the olefinic monomer exemplified above, or a copolymer including two or more types.
- the olefin-based polymer may be a copolymer of ethylene and C 3-20 alpha-olefin, preferably a copolymer of ethylene and C 4-8 alpha-olefin, but limited thereto it is not
- the content of ethylene is 55 to 99.9 weight%, and it is more preferable that it is 90 to 99.9 weight%.
- the content of the alpha-olefin-based comonomer is preferably 0.1 to 45 wt%, more preferably 10 to 40 wt%.
- the olefin-based polymer according to an embodiment of the present invention may be polymerized by, for example, a polymerization reaction such as free radical, cationic, coordination, condensation, and addition. However, it is not limited thereto.
- the olefin-based polymer may be prepared by a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method.
- the polymerization of the olefinic monomer may be carried out by slurry polymerization, and specifically, the polymerization of the olefinic monomer may be carried out in a slurry batch reactor.
- the solvent that can be used include a C 5-12 aliphatic hydrocarbon solvent 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 is not limited thereto.
- a C 5-12 aliphatic hydrocarbon solvent 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
- mixtures thereof but is not limited thereto.
- an olefin-based polymer prepared by the above method for preparing an olefin-based polymer is provided.
- the olefin-based polymer may have a gel index of 1 or less when molded into a film having a thickness of 50 ⁇ m.
- compound 1-1 (dimethylsilylene)bis(2-methyl-4-phenylindenyl)zirconium dichloride) was prepared from sPCI, compound 2-1((cyclopentadienyl)(indenyl)zirconium(IV) dichloride) and compound 3 -1 (diphenylmethylidene(n-butyl cyclopentadienyl)(2,7-tert-butyl fluoren-9-yl)zirconium dichloride) was purchased from MCN.
- Silica (XPO-2402) was purchased from Grace, and a 10% toluene solution of aluminoxane was purchased from Lake Materials. All materials were used as-is without purification unless otherwise stated.
- reaction solution was added to 2 g of silica (XPO-2402), and further 1.5 liters of toluene was added, followed by stirring at 75° C. for 3 hours. Then, it was washed 3 times with 10 ml of toluene and dried in vacuum for 1 hour to obtain 2.2 g of a supported catalyst in powder form.
- a hybrid metallocene supported catalyst was prepared in the same manner as in Preparation Example 2, but the compounds used were increased. Specifically, 2.14 g of the transition metal compound of Formula 1-1, 1.56 g of the transition metal compound of Formula 2-1, and 2.47 g of the transition metal compound of Formula 3-1 were used, and 250 g of silica and a 10% toluene solution of aluminoxane were used. 1,103 g was used. The amount of catalyst prepared was 345 g.
- Example 2 Mixed metal was prepared in the same manner as in Example 1 except that 34 mg of the transition metal compound of Formula 1-1 and 12 mg of the transition metal compound of Formula 2-1 were used, and the transition metal compound of Formula 3-1 was not used. 2.1 g of a strong supported catalyst was obtained. In this case, the molar ratio of Compound 1-1: Compound 2-1: Compound 3-1 was 60:40:0.
- the hybrid metallocene supported catalyst was carried out in the same manner as in Example 1, except that 31 mg of the transition metal compound of Formula 1-1, 12 mg of the transition metal compound of Formula 2-1, and 3 mg of the transition metal compound of Formula 3-1 were used. 2.01 g was obtained. In this case, the molar ratio of Compound 1-1: Compound 2-1: Compound 3-1 was 55:40:5.
- An olefin-based polymer was prepared using each of the hybrid metallocene-supported catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 2 using a slurry polymerization reactor. 50 mg of the supported hybrid metallocene catalyst and 1 liter of hexane were added to the reactor, and 0.6 ml of 1M triisobutyl aluminum (TiBAL) was added as a scavenger. The amount of 1-hexene shown in Table 1 below was introduced into the reactor.
- the melt index was measured at 190°C under a load of 21.6 kg and a load of 2.16 kg, and the ratio (MI 21.6 /MI 2.16 ) was calculated.
- DSC differential scanning calorimeter
- the gel properties were measured through the reference film.
- a smaller gel index (GI) means less gel.
- the gel index was measured as follows.
