JP6440268B2 - メタロセン化合物、これを含む触媒組成物およびこれを用いたオレフィン重合体の製造方法 - Google Patents
メタロセン化合物、これを含む触媒組成物およびこれを用いたオレフィン重合体の製造方法 Download PDFInfo
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- JP6440268B2 JP6440268B2 JP2016524579A JP2016524579A JP6440268B2 JP 6440268 B2 JP6440268 B2 JP 6440268B2 JP 2016524579 A JP2016524579 A JP 2016524579A JP 2016524579 A JP2016524579 A JP 2016524579A JP 6440268 B2 JP6440268 B2 JP 6440268B2
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- 239000003054 catalyst Substances 0.000 title claims description 35
- 229920000098 polyolefin Polymers 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 31
- 150000001875 compounds Chemical class 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 85
- 150000003623 transition metal compounds Chemical class 0.000 claims description 41
- -1 1-tert-butoxyhexyl Chemical group 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005353 silylalkyl group Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 2
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 claims description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 229950010765 pivalate Drugs 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims 1
- 125000005370 alkoxysilyl group Chemical group 0.000 claims 1
- 229910052795 boron group element Inorganic materials 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000003446 ligand Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- RXXXUIOZOITBII-UHFFFAOYSA-N indeno[1,2-g]indole Chemical compound C1=C2C=CC=CC2=C2C1=C1N=CC=C1C=C2 RXXXUIOZOITBII-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IYJWRBPTSUJVRY-UHFFFAOYSA-N 2-[6-[(2-methylpropan-2-yl)oxy]hexyl]-5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC(CCCCCCOC(C)(C)C)=C1 IYJWRBPTSUJVRY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-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
- 239000002244 precipitate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- YACIIBDIWPYURW-UHFFFAOYSA-N 5,8-dimethyl-10-[2-[3-[6-[(2-methylpropan-2-yl)oxy]hexyl]cyclopenta-2,4-dien-1-yl]propan-2-yl]-10H-indeno[1,2-b]indole Chemical compound C(C)(C)(C)OCCCCCCC1=CC(C=C1)C(C)(C)C1C2=CC=CC=C2C=2N(C=3C=CC(=CC=3C=21)C)C YACIIBDIWPYURW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VXNRIMPPUISTIE-UHFFFAOYSA-N C1(C=CC=C1)C(C1C2=CC=CC=C2C=2N(C=3C=CC(=CC=3C=21)C)C)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(C=CC=C1)C(C1C2=CC=CC=C2C=2N(C=3C=CC(=CC=3C=21)C)C)(C1=CC=CC=C1)C1=CC=CC=C1 VXNRIMPPUISTIE-UHFFFAOYSA-N 0.000 description 1
