JP5422208B2 - 遷移金属化合物、これを含む遷移金属触媒組成物、及びエチレン単独重合体またはエチレンとα−オレフィンの共重合体の製造方法 - Google Patents
遷移金属化合物、これを含む遷移金属触媒組成物、及びエチレン単独重合体またはエチレンとα−オレフィンの共重合体の製造方法 Download PDFInfo
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- JP5422208B2 JP5422208B2 JP2009001960A JP2009001960A JP5422208B2 JP 5422208 B2 JP5422208 B2 JP 5422208B2 JP 2009001960 A JP2009001960 A JP 2009001960A JP 2009001960 A JP2009001960 A JP 2009001960A JP 5422208 B2 JP5422208 B2 JP 5422208B2
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- ethylene
- transition metal
- alkyl
- aryl
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 74
- 239000005977 Ethylene Substances 0.000 title claims description 74
- 239000003054 catalyst Substances 0.000 title claims description 47
- 239000004711 α-olefin Substances 0.000 title claims description 30
- 229910052723 transition metal Inorganic materials 0.000 title claims description 29
- 150000003624 transition metals Chemical class 0.000 title claims description 29
- 239000000203 mixture Substances 0.000 title claims description 27
- 229920001577 copolymer Polymers 0.000 title claims description 26
- 229920001519 homopolymer Polymers 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 150000003623 transition metal compounds Chemical class 0.000 title claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 29
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 25
- 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 claims description 23
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 22
- 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 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical class 0.000 claims description 6
- 150000001639 boron compounds Chemical class 0.000 claims description 6
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical class P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 229910052735 hafnium Chemical group 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 claims description 3
- 125000004469 siloxy group Chemical class [SiH3]O* 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229940106006 1-eicosene Drugs 0.000 claims description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 claims 1
- -1 alkylaluminum compound Chemical class 0.000 description 265
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000003446 ligand Substances 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000003426 co-catalyst Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical group CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 4
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical group CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical group C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 description 3
- 150000003931 anilides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 125000005810 2,5-xylyl group Chemical group [H]C1=C([H])C(=C(*)C([H])=C1C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DXHHRLCXALPNON-UHFFFAOYSA-N 7-phenylheptylphosphane Chemical group PCCCCCCCC1=CC=CC=C1 DXHHRLCXALPNON-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- QQOBHOXREJOYBD-UHFFFAOYSA-M CC(C)(C1)OC2=C1C=CC=C2O[Ti+2]C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)(C1)OC2=C1C=CC=C2O[Ti+2]C1(C)C(C)=C(C)C(C)=C1C QQOBHOXREJOYBD-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004708 Very-low-density polyethylene Substances 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- LREAZWJEBORMTB-UHFFFAOYSA-N bis(2-methylpropyl)phosphane Chemical group CC(C)CPCC(C)C LREAZWJEBORMTB-UHFFFAOYSA-N 0.000 description 2
