JP2021525307A - 触媒組成物およびこれを用いたポリオレフィンの製造方法 - Google Patents
触媒組成物およびこれを用いたポリオレフィンの製造方法 Download PDFInfo
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- JP2021525307A JP2021525307A JP2021517181A JP2021517181A JP2021525307A JP 2021525307 A JP2021525307 A JP 2021525307A JP 2021517181 A JP2021517181 A JP 2021517181A JP 2021517181 A JP2021517181 A JP 2021517181A JP 2021525307 A JP2021525307 A JP 2021525307A
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- chemical formula
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- polyolefin
- transition metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000000126 substance Substances 0.000 claims description 63
- 150000003623 transition metal compounds Chemical class 0.000 claims description 39
- -1 cationic Lewis base Chemical class 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 23
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 17
- 239000003426 co-catalyst Substances 0.000 claims description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 8
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052795 boron group element Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 29
- 239000002002 slurry Substances 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 23
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 230000037048 polymerization activity Effects 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 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 11
- 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 9
- 229920000642 polymer Polymers 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 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
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 1
- 0 **(*)(C1C=C(*)C=C1)C1C=C(*)C=C1 Chemical compound **(*)(C1C=C(*)C=C1)C1C=C(*)C=C1 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- UMAPFJZTGMTFIR-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-tri(propan-2-yl)silylphenoxy]boronic acid Chemical compound CC(C)[Si](C(C)C)(C(C)C)C1=C(F)C(F)=C(OB(O)O)C(F)=C1F UMAPFJZTGMTFIR-UHFFFAOYSA-N 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005025 alkynylaryl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 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
- 125000002619 bicyclic group Chemical group 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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation 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
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920005679 linear ultra low density polyethylene Polymers 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 125000002950 monocyclic group Chemical group 0.000 description 1
- JZBZLRKFJWQZHU-UHFFFAOYSA-N n,n,2,4,6-pentamethylaniline Chemical compound CN(C)C1=C(C)C=C(C)C=C1C JZBZLRKFJWQZHU-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
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- 125000006606 n-butoxy group Chemical group 0.000 description 1
- GOJIVVWJAXAPGS-UHFFFAOYSA-N n-dodecyl-n-methylaniline Chemical compound CCCCCCCCCCCCN(C)C1=CC=CC=C1 GOJIVVWJAXAPGS-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000012071 phase Substances 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
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 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
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 125000003944 tolyl 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
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-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
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
Description
本出願は、2019年2月20日付韓国特許出願第10−2019−0020024号及び2020年2月20日付韓国特許出願第10−2020−0020903号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