- Each of the polymerized resins in Examples and Comparative Examples was molded using an in-house micro blown film extruder (Labtech). The film was molded by controlling the extrusion speed and the molding speed so that the film width was about 5 cm and the thickness was 50 ⁇ m. For a film of 5 cm ⁇ 5 cm, the total number of gels was visually inspected and evaluated according to the following criteria.
- the olefin-based polymer prepared according to the embodiment of the present invention had a good degree of gel generation, but Comparative Example 1 and the third transition metal compound were prepared without using the third transition metal compound.
- Comparative Example 1 in which the amount used was small, the generation of gel increased and thus it was not suitable for use as a film or a pipe.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
수소 (cc/min) |
중합체 (g) |
촉매 활성 (gPE/gCat-hr) |
MI2.16
(g/10분) |
MI21.6
(g/10분) |
MFR | |
실시예 1-1 | 10 | 135 | 2,700 | 0.014 | 4.220 | 301.4 |
실시예 1-2 | 10 | 109 | 2,180 | 0.005 | 1.430 | 297.9 |
실시예 2 | 10 | 132 | 2,640 | 0.006 | 1.305 | 227.0 |
실시예 3 | 5 | 76 | 1,520 | 0.3 | 8.212 | 27.4 |
실시예 4 | 5 | 198 | 3,960 | 0.006 | 1.72 | 286. 7 |
비교예 1-1 | 5 | 162 | 3,240 | 0.270 | 17.940 | 66.4 |
비교예 1-2 | 5 | 244 | 4,880 | 0.012 | 0.366 | 30.5 |
비교예 2 | 5 | 172 | 3,440 | 0.28 | 21.54 | 76.9 |
Mn (g/mole) |
Mw (g/mole) |
MWD | Tm (℃) |
Tc (℃) |
결정화도 (%) |
밀도 (g/cc) |
GI | |
실시예 1-1 | 25,300 | 210,335 | 8.31 | 133.2 | 119.7 | 70.6 | 0.9545 | 1 |
실시예 1-2 | 32,821 | 235,098 | 7.16 | 132.9 | 119.1 | 69.1 | 0.9525 | 1 |
실시예 2 | 27,653 | 242,186 | 8.76 | 133.0 | 119.3 | 67.4 | 0.9500 | 1 |
실시예 3 | 42,455 | 156,272 | 3.68 | 133.4 | 117.9 | 72.5 | 0.947 | 1 |
실시예 4 | 36,285 | 252,162 | 6.95 | 134.0 | 118.9 | 68.9 | 0.9510 | 1 |
비교예 1-1 | 19,900 | 181,989 | 9.15 | 133.9 | 118.9 | 72.7 | 0.9506 | 4 |
비교예 1-2 | 29,490 | 176,943 | 6.00 | 134.5 | 118.7 | 71.4 | 0.9515 | 5 |
비교예 2 | 23,330 | 218,844 | 9.38 | 133.6 | 117.5 | 73.1 | 0.9540 | 4 |
Claims (16)
- 아래 화학식 1로 표시되는 제1 전이금속 화합물, 아래 화학식 2로 표시되는 제2 전이금속 화합물 및 아래 화학식 3으로 표시되는 제3 전이금속 화합물을 포함하되, 제1 전이금속 화합물 대 제2 전이금속 화합물의 몰 비가 1:100~100:1의 범위이고, 혼성 촉매 조성물의 총 몰 수를 기준으로 제3 전이금속 화합물의 함량이 10~90 몰%인 혼성 촉매 조성물:[화학식 1][화학식 2][화학식 3]위 화학식 1 내지 3에서, l, n, p와 q는 각각 독립적으로 0 내지 4의 정수이고, m은 각각 독립적으로 0 내지 2의 정수이고, o는 0 내지 5의 정수이고;M은 각각 독립적으로 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이고;X는 각각 독립적으로 할로겐, 니트로, 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;Q는 각각 독립적으로 탄소(C), 실리콘(Si), 게르마늄(Ge) 또는 주석(Sn)이고;R1 내지 R8은 각각 독립적으로 수소, 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 R6은 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있다.
