KR102034807B1 - Novel transition metal compound - Google Patents
Novel transition metal compound Download PDFInfo
- Publication number
- KR102034807B1 KR102034807B1 KR1020150175390A KR20150175390A KR102034807B1 KR 102034807 B1 KR102034807 B1 KR 102034807B1 KR 1020150175390 A KR1020150175390 A KR 1020150175390A KR 20150175390 A KR20150175390 A KR 20150175390A KR 102034807 B1 KR102034807 B1 KR 102034807B1
- Authority
- KR
- South Korea
- Prior art keywords
- carbon atoms
- formula
- compound
- transition metal
- alkyl
- Prior art date
Links
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 109
- 150000001875 compounds Chemical class 0.000 claims description 58
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052752 metalloid Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 79
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 34
- -1 trimethylsilylmethyl group Chemical group 0.000 description 32
- 239000000126 substance Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003446 ligand Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 150000002900 organolithium compounds Chemical class 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- 239000012190 activator Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910007926 ZrCl Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Chemical group 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 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
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010936 titanium Substances 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
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- 0 *C(C*c1c(*)c(*)c2*)Nc1c2P(*)* Chemical compound *C(C*c1c(*)c(*)c2*)Nc1c2P(*)* 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- 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
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- DQJAXJFUKANNOU-UHFFFAOYSA-N (2-methyl-2,3-dihydro-1H-indol-7-yl)-di(propan-2-yl)phosphane Chemical compound C(C)(C)P(C=1C=CC=C2CC(NC=12)C)C(C)C DQJAXJFUKANNOU-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
- CPJNRDNEPBTGFU-UHFFFAOYSA-N 2,3-dihydro-1H-indol-7-yl-di(propan-2-yl)phosphane Chemical compound C(C)(C)P(C=1C=CC=C2CCNC=12)C(C)C CPJNRDNEPBTGFU-UHFFFAOYSA-N 0.000 description 1
- QRWRJDVVXAXGBT-UHFFFAOYSA-N 2-Methylindoline Chemical compound C1=CC=C2NC(C)CC2=C1 QRWRJDVVXAXGBT-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZWALXTIERAJHRE-UHFFFAOYSA-N C(C)(C)P(C=1C=CC=C2CC(NC12)C)C(C)C.C(C)(C)P(C=1C=CC=C2CC(NC12)C)C(C)C Chemical compound C(C)(C)P(C=1C=CC=C2CC(NC12)C)C(C)C.C(C)(C)P(C=1C=CC=C2CC(NC12)C)C(C)C ZWALXTIERAJHRE-UHFFFAOYSA-N 0.000 description 1
- WZEZREHCYSILLE-UHFFFAOYSA-N C(C)(C)P(C=1C=CC=C2CCCNC12)C(C)C.C(C)(C)P(C=1C=CC=C2CCCNC12)C(C)C Chemical compound C(C)(C)P(C=1C=CC=C2CCCNC12)C(C)C.C(C)(C)P(C=1C=CC=C2CCCNC12)C(C)C WZEZREHCYSILLE-UHFFFAOYSA-N 0.000 description 1
- AEHHPFFJCRRHSL-UHFFFAOYSA-N C(C)(C)P(C=1C=CC=C2CCNC12)C(C)C.C(C)(C)P(C=1C=CC=C2CCNC12)C(C)C Chemical compound C(C)(C)P(C=1C=CC=C2CCNC12)C(C)C.C(C)(C)P(C=1C=CC=C2CCNC12)C(C)C AEHHPFFJCRRHSL-UHFFFAOYSA-N 0.000 description 1
- YDZLXJNSECFXRK-UHFFFAOYSA-N C1(CCCCC1)P(C=1C=CC=C2CCCNC12)C1CCCCC1.C1(CCCCC1)P(C=1C=CC=C2CCCNC12)C1CCCCC1 Chemical compound C1(CCCCC1)P(C=1C=CC=C2CCCNC12)C1CCCCC1.C1(CCCCC1)P(C=1C=CC=C2CCCNC12)C1CCCCC1 YDZLXJNSECFXRK-UHFFFAOYSA-N 0.000 description 1
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 description 1
- JEVCOCKVSCRHMR-UHFFFAOYSA-N CCN(CC)C1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCN(CC)C1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F JEVCOCKVSCRHMR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- COEKAXZKYDOOTK-UHFFFAOYSA-N FC(CCCC1=CC=C(C=C1)[B])(F)F Chemical compound FC(CCCC1=CC=C(C=C1)[B])(F)F COEKAXZKYDOOTK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 1
- XIOUGOKEVVETOO-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN XIOUGOKEVVETOO-UHFFFAOYSA-N 0.000 description 1
- XIBZTAIPROXEDH-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 XIBZTAIPROXEDH-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- AJHCTKUNQALHOA-UHFFFAOYSA-N di(propan-2-yl)-(1,2,3,4-tetrahydroquinolin-8-yl)phosphane Chemical compound C(C)(C)P(C=1C=CC=C2CCCNC=12)C(C)C AJHCTKUNQALHOA-UHFFFAOYSA-N 0.000 description 1