- BGRHHZMSJQNFLL-UHFFFAOYSA-N C1(C=CC=C1)C1(CCCCC1)C1C2=CC=CC=C2C=2N(C=3C=CC(=CC=3C=21)C)C Chemical compound C1(C=CC=C1)C1(CCCCC1)C1C2=CC=CC=C2C=2N(C=3C=CC(=CC=3C=21)C)C BGRHHZMSJQNFLL-UHFFFAOYSA-N 0.000 description 1
- WEJGVUHSPQCUGF-UHFFFAOYSA-N CC(C)(C)CCCCCCC1=CCC=C1 Chemical compound CC(C)(C)CCCCCCC1=CCC=C1 WEJGVUHSPQCUGF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 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
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion 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
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
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Description
しかし、このような全ての試みの中で、実際に商業工場に適用されているメタロセン触媒はいくつかに過ぎない水準であり、これによって、より高い重合性能を実現することができ、加工性向上のために中低分子量のポリオレフィンを提供することができる重合触媒として使用可能なメタロセン化合物に対する研究が依然として必要である。
本発明の一実施形態によれば、下記化学式1で表される遷移金属化合物が提供できる。
一方、発明の他の実施形態によれば、前記化学式1の遷移金属化合物と助触媒とを含む遷移金属触媒組成物が提供できる。
後述する実施例、比較例および実験例において、有機試薬および溶媒は、アルドリッチ(Aldrich)社とメルク(Merck)社から購入し、標準方法で精製して使用した。合成の全ての段階において空気と水分の接触を遮断して実験の再現性を高めた。また、化合物の構造を立証するために、500MHz核磁気共鳴器(NMR)を用いてスペクトルを得た。
実施例1:[(10−(2−(3−(6−tert−butoxyhexyl)cyclopenta−2,4−dienyl)propan−2−yl)−5,8−dimethyl−5,10−dihydroindeno[1,2−b]indole)]zirconium chlorideの合成
(1)リガンド化合物(10−(2−(3−(6−tert−butoxyhexyl)cyclopenta−2,4−dienyl)propan−2−yl)−5,8−dimethyl−5,10−dihydroindeno[1,2−b]indole)の合成
1H−NMR(500MHz,CDCl3):0.87,1.17,1.27,1.34(6H,m),1.20(9H,s),1.44(4H,m),1.54(2H,m),1.54−1.69(4H,m),2.42,2.48(3H,s),3.35(2H,m),4.03(3H,m),5.73,6.01,6.05,6.13,6.61(3H,s),6.97−7.04(2H,m),7.07−7.18(2H,m),7.32(1H,m),7.55−7.63(2H,m)
そして、Glove box内から2.1当量のZrCl4(THF)2を取って250mlのSchlenk flaskに入れて、Etherを入れたZr suspensionを準備した。
1H−NMR(500MHz,CDCl3):0.81(2H,m),1.13(9H,d),1.22(2H,m),1.32(2H,m),1.43(4H,m),2.34(3H,d),2.49(6H,t),3.23(2H,m),4.14(3H,s),5.09,5.35,5.45,5.69,5.86,6.01(3H,s),6.99(1H,m),7.32(3H,m),7.74(1H,q),7.94(1H,d),7.97(1H,d)
(1)リガンド化合物(10−(cyclopenta−2,4−dienyldiphenylmethyl)−5,8−dimethyl−5,10−dihydroindeno[1,2−b]indole)の合成
(1)リガンド化合物10−(1−(cyclopenta−2,4−dien−1−yl)cyclohexyl)−5,8−dimethyl−5,10−dihydroindeno[1,2−b]indoleの合成
(2)遷移金属化合物[10−(1−(cyclopenta−2,4−dien−1−yl)cyclohexyl)−5,8−dimethyl−5,10−dihydroindeno[1,2−b]indole]zirconium chlorideの合成