- 제1항의 혼성 촉매 조성물 및 조촉매 화합물을 포함하되, 제1 전이금속 화합물 대 제2 전이금속 화합물의 몰 비가 1:100~100:1의 범위이고, 혼성 촉매 조성물의 총 몰 수를 기준으로 제3 전이금속 화합물의 함량이 10~90 몰%인 올레핀 중합용 촉매.
- 제3항에 있어서, 조촉매 화합물이 아래 화학식 4로 표시되는 화합물, 아래 화학식 5로 표시되는 화합물 및 아래 화학식 6으로 표시되는 화합물로부터 선택되는 적어도 하나를 포함하는 올레핀 중합용 촉매:[화학식 4][화학식 5][화학식 6][L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]-위 화학식 4에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, 탄소수 1~20의 탄화수소기 또는 할로겐으로 치환된 탄소수 1~20의 탄화수소기이고,위 화학식 5에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, 탄소수 1~20의 탄화수소기, 할로겐으로 치환된 탄소수 1~20의 탄화수소기 또는 탄소수 1~20의 알콕시기이며,위 화학식 6에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 탄소수 6~20의 아릴기이거나 치환 또는 비치환된 탄소수 1~20의 알킬기이다.
- 제4항에 있어서, 화학식 4로 표시되는 화합물이 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산 및 부틸알루미녹산으로 구성되는 군으로부터 선택되는 적어도 하나인 올레핀계 중합체의 제조방법.
- 제4항에 있어서, 화학식 5로 표시되는 화합물이 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 하나인 올레핀계 중합체의 제조방법.
- 제4항에 있어서, 화학식 6으로 표시되는 화합물이 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 하나인 올레핀계 중합체의 제조방법.
- 제3항에 있어서, 혼성 촉매 조성물, 조촉매 화합물 또는 이 둘 모두를 담지하는 담체를 더 포함하는 올레핀 중합용 촉매.
- 제8항에 있어서, 담체가 실리카, 알루미나 및 마그네시아로 구성되는 군으로부터 선택되는 적어도 하나를 포함하는 올레핀 중합용 촉매.
- 제8항에 있어서, 담체에 담지되는 혼성 촉매 조성물의 총량이 담체 1 g을 기준으로 0.001~1 mmole이고, 담체에 담지되는 조촉매 화합물의 총량이 담체 1 g을 기준으로 2~15 mmole인 올레핀 중합용 촉매.
- 제3항의 올레핀 중합용 촉매의 존재하에 올레핀계 단량체를 중합하는 단계를 포함하는 올레핀계 중합체의 제조방법.
- 제11항에 있어서, 올레핀계 중합체가 올레핀계 단량체와 올레핀계 공단량체의 공중합체인 올레핀계 중합체의 제조방법.
- 제12항에 있어서, 올레핀계 단량체가 에틸렌이고, 올레핀계 공단량체가 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센 및 1-헥사데센으로 구성되는 군으로부터 선택되는 하나 이상인 올레핀계 중합체의 제조방법.
- 제13항에 있어서, 올레핀계 단량체가 에틸렌이고 올레핀계 공단량체가 1-헥센이며, 올레핀계 중합체가 선형 저밀도 폴리에틸렌인 올레핀계 중합체의 제조방법.
- 제11항에 있어서, 올레핀계 단량체의 중합이 슬러리 중합으로 수행되는, 올레핀계 중합체의 제조방법.