- IUFAPELNAPVEOD-UHFFFAOYSA-N dicyclohexyl(1,2,3,4-tetrahydroquinolin-8-yl)phosphane Chemical compound C1(CCCCC1)P(C=1C=CC=C2CCCNC=12)C1CCCCC1 IUFAPELNAPVEOD-UHFFFAOYSA-N 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- LPAGFVYQRIESJQ-UHFFFAOYSA-N indoline Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000369 oxido group Chemical group [*]=O 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- BPTLKYDJMWXDMY-UHFFFAOYSA-N pentane;toluene Chemical compound CCCCC.CC1=CC=CC=C1 BPTLKYDJMWXDMY-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a novel transition metal compound represented by the formula (1), the transition metal compound according to the present invention can be usefully used as a catalyst for the polymerization reaction in the production of olefin polymers having high crystallinity, high density and high molecular weight have.
Description
The present invention relates to novel transition metal compounds.
Metallocene catalysts for olefin polymerization have been developed for a long time. Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (eg, benzyl or trimethylsilylmethyl group (—CH 2 SiMe 3 )), an example showing an effect such as increased catalytic activity has been reported.
Dow disclosed [Me 2 Si (Me 4 C 5 ) NtBu] TiCl 2 (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802 and the like in the early 1990s. The advantages over the known metallocene catalysts can be summarized in two main ways:
(1) to produce high molecular weight polymers with high activity even at high polymerization temperatures;
(2) The copolymerization of alpha-olefins with high steric hindrances such as 1-hexene and 1-octene is also excellent.
In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.
One approach has been to synthesize metal compounds in which various bridges and nitrogen substituents are introduced instead of silicon bridges and to polymerize them. Representative metal compounds known until recently are phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges, but polymerized against CGC when applied to ethylene polymerization or copolymerization of ethylene and alphaolefin. It did not show excellent results in terms of activity or copolymerization performance.
In another approach, many compounds composed of an oxido ligand instead of the amido ligand of CGC have been synthesized, and some polymerization has been attempted using the compound.
In addition, various asymmetric uncrosslinked metallocenes have been developed. For example, metallocenes composed of (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene, (substituted indenyl) (cyclopentadienyl), and the like are known. have.
However, in terms of commercial applications, the catalyst compositions of the non-crosslinkable metallocenes do not sufficiently exhibit the polymerization activity of olefins and have difficulty in polymerizing high molecular weight polyolefins.
The problem to be solved of the present invention is to provide a novel transition metal compound.
In order to solve the above problems, the present invention
It provides a transition metal compound represented by the formula (1):
[Formula 1]
In the above formula, Q 1 and Q 2 are each independently hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, 7 to 7 carbon atoms Arylalkyl of 20, alkyl amido of 1 to 20 carbon atoms, aryl amido of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms; M is Ti, Zr or hf;
R 1 to R 6 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; At least two of R 4 to R 6 may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
The novel transition metal compound according to the present invention can be usefully used as a catalyst for the polymerization reaction in the preparation of olefin polymers having high crystallinity, high density and high molecular weight.
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
The transition metal compound according to the present invention is represented by the following formula (1).
[Formula 1]
In the above formula, Q 1 and Q 2 are each independently hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, 7 to 7 carbon atoms Arylalkyl of 20, alkyl amido of 1 to 20 carbon atoms, aryl amido of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms; M is Ti, Zr or hf;
R 1 to R 6 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; At least two of R 4 to R 6 may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2.
In addition, in Formula 1, Q 1 and Q 2 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. have.