- CJJRJEPKDXKZOE-UHFFFAOYSA-N bis[tert-butyl(dimethyl)silyl]phosphane Chemical group CC(C)(C)[Si](C)(C)P[Si](C)(C)C(C)(C)C CJJRJEPKDXKZOE-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- DHCKTCPNOVJOEZ-UHFFFAOYSA-N di(butan-2-yl)phosphane Chemical group CCC(C)PC(C)CC DHCKTCPNOVJOEZ-UHFFFAOYSA-N 0.000 description 2
- WDIIYWASEVHBBT-UHFFFAOYSA-N di(propan-2-yl)phosphane Chemical group CC(C)PC(C)C WDIIYWASEVHBBT-UHFFFAOYSA-N 0.000 description 2
- SBWJERDWKYNUFP-UHFFFAOYSA-N dibenzylphosphane Chemical group C=1C=CC=CC=1CPCC1=CC=CC=C1 SBWJERDWKYNUFP-UHFFFAOYSA-N 0.000 description 2
- LKKRAZFAACYENL-UHFFFAOYSA-N didecylphosphane Chemical group CCCCCCCCCCPCCCCCCCCCC LKKRAZFAACYENL-UHFFFAOYSA-N 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- IWQIEVOJUWFMSB-UHFFFAOYSA-N dihexylphosphane Chemical group CCCCCCPCCCCCC IWQIEVOJUWFMSB-UHFFFAOYSA-N 0.000 description 2
- BYYQOWAAZOHHFN-UHFFFAOYSA-N dioctylphosphane Chemical group CCCCCCCCPCCCCCCCC BYYQOWAAZOHHFN-UHFFFAOYSA-N 0.000 description 2
- MTWCVKTUVWXLFS-UHFFFAOYSA-N dipropylphosphane Chemical group CCCPCCC MTWCVKTUVWXLFS-UHFFFAOYSA-N 0.000 description 2
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical group CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- BXDCELKJGGVUHD-UHFFFAOYSA-N ethyl(methyl)phosphane Chemical group CCPC BXDCELKJGGVUHD-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MHERPFVRWOTBSF-UHFFFAOYSA-N methyl(phenyl)phosphane Chemical group CPC1=CC=CC=C1 MHERPFVRWOTBSF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
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- LXEPFXNKXVLJCN-UHFFFAOYSA-N tert-butyl(propan-2-yl)phosphane Chemical group CC(C)PC(C)(C)C LXEPFXNKXVLJCN-UHFFFAOYSA-N 0.000 description 2
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
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- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- WDZHBOCICCGMDL-UHFFFAOYSA-M CC(C)(C1)OC2=C1C=CC=C2O[Ti]C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)(C1)OC2=C1C=CC=C2O[Ti]C1(C)C(C)=C(C)C(C)=C1C WDZHBOCICCGMDL-UHFFFAOYSA-M 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 230000003213 activating effect Effects 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
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- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 0.000 description 1
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- ZMXPNWBFRPIZFV-UHFFFAOYSA-M dipropylalumanylium;chloride Chemical compound [Cl-].CCC[Al+]CCC ZMXPNWBFRPIZFV-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 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
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 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
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- OHSJPLSEQNCRLW-UHFFFAOYSA-N triphenylmethyl radical Chemical compound C1=CC=CC=C1[C](C=1C=CC=CC=1)C1=CC=CC=C1 OHSJPLSEQNCRLW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- NPHLURKGGOFSPO-UHFFFAOYSA-N tris(2,3,4,5-tetrafluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C(=C(F)C(F)=C(F)C=2)F)C=2C(=C(F)C(F)=C(F)C=2)F)=C1F NPHLURKGGOFSPO-UHFFFAOYSA-N 0.000 description 1
- BMKAZNZYKFHZCV-UHFFFAOYSA-N tris(2,3,4-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC=C1B(C=1C(=C(F)C(F)=CC=1)F)C1=CC=C(F)C(F)=C1F BMKAZNZYKFHZCV-UHFFFAOYSA-N 0.000 description 1