- 제11항 내지 제15항 중 어느 한 항의 올레핀계 중합체의 제조방법에 의해 제조되며, 50 ㎛ 두께의 필름으로 성형 시 1 이하의 젤 인덱스를 갖는 올레핀계 중합체.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202180091382.1A CN116710495A (zh) | 2020-12-23 | 2021-12-16 | 混合催化剂组合物、包含其的催化剂和使用其制备基于烯烃的聚合物的方法 |
EP21911384.2A EP4269453A1 (en) | 2020-12-23 | 2021-12-16 | Hybrid catalyst composition, catalyst comprising same, and method for preparing olefin-based polymer using same |
US18/269,393 US20240101728A1 (en) | 2020-12-23 | 2021-12-16 | Hybrid catalyst composition, catalyst comprising same, and method for preparing olefin-based polymer using same |
JP2023538880A JP2024501946A (ja) | 2020-12-23 | 2021-12-16 | ハイブリッド触媒組成物、それを含む触媒およびそれを用いたオレフィン系重合体の製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2020-0181750 | 2020-12-23 | ||
KR1020200181750A KR102613125B1 (ko) | 2020-12-23 | 2020-12-23 | 혼성 촉매 조성물, 이를 포함하는 촉매 및 이를 이용한 올레핀계 중합체의 제조방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022139317A1 true WO2022139317A1 (ko) | 2022-06-30 |
Family
ID=82159636
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2021/019133 WO2022139317A1 (ko) | 2020-12-23 | 2021-12-16 | 혼성 촉매 조성물, 이를 포함하는 촉매 및 이를 이용한 올레핀계 중합체의 제조방법 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20240101728A1 (ko) |
EP (1) | EP4269453A1 (ko) |
JP (1) | JP2024501946A (ko) |
KR (1) | KR102613125B1 (ko) |
CN (1) | CN116710495A (ko) |
WO (1) | WO2022139317A1 (ko) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4935474A (en) | 1983-06-06 | 1990-06-19 | Exxon Research & Engineering Company | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
US6828394B2 (en) | 2001-07-19 | 2004-12-07 | Univation Technologies, Llc | Mixed metallocene catalyst systems containing a poor comonomer incorporator and a good comonomer incorporator |
US6841631B2 (en) | 1999-10-22 | 2005-01-11 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US20110201770A1 (en) * | 2006-02-22 | 2011-08-18 | Chevron Phillips Chemical Company Lp | Dual metallocene catalysts for polymerization of bimodal polymers |
KR101437509B1 (ko) | 2012-12-03 | 2014-09-03 | 대림산업 주식회사 | 성형성 및 기계적 물성이 우수한 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 중합 방법 |
US20150203617A1 (en) * | 2013-07-15 | 2015-07-23 | Chevron Phillips Chemical Company Lp | Methods for Producing Fluorided-Chlorided Silica-Coated Alumina Activator-Supports and Catalyst Systems Containing the Same |
KR101711788B1 (ko) * | 2016-03-09 | 2017-03-14 | 한화케미칼 주식회사 | 혼성 촉매 조성물, 이의 제조방법, 및 이를 이용하여 제조된 폴리올레핀 |
KR20190096290A (ko) * | 2018-02-08 | 2019-08-19 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매의 제조방법 |
KR20200075963A (ko) * | 2018-12-18 | 2020-06-29 | 한화솔루션 주식회사 | 올레핀 중합용 촉매 및 이를 이용하여 제조된 올레핀계 중합체 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102372974B1 (ko) * | 2019-04-05 | 2022-03-10 | 한화솔루션 주식회사 | 혼성 촉매 조성물, 이를 포함하는 촉매 및 이들의 제조방법 |
-
2020
- 2020-12-23 KR KR1020200181750A patent/KR102613125B1/ko active IP Right Grant
-
2021
- 2021-12-16 CN CN202180091382.1A patent/CN116710495A/zh active Pending
- 2021-12-16 WO PCT/KR2021/019133 patent/WO2022139317A1/ko active Application Filing
- 2021-12-16 US US18/269,393 patent/US20240101728A1/en active Pending
- 2021-12-16 JP JP2023538880A patent/JP2024501946A/ja active Pending
- 2021-12-16 EP EP21911384.2A patent/EP4269453A1/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4935474A (en) | 1983-06-06 | 1990-06-19 | Exxon Research & Engineering Company | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