In addition, in Formula 1, R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. There is; At least two of R 4 to R 6 may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
In the transition metal compound according to the present invention, the ligand compound may be represented by the following formula (2).
[Formula 2]
In the above formula,
R 1 to R 6 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and arylalkyl having 7 to 20 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; At least two of R 4 to R 6 may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;
n is 1 or 2.
In addition, in Formula 2, R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent to each other of R 4 to R 6 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
In one embodiment of the present invention, the ligand compound of Formula 2 may be any one of the following compounds:
One)
2)
3)
or
4)
.
On the other hand, the compound of Formula 1 of the present invention may be specifically any one of the following compounds.
A)
B)
C)
D)
or
E)
.
Each substituent defined in the present specification will be described in detail as follows.
As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine, unless stated otherwise.
As used herein, the term 'alkyl' refers to a straight or branched chain hydrocarbon residue unless otherwise indicated.
As used herein, the term 'alkenyl' refers to a straight or branched alkenyl group unless otherwise indicated.
The branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.
According to one embodiment of the present invention, the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris ( Trimethylsilyl) silyl and the like, but are not limited to these examples.
According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
The alkylaryl group means an aryl group substituted by the alkyl group.
The arylalkyl group means an alkyl group substituted by the aryl group.
The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and containing one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indolin, tetrahydroquinoline, and the like, but the present invention is not limited thereto.
The alkyl amino group means an amino group substituted by the alkyl group, and there are a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.
According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.
The transition metal compound of the present invention may be prepared by the following preparation method, specifically, the transition metal compound of the present invention may be prepared by (1) reacting a compound of Formula 3 with an organolithium compound to prepare a compound of Formula 4 Making; And (2) reacting a compound of Formula 4 with a compound of Formula 5 to produce a compound of Formula 1.
[Formula 3]
[Formula 4]
[Formula 5]
(1) preparing a compound of formula 4 by reacting a compound of formula 3 with an organolithium compound
In step (1), a compound of formula 4 is prepared by reacting a compound of formula 3 with an organolithium compound.
In the step (1), the compound of Formula 3 and the organolithium compound may be reacted with a molar ratio of 1: 0.8 to 1: 1.8, and specifically, may be reacted at a molar ratio of 1: 1 to 1: 1.1.
The reaction of step (1) may be performed under an organic solvent such as ether, and may be performed by adding the organolithium compound to the compound of Formula 3 under an organic solvent.
The organolithium compound may be at least one selected from the group consisting of n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexylithium, allyllithium, vinyllithium, phenyllithium and benzyllithium. .
In the reaction of step (1), after adding the organolithium compound to the compound of Formula 3 at a temperature range of −80 ° C. to 0 ° C., the temperature is raised to a temperature range of 0 ° C. to 140 ° C., and then 1 to 48 hours. It may be carried out by the reaction method, and in particular, after adding the organolithium compound to the compound of Formula 3 in the temperature range of -60 ℃ to 0 ℃, after heating to a temperature range of 10 ℃ to 60 ℃, 1 To reaction for 48 hours.
(2) reacting a compound of Formula 4 with a compound of Formula 5 to produce a compound of Formula 1
In step (2), the compound of Formula 4 is prepared by reacting the compound of Formula 4 with the compound of Formula 5.
In the step (2), the compound of Formula 4 and the compound of Formula 5 may be reacted with a molar ratio of 1: 0.4 to 1: 0.8, specifically, may be reacted at a molar ratio of 1: 0.45 to 1: 0.5. .
The reaction of step (2) may be carried out by adding the compound of formula 5 to the compound of formula 4 at a temperature range of -20 ° C. to 60 ° C. and then reacting for 1 to 48 hours. After the compound of Formula 5 is added to the compound of Formula 4 at a temperature in the range of 0 ° C. to 40 ° C., the reaction may be performed for 3 to 24 hours.
The compound of Chemical Formula 1 prepared through the steps (1) and (2) may additionally undergo a recrystallization step (3), thus, the method for preparing a transition metal compound according to an example of the present invention may be performed after the step (2). (3) The method may further comprise recrystallizing the compound of Chemical Formula 2.
The recrystallization may be performed using an organic solvent such as ether such as a reaction solvent, and purified through recrystallization to obtain a pure compound of Chemical Formula 1.