R1およびR2は、それぞれ独立して、水素、ハロゲン、C1〜20アルキル、C2〜20アルケニル、C1〜20アルコキシ、またはC2〜20アルコキシアルキルであり、
X1およびX2は、それぞれ独立して、ハロゲンまたはC1〜20アルキルであり、
R3およびR4は、それぞれ独立して、水素、ハロゲン、C1〜20アルキル、C2〜20アルケニル、C1〜20アルコキシ、またはC2〜20アルコキシアルキルであり、
X3およびX4は、それぞれ独立して、ハロゲンまたはC1〜20アルキルである。
R1およびR2は、それぞれ独立して、水素、ハロゲン、C1〜20アルキル、C2〜20アルケニル、C1〜20アルコキシ、またはC2〜20アルコキシアルキルであり、
X1およびX2は、それぞれ独立して、ハロゲンまたはC1〜20アルキルであり、
R3およびR4は、それぞれ独立して、水素、ハロゲン、C1〜20アルキル、C2〜20アルケニル、C1〜20アルコキシ、またはC2〜20アルコキシアルキルであり、
X3およびX4は、それぞれ独立して、ハロゲンまたはC1〜20アルキルである。
R6−[Al(R5)−O]n−R7
R5、R6およびR7は、それぞれ独立して、水素、ハロゲン、C1〜20ヒドロカルビル基、またはハロゲンで置換されたC1〜20ヒドロカルビル基であり、
nは、2以上の整数であり、
D(R8)3
Dは、アルミニウムまたはホウ素であり、
R8は、それぞれ独立して、ハロゲン、C1〜20ヒドロカルビル基、C1〜20ヒドロカルビルオキシ基、またはハロゲンで置換されたC1〜20ヒドロカルビル基であり、
[L−H]+[W(A)4]−または[L]+[W(A)4]−
Lは、中性または陽イオン性ルイス塩基であり、
Hは、水素原子であり、
Wは、13族元素であり、
Aは、それぞれ独立して、C1〜20ヒドロカルビル基;C1〜20ヒドロカルビルオキシ基;およびこれら置換基の1以上の水素原子がハロゲン、C1〜20ヒドロカルビルオキシ基およびC1〜20ヒドロカルビル(オキシ)シリル基のうちの1以上の置換基で置換された置換基のうちのいずれか一つである。
シリカ(Grace Davison社製造 SP952)を200℃の温度で12時間真空を加えた状態で脱水および乾燥した。
前記実施例1で化学式1bで表される化合物0.01mmolおよび化学式2aで表される化合物0.01mmolの代わりに、化学式1bで表される化合物0.01mmolおよび化学式2aで表される化合物0.003mmolを使用することを除いては、実施例1と同様の方法で混成担持触媒およびオレフィン重合体を製造した。
前記実施例1で化学式1bで表される化合物0.01mmolおよび化学式2aで表される化合物0.01mmolの代わりに、化学式1bで表される化合物0.01mmolおよび化学式2aで表される化合物0.035mmolを使用することを除いては、実施例1と同様の方法で混成担持触媒およびオレフィン重合体を製造した。
シリカ(Grace Davison社製造SP952)を200℃の温度で12時間真空を加えた状態で脱水および乾燥した。
前記実施例1で化学式1bで表される化合物および化学式2aで表される化合物の代わりに、ビス[1−(p−ジメチルアミノフェニル)−3,4−ジメチルシクロペンタジエニル]ジルコニウムジクロリド([1−(p−Me2NC6H4)−3,4−Me2C5H2]2ZrCl2)0.01mmolおよびビス[1−(p−ジメチルアミノフェニル)−3,4−ジメチルシクロペンタジエニル]ハフニウムジクロリド([1−(p−Me2NC6H4)−3,4−Me2C5H2]2HfCl2)0.01mmolを使用することを除いては、実施例1と同様の方法で混成担持触媒およびオレフィン重合体を製造した。
下記表1に示した条件下で、前記実施例および比較例で製造したそれぞれの担持触媒の存在下にエチレン−1−ヘキセンをスラリー重合した。
前記実施例および比較例の触媒活性、工程安定性およびポリオレフィンの物性を下記の方法で測定し、その結果を下記表2に示した。
単位時間(h)当り使用された触媒含量(g Cat)当り生成された重合体の重量(kg PE)の比で計算した。
ASTM D 1238に基づいて190℃下で2.16kgの荷重で溶融指数(MI 2.16)を測定し、10分間溶融して出た重合体の重量(g)で示した。
ASTM D−792によって密度を測定した。
ASTM D1895によって見かけ密度(Bulk Density)を測定した。
ポリオレフィン製造工程で、固体生成物などが反応器内部装置および壁面に付着するファウリング現象が発生するかどうかを確認して、その結果を下記表2に示した。
ASTM D 1709を基準にしたフィルム試料当り20回以上測定して落下衝撃強度を求めた。
Claims (12)
- 下記化学式1で表される第1遷移金属化合物(A)および下記化学式2で表される第2遷移金属化合物(B)を1:0.3〜1:3.5のモル比(A:B)で含む、触媒組成物:
R1およびR2は、それぞれ独立して、水素、ハロゲン、C1〜20アルキル、C2〜20アルケニル、C1〜20アルコキシ、またはC2〜20アルコキシアルキルであり、
X1およびX2は、それぞれ独立して、ハロゲンまたはC1〜20アルキルであり、
R3およびR4は、それぞれ独立して、水素、ハロゲン、C1〜20アルキル、C2〜20アルケニル、C1〜20アルコキシ、またはC2〜20アルコキシアルキルであり、
X3およびX4は、それぞれ独立して、ハロゲンまたはC1〜20アルキルである。 - 前記R1およびR2は、それぞれ独立して、C4〜20アルキルまたはtert−ブトキシで置換されたC5〜9直鎖アルキルである、請求項1に記載の触媒組成物。
- 前記R3およびR4は、それぞれ独立して、C1〜3アルキルである、請求項1または2に記載の触媒組成物。
- 前記第1遷移金属化合物および第2遷移金属化合物を担持する担体をさらに含む、請求項1から5のいずれか一項に記載の触媒組成物。
- 前記担体は、シリカ、アルミナおよびマグネシアからなる群より選択されるいずれか一つまたは二つ以上の混合物を含む、請求項6に記載の触媒組成物。
- 下記化学式3〜5で表される化合物からなる群より選択される1種以上の助触媒をさらに含む、請求項1から7のいずれか一項に記載の触媒組成物:
[化学式3]
R6−[Al(R5)−O]n−R7
上記化学式3中、
R5、R6およびR7は、それぞれ独立して、水素、ハロゲン、C1〜20ヒドロカルビル基、またはハロゲンで置換されたC1〜20ヒドロカルビル基であり、
nは、2以上の整数であり、
[化学式4]
D(R8)3
上記化学式4中、
Dは、アルミニウムまたはホウ素であり、
R8は、それぞれ独立して、ハロゲン、C1〜20ヒドロカルビル基、C1〜20ヒドロカルビルオキシ基、またはハロゲンで置換されたC1〜20ヒドロカルビル基であり、
[化学式5]
[L−H]+[W(A)4]−または[L]+[W(A)4]−
上記化学式5中、
Lは、中性または陽イオン性ルイス塩基であり、
Hは、水素原子であり、
Wは、13族元素であり、
Aは、それぞれ独立して、C1〜20ヒドロカルビル基;C1〜20ヒドロカルビルオキシ基;およびこれら置換基の1以上の水素原子がハロゲン、C1〜20ヒドロカルビルオキシ基およびC1〜20ヒドロカルビル(オキシ)シリル基のうちの1以上の置換基で置換された置換基のうちのいずれか一つである。 - 請求項1から8のいずれか一項の触媒組成物存在下で、オレフィン単量体をスラリー重合する段階を含む、ポリオレフィンの製造方法。
- 前記オレフィン単量体は、エチレンおよび1−ヘキセンを含む、請求項9に記載のポリオレフィンの製造方法。
- 請求項9または10に記載のポリオレフィンの製造方法によって製造され、
0.900〜0.915g/cm3の密度を有する超低密度ポリエチレン共重合体を含む、ポリオレフィン。 - 前記ポリオレフィンは、溶融指数(MI)が0.5〜2.5g/10min(190℃、2.16kg)であり、
見かけ密度(BD、Bulk Density)が0.2〜0.5g/mlであり、
重量平均分子量が50,000〜200,000であり、
分子量分布指数(PDI)が2.0〜4.0であり、
ASTM D 1709を基準にして、落下衝撃強度が1000g以上である、請求項11に記載のポリオレフィン。
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