US6841631B2 (en) | 1999-10-22 | 2005-01-11 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US6894128B2 (en) | 1999-10-22 | 2005-05-17 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US6828394B2 (en) | 2001-07-19 | 2004-12-07 | Univation Technologies, Llc | Mixed metallocene catalyst systems containing a poor comonomer incorporator and a good comonomer incorporator |
US20110201770A1 (en) * | 2006-02-22 | 2011-08-18 | Chevron Phillips Chemical Company Lp | Dual metallocene catalysts for polymerization of bimodal polymers |
KR101437509B1 (ko) | 2012-12-03 | 2014-09-03 | 대림산업 주식회사 | 성형성 및 기계적 물성이 우수한 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 중합 방법 |
US20150203617A1 (en) * | 2013-07-15 | 2015-07-23 | Chevron Phillips Chemical Company Lp | Methods for Producing Fluorided-Chlorided Silica-Coated Alumina Activator-Supports and Catalyst Systems Containing the Same |
KR101711788B1 (ko) * | 2016-03-09 | 2017-03-14 | 한화케미칼 주식회사 | 혼성 촉매 조성물, 이의 제조방법, 및 이를 이용하여 제조된 폴리올레핀 |
KR20190096290A (ko) * | 2018-02-08 | 2019-08-19 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매의 제조방법 |
KR20200075963A (ko) * | 2018-12-18 | 2020-06-29 | 한화솔루션 주식회사 | 올레핀 중합용 촉매 및 이를 이용하여 제조된 올레핀계 중합체 |
Also Published As
Publication number | Publication date |
---|---|
KR20220090839A (ko) | 2022-06-30 |
EP4269453A1 (en) | 2023-11-01 |
US20240101728A1 (en) | 2024-03-28 |
KR102613125B1 (ko) | 2023-12-14 |
CN116710495A (zh) | 2023-09-05 |
JP2024501946A (ja) | 2024-01-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017155149A1 (ko) | 혼성 촉매 조성물, 이의 제조방법, 및 이를 이용하여 제조된 폴리올레핀 | |
WO2014088287A1 (ko) | 성형성 및 기계적 물성이 우수한 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 중합 방법 | |
WO2010128826A2 (ko) | 올레핀계 중합체 및 이를 포함하는 섬유 | |
WO2020080745A1 (ko) | 올레핀 중합용 촉매 | |
WO2022131693A1 (ko) | 올레핀계 중합체 및 그 제조방법 | |
WO2020130452A1 (ko) | 올레핀 중합용 촉매 및 이를 이용하여 제조된 올레핀계 중합체 | |
WO2020080744A1 (ko) | 올레핀계 중합체 | |
WO2021075788A1 (ko) | 올레핀 중합용 혼성 촉매의 제조방법, 올레핀 중합용 혼성 촉매 및 올레핀계 중합체 | |
WO2022108252A1 (ko) | 올레핀계 중합체, 그로부터 제조된 필름 및 그 제조방법 | |
WO2020130517A1 (ko) | 올레핀 중합용 촉매의 제조방법, 올레핀 중합용 촉매 및 올레핀계 중합체 | |
WO2022124692A1 (ko) | 올레핀계 중합체 및 그 제조방법 | |
WO2022124695A1 (ko) | 올레핀계 중합체 및 그 제조방법 | |
WO2022108233A1 (ko) | 올레핀계 중합체, 그로부터 제조된 필름 및 그 제조방법 | |
WO2022139317A1 (ko) | 혼성 촉매 조성물, 이를 포함하는 촉매 및 이를 이용한 올레핀계 중합체의 제조방법 | |
WO2018074897A1 (ko) | 용융강도가 높은 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 멀티모달 폴리올레핀 공중합체 | |
WO2023038351A1 (ko) | 올레핀계 중합체의 제조방법 및 이를 이용하여 제조된 올레핀계 중합체 | |
WO2017115927A1 (ko) | 혼성 메탈로센 담지 촉매, 이를 이용한 올레핀 중합체의 제조방법 및 용융강도가 향상된 올레핀 중합체 | |
WO2022124694A1 (ko) | 올레핀계 중합체, 그로부터 제조된 필름 및 그 제조방법 | |
WO2022108254A1 (ko) | 올레핀계 중합체 및 그 제조방법 | |
WO2022131690A1 (ko) | 올레핀계 중합체 및 그 제조방법 | |
WO2021085929A1 (ko) | 올레핀계 중합체 | |
WO2020111777A1 (ko) | 우수한 용융 특성을 지닌 폴리프로필렌 수지 및 그 제조 방법 | |
WO2020116842A1 (ko) | 올레핀 중합용 촉매의 제조방법 | |
WO2024128685A1 (ko) | 올레핀계 중합체의 제조방법 및 그에 의해 제조되고 가공성이 우수한 올레핀계 중합체 | |
WO2021112489A1 (ko) | 올레핀계 중합체의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21911384 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023538880 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18269393 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202180091382.1 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021911384 Country of ref document: EP Effective date: 20230724 |