The transition metal compound represented by Chemical Formula 1 according to the present invention, when activated by reacting with an additional promoter and then applied to olefin polymerization, produces a polyolefin having high crystallinity, high density, and high molecular weight even at a high polymerization temperature. It is possible.
In particular, by using the catalyst composition containing the transition metal compound, it is possible to prepare a polymer having a narrow MWD compared to CGC, excellent copolymerizability, and high molecular weight even in a low density region.
More specifically, the transition metal compound according to the present invention alone or in addition to the transition metal compound in the form of a composition further comprising one or more of the cocatalyst compounds represented by the following formulas (6), (7) and (8), the polymerization reaction It can be used as a catalyst.
[Formula 6]
-[Al (R 7 ) -O] m-
In Chemical Formula 6,
R 7 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
m is an integer of 2 or more;
[Formula 7]
J (R 7 ) 3
In Chemical Formula 7,
R 7 is as defined in Formula 6 above;
J is aluminum or boron;
[Formula 8]
[EH] + [ZA 4] - or [E] + [ZA 4] -
In Chemical Formula 8,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a Group 13 element;
A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .
Examples of the compound represented by Chemical Formula 6 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.
Examples of the compound represented by Chemical Formula 7 include 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, 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 more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
Examples of the compound represented by the formula (8) include 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-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, ethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetra Phenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tri Propyl Ammonium Tetraphenyl Aluminum, Trimethyl Ammonium Tetra (p-tolyl) Aluminum, Tripropyl Ammonium Tetra (p-tolyl) Aluminum, Triethyl Ammonium Tetra (o, p-dimethylphenyl) Aluminum, Tributyl Ammonium Tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p-tolyl) boron , Triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoro Butyl phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.
Preferably, alumoxane can be used, more preferably methylalumoxane (MAO) which is alkylalumoxane.
The catalyst composition may comprise the steps of: 1) contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 6 or Formula 7 to obtain a mixture; And 2) it may be prepared by a method comprising the step of adding a compound represented by the formula (8) to the mixture.
In addition, the catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 6 as a second method.
In the case of the first method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by the formula (1) / compound represented by the formula (6) or formula (7) is preferably 1 / 5,000 to 1/2, more Preferably it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the transition metal compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 6 or Chemical Formula 7 is more than 1/2, the amount of alkylating agent is so small that there is a problem that alkylation of the metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that the activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of the compound of Formula 8. . In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 8 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5. To 1; When the molar ratio of the transition metal compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 8 is greater than 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound. If the molar ratio is less than 1/25, the activation of the metal compound is completely made, but the excess of the activator, the cost of the catalyst composition is not economical or the purity of the resulting polymer is poor.
In the second method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Chemical Formula 1 / Compound 6 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, most preferably 1 / 3,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.
In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.
Specifically, the polymerization reaction for polymerizing the olefinic monomer in the presence of the catalyst composition comprising the transition metal compound is a solution polymerization process, using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or a solution reactor, It may be carried out by a slurry process or a gas phase process. It can also proceed by homopolymerization with one olefin monomer or copolymerization with two or more monomers.
The polymerization of the polyolefin may be carried out by reacting at a temperature of about 25 to about 500 ℃ and about 1 to about 100 kgf / cm 2 .
Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 to about 500 ℃, preferably about 25 to 200 ℃, more preferably about 50 to 100 ℃. The reaction pressure can also be carried out at about 1 to about 100 kgf / cm 2 , preferably at about 1 to about 50 kgf / cm 2 , more preferably at about 5 to about 40 kgf / cm 2 .
In addition, examples of the polymerizable olefin monomer using the transition metal compound and the promoter according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin having two or more double bonds. The monomer or the triene olefin monomer can also be polymerized.
In the polyolefin prepared according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- itocene and the like, may be a copolymer copolymerized by mixing two or more thereof.
The polyolefin may be a propylene polymer, but is not limited thereto.
The polymer may be either a homo polymer or a copolymer. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer consist of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected from the group.
Hereinafter, preferred examples will be described to aid in understanding the present invention. The following examples are merely to illustrate the invention, but are not intended to limit the scope of the invention.
Synthesis of Ligands and Transition Metal Compounds
Organic reagents and solvents were purchased from Aldrich and Merck and purified using standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. To verify the structure of the compounds, spectra and plots were obtained using 500 MHz nuclear magnetic resonance (NMR), respectively.