実験例1:エチレン単独重合体の製造
600mLのパール反応器を120℃で1時間真空乾燥を実施し、温度を50℃に下げてアルゴンを加えた。これに、アルゴン環境下、ヘキサン溶媒(400mL)とTEAL助触媒0.46gをcannulaで反応器に投入した。そして、ファウリングを防止するために、静電気防止剤(ASA)0.17mlをシリンジを用いて投入し、5分間撹拌した。次に、前記実施例1または比較例1で製造した遷移金属化合物10mgを反応器に入れて、反応器内のアルゴンを除去した。温度を80℃に昇温させた後、反応器に40barのエチレンを入れながら、60分間500rpmで撹拌しながら重合反応を実施した。重合反応後、温度を60℃に下げて、反応器内の圧力を除去し、反応器と撹拌機を分離した後、準備したフラスコ(1Lビーカー)に重合した高分子を入れた。そして、Aspiratorを用いて高分子をフィルターした後、オーブンで高分子を乾燥させ、物性を測定した。
Claims (8)
- 下記化学式1で表される遷移金属化合物:
R 1 およびR 5 は、炭素数1〜20のアルキル基であり、
R 8 は、炭素数1〜20のアルキル基、炭素数1〜20のアルコキシ基、炭素数1〜20のアルキルシリル基、炭素数1〜20のシリルアルキル基、炭素数6〜20のアリール基、または炭素数7〜20のアリールアルキル基であり、
R 2 〜R 4 、R 6 、R 7 、R 9 〜R12は、それぞれ独立に、水素、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数1〜20のアルキルシリル基、炭素数1〜20のシリルアルキル基、炭素数1〜20のアルコキシシリル基、炭素数1〜20のエーテル基、炭素数1〜20のシリルエーテル基、炭素数1〜20のアルコキシ基、炭素数6〜20のアリール基、炭素数7〜20のアルキルアリール基、および炭素数7〜20のアリールアルキル基からなる群より選択された官能基であり、
Q1およびQ2は、それぞれ独立に、水素、ハロゲン、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数1〜20のアルコキシ基、炭素数6〜20のアリール基、炭素数2〜20のアルコキシアルキル基、炭素数3〜20のヘテロシクロアルキル基、炭素数5〜20のヘテロアリール基、1−tert−butoxyhexyl、またはpivalateであり、
Mは、4族の遷移金属であり、
Xは、それぞれ独立に、ハロゲン、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数6〜20のアリール基、ニトロ基、アミド基、炭素数1〜20のアルキルシリル基、炭素数1〜20のアルコキシ基、または炭素数1〜20のスルホネート基であり、
nは、1〜10の整数である。 - 前記Mは、Ti、Zr、およびHfからなる群より選択される、請求項1に記載の遷移金属化合物。
- Q1およびQ2は、それぞれ独立に、炭素数1〜20のアルキル基、炭素数1〜20のアルケニル基、炭素数1〜20のアルコキシ基、または炭素数6〜20のアリール基である、請求項1に記載の遷移金属化合物。
- 請求項1に記載の化学式1で表される遷移金属化合物;および下記化学式2〜4の化合物からなる群より選択された1種以上を含む助触媒;を含む触媒組成物:
Lは、中性または陽イオン性ルイス塩基であり、
[L−H]+または[L]+は、ブレンステッド酸であり、
Hは、水素原子であり、
Zは、13族元素であり、
Eは、それぞれ独立に、1以上の水素原子がハロゲン、炭素数1〜20のヒドロカルビル、アルコキシまたはフェノキシで置換もしくは非置換の炭素数6〜20のアリール基または炭素数1〜20のアルキル基であり、
Dは、アルミニウムまたはホウ素であり、
R13は、それぞれ独立に、ハロゲン;炭素数1〜20のヒドロカルビル基;またはハロゲンで置換された炭素数1〜20のヒドロカルビル基であり、
R14、R15およびR16は、それぞれ、水素;ハロゲン基;炭素数1〜20のヒドロカルビル基;またはハロゲンで置換された炭素数1〜20のヒドロカルビル基;であり、aは、2以上の整数である。 - 溶媒をさらに含む、請求項4に記載の触媒組成物。
- 前記遷移金属化合物および助触媒化合物は、担体に固定された形態である、請求項4に記載の触媒組成物。
- 請求項4に記載の触媒組成物の存在下、オレフィン単量体を重合反応させる段階を含む、オレフィン重合体の製造方法。
- 前記オレフィン単量体は、エチレン、プロピレン、1−ブテン、1−ペンテン、4−メチル−1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−デセン、1−ウンデセン、1−ドデセン、1−テトラデセン、1−ヘキサデセン、1−アイトセン、ノルボルネン、ノルボルナジエン、エチリデンノルボルネン、フェニルノルボルネン、ビニルノルボルネン、ジシクロペンタジエン、1,4−ブタジエン、1,5−ペンタジエン、1,6−ヘキサジエン、スチレン、アルファ−メチルスチレン、ジビニルベンゼン、および3−クロロメチルスチレンからなる群より選択される1種以上を含む、請求項7に記載のオレフィン重合体の製造方法。
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