< Example >
Production Example One
Preparation of 8- (diisopropylphosphanyl) -1,2,3,4-tetrahydroquinoline [8- (diisopropyl phosphanyl) -1,2,3,4-tetrahydroquinoline]
THQ (5.36 ml, 40.2 mmol) and hexane (0.536 M, 75.15 ml) were added to a 250 ml Schlenk flask. N-BuLi (1.1 eq, 17.7 ml) was added at -20 ° C and allowed to stand overnight at room temperature. Filtration using glass frit (G4) and vacuum drying yielded phosphine-amine lithium. The phosphine-amine lithium (3.0 g, 21.6 mmol) was added to diethyl ether (0.423 M, 51.0 ml), and CO 2 bubbling was added at −78 ° C. for 1 hour. After slowly warming and reacting at room temperature overnight, THF (1.1 eq, 1.92 ml) and t-BuLi (1.1 eq, 14.0 ml) were added and maintained at -20 ° C for 2 hours. At the same temperature, i Pr 2 PCl (0.85 eq, 2.80 g) and diethyl ether (0.359 M, 51.0 ml) were added and maintained at the same temperature for 1 hour. After slowly reacting at room temperature overnight, 50 ml of distilled water was added at 0 ° C., followed by stirring at room temperature for 30 minutes. Work-up with diethyl ether, drying with MgSO 4 and hexane, diethyl ether 50: 1 column gave yellow oil in 3.3 g, 62% yield.
1 H-NMR (C 6 D 6 ): 7.07 (d, 1H), 6.92 (d, 1H), 6.70 (t, 1H), 5.60 (s, 1H), 2.89 (t, 2H), 2.52 (t, 2H), 1.99 (q, 2H), 1.55 (q, 2H), 1.15 (m, 6H), 1.00 (m, 6H)
Production Example 2
Synthesis of 7- (diisopropylphosphanyl) indoline [7- (diisopropylphosphanyl) indoline]
Intoline (3.26 g, 27.9 mmol) and hexane (0.536 M, 52.1 ml) were added to a 250 ml Schlenk flask. N-BuLi (1.1 eq, 12.3 ml) was added at -20 ° C and allowed to stand overnight at room temperature. Filtration using glass frit (G4) and vacuum drying yielded phosphine-amine lithium. The phosphine-amine lithium (3.49 g, 27.9 mmol) was added to diethyl ether (0.423 M, 66.0 ml) and CO 2 bubbling was added at -78 ° C for 1 hour. After slowly reacting at room temperature overnight, THF (1.1 eq, 2.49 ml) and t-BuLi (1.1 eq, 18.0 ml) were added and maintained at -20 ° C for 2 hours. At the same temperature, i Pr 2 PCl (0.85 eq, 3.62 g) and diethyl ether (0.359 M, 66.0 ml) were added and maintained at the same temperature for 1 hour. After slowly reacting at room temperature overnight, 50 ml of distilled water was added at 0 ° C., followed by stirring at room temperature for 30 minutes. Work-up with diethyl ether, dried over MgSO 4 and through a hexane, diethyl ether 50: 1 column yielded a yellow oil in 0.88 g, 13.4% yield.
1 H-NMR (C 6 D 6 ): 7.05 (m, 1H), 7.00 (d, 1H), 6.74 (t, 1H), 4.47 (s, 1H), 3.00 (t, 2H), 2.66 (t, 2H), 2.02 (q, 2H), 1.15 (m, 6H), 1.02 (m, 6H)
Production Example 3
Synthesis of 7- (diisopropylphosphanyl) -2-methylindoline [7- (diisopropylphosphanyl) -2-methylindoline]
In a 100 ml Schlenk flask, 2-methyl indolin (3.26 g, 24.5 mmol) and hexane (0.536 M, 45.7 ml) were added. N-BuLi (1.1 eq, 10.8 ml) was added at -20 ° C and allowed to stand overnight at room temperature. Filtration using glass frit (G4) and vacuum drying yielded phosphine-amine lithium. In a 250 ml Schlenk flask, the phosphine-amine lithium (3.37 g, 24.2 mmol) was added to diethyl ether (0.423 M, 57.3 ml) and CO 2 bubbling was added at −78 ° C. for 1 hour. After slowly reacting at room temperature overnight, THF (1.1 eq, 2.16 ml) and t-BuLi (1.1 eq, 15.7 ml) were added and maintained at -20 ° C for 2 hours. At the same temperature, i Pr 2 PCl (0.85 eq, 3.14 g) and diethyl ether (0.359 M, 57.3 ml) were added and maintained at the same temperature for 1 hour. After slowly reacting at room temperature overnight, 50 ml of distilled water was added at 0 ° C., followed by stirring at room temperature for 30 minutes. Work-up with diethyl ether, dried over MgSO 4, and red oil in 2.23 g, 37% yield through a hexane, diethyl ether 50: 1 column.
1 H-NMR (C 6 D 6 ): 7.06 (m, 1H), 6.99 (d, 1H), 6.75 (t, 1H), 4.63 (s, 1H), 3.56 (m, 1H), 2.85 (m, 1H), 2.39 (m, 1H), 2.05 (m, 2H), 1.16 (m, 6H), 1.04 (m, 6H), 0.90 (d, 3H)
Production Example 4
Synthesis of 8- (dicyclohexylphosphanyl) -1,2,3,4-tetrahydroquinoline [8- (dicyclohexyl phosphanyl) -1,2,3,4-tetrahydroquinoline]
To a 100 ml Schlenk flask was placed THQ (3.4 g, 25.5 mmol) and hexane (0.536 M, 47.6 ml). N-BuLi (1.1 eq, 11.2 ml) was added at -20 ° C and allowed to stand overnight at room temperature. Filtration using glass frit (G4) and vacuum drying yielded phosphine-amine lithium. In a 250 ml Schlenk flask, the phosphine-amine lithium (2.6 g, 18.7 mmol) was added to diethyl ether (0.423 M, 44.2 ml) and CO 2 bubbling was added at −78 ° C. for 1 hour. After slowly reacting at room temperature overnight, THF (1.1 eq, 1.67 ml) and t-BuLi (1.1 eq, 13.1 ml) were added and maintained at -20 ° C for 2 hours. Cy 2 PCl (0.85 eq, 3.7 g) and diethyl ether (0.359 M, 44.2 ml) were added at the same temperature and maintained at the same temperature for 1 hour. After slowly reacting at room temperature overnight, 50 ml of distilled water was added at 0 ° C., followed by stirring at room temperature for 30 minutes. Work-up with diethyl ether, dried over MgSO 4 and through a hexane, diethyl ether 50: 1 column yielded a yellow oil in 3.98 g, 64.6% yield.
1 H-NMR (C 6 D 6 ): 7.10 (d, 1H), 6.86 (d, 1H), 6.65 (t, 1H), 5.61 (d, 1H), 2.86 (t, 2H), 2.47 (t, 2H), 1.90 (m, 4H), 1.72 (m, 24H)
Example One
Synthesis of Bis-8- (diisopropylphosphanyl) -1,2,3,4-tetrahydroquinoline-zirconium chloride [Bis-8- (diisopropylphosphanyl) -1,2,3,4-tetrahydroquinoline-Zirconium chloride]
Into a 100 ml Schlenk flask, 8- (diisopropylphosphanyl) -1,2,3,4-tetraquinoline (0.81 g, 3.25 mmol) was added and vacuum dried. Toluene / diethyl ether (0.2 M, 10/1, 14.7 / 1.5 ml) was added thereto, n-BuLi (1.01 eq, 1.31 ml) was added at -30 ° C, and reacted overnight at 25 ° C. ZrCl 4 (0.5 eq, 0.380 g), toluene (14.7 ml), and THF (1.5 eq, 0.40 ml) were sequentially added to a 250 ml Schlenk flask, followed by washing with diethyl ether (1.5 ml). Then, the mixture was stirred at room temperature for 1 hour. The contents of the 100 ml Schlenk flask were transferred to a 250 ml Schlenk flask at low temperature, and then reacted at 25 ° C. overnight. After the reaction, the mixture was filtered using celite-coated glass frit (G4) and washed with hexane to remove impurities and ligands. This gave 210 mg of a yellow solid.
1 H-NMR (C6D6): 6.90 (m, 4H), 6.63 (m, 2H), 3.23 (br, 2H), 3.38 (m, 8H), 1.45 (m, 16H), 1.26 (m, 12H)
Example 2
Synthesis of Bis-7- (diisopropylphosphanyl) indolin-zirconium chloride [Bis-7- (diisopropylphosphanyl) indoline-Zirconium chloride]
In a 100 ml Schlenk flask, 7- (diisopropylphosphanyl) indoline (0.85 g, 3.61 mmol) was added thereto, followed by vacuum drying. Toluene / diethyl ether (0.2 M, 10/1, 16.5 / 1.65 ml) was added thereto, n-BuLi (1.01 eq, 1.46 ml) was added at -30 ° C, and reacted overnight at 25 ° C. ZrCl 4 (0.5 eq, 0.421 g), toluene (16.5 ml), and THF (1.5 eq, 0.44 ml) were sequentially added to a 250 ml Schlenk flask, followed by washing with diethyl ether (1.65 ml). Then, the mixture was stirred at room temperature for 1 hour. The contents of the 100 ml Schlenk flask were transferred to a 250 ml Schlenk flask at low temperature, and then reacted at 25 ° C. overnight. After the reaction was filtered using a glass frit (G4) with celite and washed with hexane to remove impurities and ligands. This gave 540 mg of a yellow solid in 47.4% yield.
1 H-NMR (C 6 D 6 ): 7.00 (m, 2H), 6.81 (m, 2H), 6.62 (m, 2H), 4.22 (m, 4H), 2.67 (m, 4H), 2.38 (m, 4H), 1.26 (m, 12H), 1.11 (m, 12H)
Example 3
Synthesis of Bis-7- (diisopropylphosphanyl) 2-methylindolin-zirconium chloride [Bis-7- (diisopropylphosphanyl) -2-methylindoline-Zirconium chloride]
Into a 100 ml Schlenk flask, 7- (diisopropylphosphanyl) -2-methylindolin (0.76 g, 3.05 mmol) was added and dried in vacuo. Toluene / diethyl ether (0.2 M, 10/1, 13.9 / 1.40 ml) was added thereto, n-BuLi (1.01 eq, 1.23 ml) was added at -30 ° C, and reacted overnight at 25 ° C. ZrCl 4 (0.5 eq, 0.355 g), toluene (13.9 ml), and THF (1.5 eq, 0.37 ml) were sequentially added to a 250 ml Schlenk flask, followed by washing with diethyl ether (1.40 ml). Then, the mixture was stirred at room temperature for 1 hour. The contents of the 100 ml Schlenk flask were transferred to a 250 ml Schlenk flask at low temperature, and then reacted at 25 ° C. overnight. After the reaction was filtered using a glass frit (G4) with celite and washed with hexane to remove impurities and ligands. This gave 490 mg of a wine-colored solid in 49% yield.
1 H-NMR (C 6 D 6 ): 7.01 (m, 2H), 6.66 (m, 2H), 6.58 (m, 2H), 5.16 (m, 2H), 3.22 (m, 2H), 2.45 (m, 2H), 2.27 (m, 2H), 2.05 (m, 2H), 1.63 (m, 6H), 1.26 (m, 6H), 0.95 (m, 12H), 0.65 (m, 6H)
Example 4
Synthesis of Bis-8- (dicyclohexylphosphanyl) -1,2,3,4-tetrahydroquinoline-zirconium chloride [Bis-8- (dicyclohexylphosphanyl) -1,2,3,4-tetrahydroquinoline-Zirconium chloride]
8- (dicyclohexylphosphanyl) -1,2,3,4-tetrahydroquinoline (1 g, 3.03 mmol) was added to a 100 ml Schlenk flask, followed by vacuum drying. Toluene / diethyl ether (0.2 M, 10/1, 13.8 / 1.40 ml) was added thereto, n-BuLi (1.01 eq, 1.23 ml) was added at -30 ° C, and reacted overnight at 25 ° C. ZrCl 4 (0.5 eq, 0.354 g), toluene (13.9 ml), and THF (1.5 eq, 0.37 ml) were sequentially added to a 250 ml Schlenk flask, followed by washing with diethyl ether (1.40 ml). Then, the mixture was stirred at room temperature for 1 hour. The contents of the 100 ml Schlenk flask were transferred to a 250 ml Schlenk flask at low temperature, and then reacted at 25 ° C. overnight. After the reaction was filtered using a glass frit (G4) with celite and washed with hexane to remove impurities and ligands. This gave 300 mg of a yellow solid.
1 H-NMR (C 6 D 6 ): 7.05 (m, 2H), 6.94 (m, 2H), 6.69 (m, 2H), 3.40 (m, 4H), 2.42 (m, 10H), 2.01 (m, 12H), 1.70 (m, 12H), 1.57 (m, 6H), 1.21 (m, 12H)
Example 5
Synthesis of Bis-8- (diisopropylphosphanyl) -1,2,3,4-tetrahydroquinoline-zirconium methyl [Bis-8- (diisopropylphosphanyl) -1,2,3,4-tetrahydroquinoline-Zirconium methyl]
Into a 100 ml Schlenk flask, 8- (diisopropylphosphanyl) -1,2,3,4-tetrahydroquinoline (0.95 g, 3.81 mmol) was added and vacuum dried. Toluene / diethyl ether (0.2 M, 10/1, 17.3 / 1.70 ml) was added thereto, n-BuLi (1.01 eq, 1.54 ml) was added at -30 ° C, and reacted overnight at 25 ° C. ZrCl 4 (0.5 eq, 0.444 g), toluene (17.3 ml), and THF (9.5 ml) were sequentially added to a 250 ml Schlenk flask, followed by MeLi (2.02 eq, 2.4 ml) at 0 ° C. It was stirred at 0 ° C. for 1 hour. The contents of the 100 ml Schlenk flask were transferred to a 250 ml Schlenk flask at low temperature, and then reacted at 25 ° C. overnight. After the reaction was filtered using a glass frit (G4) covered with celite. Impurities and ligands were removed via toluene-pentane precipitation. This gave 30 mg of a yellow solid.
1 H-NMR (CDCl 3): 7.03 (m, 2H), 6.90 (m, 2H), 6.50 (m, 2H), 3.29 (m, 2H), 2.86 (m, 4H), 2.73 (m, 2H), 2.57 (m, 4H), 1.50 (m, 4H), 1.34 (m, 24H), 0.16 (m, 6H)
Example 6
<Production of Copolymer>
Toluene solvent (0.8 L), butene (3.0 M), and ethylene (35 bar) were added to a 2 L autoclave reactor, the pressure was increased to 500 psi with high pressure argon, and the reactor was preheated to 120 ° C. It was. 10 equivalents of dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst of 5x10 -6 M was added to a reactor under high pressure argon pressure, and the transition metal compound prepared in Example 1 was treated with triisobutylaluminum compound ( 1 × 10 -6 M, 2.0 mL) was added to the catalyst storage tank and placed in a reactor under high pressure argon. The polymerization reaction was carried out for 10 minutes. The heat of reaction was removed through a cooling coil inside the reactor to keep the polymerization temperature as constant as possible. After the polymerization reaction was performed for 10 minutes, the remaining gas was drained, and then the polymer solution was discharged to the lower part of the reactor, and excess ethanol was added to cool, thereby inducing precipitation. After washing the obtained polymer with ethanol and acetone two to three times, and then dried in a 90 ° C vacuum oven for at least 12 hours, the physical properties were measured.
Example 7 to 9
<Production of Copolymer>
Except for using the transition metal compound prepared in Examples 2 to 4 instead of the transition metal compound prepared in Example 1, the copolymers were prepared in the same manner as in Example 6, respectively, Physical properties were measured.
The melt index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 190 ° C., 2.16 kg load). Melting point (Tm) was measured using TA Q100. The measurements were taken via a second melt, warmed to 10 ° C per minute to eliminate the thermal history of the polymer. The results are shown in Table 1 below.
(KgPE / mmolhr)
(℃)
(g / 10 min)
Claims (8)
[Formula 1]
In the above formula, Q 1 and Q 2 are each independently hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, 7 to 7 carbon atoms Arylalkyl of 20, alkyl amido of 1 to 20 carbon atoms, aryl amido of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms; M is Ti, Zr or hf;
R 1 , R 2 , R 4 to R 6 are each independently hydrogen, silyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and carbon atoms. A metalloid radical of group 14 metal substituted with arylalkyl of 7 to 20, or hydrocarbyl having 1 to 20 carbon atoms;
R 3 is hydrogen,
At least two of R 4 to R 6 may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1.
In Formula 1, Q 1 and Q 2 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. compound.
In Formula 1, R 1 , R 2 , R 4 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or having 7 to 20 carbon atoms. Arylalkyl; R 3 is hydrogen; At least two of R 4 to R 6 may be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
The compound of Formula 1 is a transition metal compound which is a compound of Formula B:
B)
.
The polymer is a polyolefin-based polymer.
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