- GZQXROYFQLBBPK-UHFFFAOYSA-N tris(2,3,5,6-tetrafluorophenyl)borane Chemical compound FC1=CC(F)=C(F)C(B(C=2C(=C(F)C=C(F)C=2F)F)C=2C(=C(F)C=C(F)C=2F)F)=C1F GZQXROYFQLBBPK-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- LKNHGIFPRLUGEG-UHFFFAOYSA-N tris(3,4,5-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C=C(F)C(F)=C(F)C=2)C=2C=C(F)C(F)=C(F)C=2)=C1 LKNHGIFPRLUGEG-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- 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
- C07F17/00—Metallocenes
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- 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
- C08F10/02—Ethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Description
[化1]
[化学式1]
式中、Mは、周期律表上、4族の遷移金属であり、Cpは、Mとη5−結合できるシクロペンタジエニル環、またはシクロペンタジエニル環を含む融合環であって、前記シクロペンタジエニル環またはシクロペンタジエニル融合環は、(C1〜C20)アルキル基、(C6〜C30)アリール基、(C2〜C20)アルケニル基、(C6〜C30)アリール(C1〜C20)アルキル基でさらに置換できて、R1及びR2は、互いに独立して、水素原子、(C1〜C20)アルキル基、(C3〜C20)シクロアルキル基、(C6〜C30)アリール基、(C1〜C20)アルキル(C6〜C30)アリール基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換シリル基、(C6〜C30)アリール基、(C6〜C30)アリール(C1〜C10)アルキル基、(C1〜C20)アルコキシ基、(C1〜C20)アルキル置換または(C6〜C20)アリール置換シロキシ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換アミノ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換ホスフィド基、(C1〜C20)アルキル置換メルカプト基、または、ニトロ基であり、R3及びR4は、互いに独立して、水素原子、(C1〜C20)アルキル基、(C3〜C20)シクロアルキル基、(C6〜C30)アリール基、(C1〜C20)アルキル(C6〜C30)アリール基、または、(C6〜C30)アリール(C1〜C20)アルキル基であって、aは、1または2の整数であり、nは、1または2の整数であって、Xは、互いに独立して、ハロゲン原子、(C1〜C20)アルキル基、(C3〜C20)シクロアルキル基、(C6〜C30)アリール(C1〜C20)アルキル基、(C1〜C20)アルコキシ基、(C3〜C20)アルキルシロキシ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換アミノ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換ホスフィン基、及び(C1〜C20)アルキル置換メルカプト基からなる群から選択される。
[化学式2]
B(R5)3
[化3]
[化学式3]
[R6]+[B(R5)4]−
[化4]
[化学式4]
[(R7)pZH]+[B(R5)4]−
[化学式5]
(−Al(R8)−O−)m
[化6]
[化学式6]
(R8)2Al−(−O(R8)−)q−(R8)2
[化7]
[化学式7]
(R9)rAl(E)3−r
[化8]
[化学式8]
(R10)2AlOR11
[化9]
[化学式9]
R10Al(OR11)2
ASTM D 2839に基づいて測定した。
2.密度
ASTM D 1505に基づき、密度勾配管を使用して測定した。
3.溶融点(Tm)分析
Dupont DSC2910を利用して窒素雰囲気下で10℃/minの速度で2nd加熱条件で測定した。
4.分子量及び分子量分布
PL Mixed−BX2+preCo1付きPL210 GPCを用いて、135℃で1.0mL/minの速度で1,2,3−トリクロロベンゼン溶媒下で測定して、PLポリスチレン標準物質を使用して分子量を補正した。
5.共重合体中のα−オレフィン含量(重量%)
Bruker DRX500核磁気共鳴分光器を用いて、125MHzで1,2,4−トリクロロベンゼン/C6D6(7/3重量分率)混合溶媒を使用し、120℃で13C−NMRモードで測定した(参考文献: Randal, J. C. JMS-Rev. Macromol. Chem. Phys. 1980, C29, 201)
(2,3−ジヒドロ−2,2−ジメチル−7−ベンゾフラノキシ)(ペンタメチルシクロペンタジエニル)チタニウム(IV)ジクロライドの合成
2,3−ジヒドロ−2,2−ジメチル−7−ベンゾフラニル(1.35g, 5.5mmol)を100mLノルマルヘキサンに溶かした後、−78℃でノルマルブチルリチウム(2.5Mヘキサン溶液, 2.6mL)を徐々に注入した後、常温で3時間攪拌する。反応が終わった後、ヘキサンを除去し、ヘキサンで洗浄して得た白色固体を50mLのトルエンに溶かした後、−78℃で(ペンタメチルシクロペンタジエニル)チタニウム(IV)トリクロライド(0.56g, 2.0mmol)を5mLのトルエンに溶かした溶液を徐々に滴下し、12時間常温で反応させた。反応が終わると、セラアイトでろ過し、揮発物質を除去して、精製されたトルエンとヘキサンで−35℃で再結晶してろ過した後、減圧乾燥させ、赤色の固体成分0.38gを得た。
収率 48%, 1H-NMR (C6D6) δ= 1.16 (s, 6H), 2.02 (s, 15H), 2.54 (s, 2H), 6.54-6.59 (m, 2H), 7.01-7.13 (m, 1H) ppm
Mass (APCI mode, m/z): 417
回分式重合装置を使用して、次のようにエチレンの重合を行った。十分に乾燥後窒素で置換させた200mL容量のステンレススチール反応器にシクロヘキサン97mLを入れた後、改良メチルアルミノキサン−7(Akzo Nobel社, modified MAO-7, 7wt% Al Isopar溶液)36.4mMトルエン溶液4.12mLを反応器に投入した。その後、反応器の温度を140℃まで加熱した後、製造例1で合成した(2,3−ジヒドロ−2,2−ジメチル−7−ベンゾフラノキシ)(ペンタメチルシクロペンタジエニル)チタニウム(IV)ジクロライド(1mMトルエン溶液)1.192mLと0.65mLのトリフェニルメチリニウムテトラキスペンタフルオロフェニルボレート(99%、Boulder Scientific)4.65mMトルエン溶液を順に投入した後、エチレンで反応器内の圧力を30kg/cm2まで満たした後、連続的に供給して重合されるようにした。反応開始3分後に最大温度188℃まで到達して、10分後、10mLの10vol%塩酸水溶液を含有したエタノールを投入して重合を終了した後、1500mLのエタノールで4時間攪拌した後、反応生成物をろ過、分離した。回収された反応生成物を60℃の真空オーブンで8時間乾燥した結果、5.28gの重合体が得られた。重合体のメルトインデクスは、測定不可能であって、ゲルクロマトグラフィーによる分析時、重量平均分子量(Mw)が440,000g/mol、分子量分布(Mw/Mn)が3.03であった。
回分式重合装置を使用して、次のようにエチレンと1−オクテンとの共重合を行った。
十分に乾燥後窒素で置換させた200mL容量のステンレススチール反応器にシクロへキサン88mLと1−オクテン5mLを入れた後、改良メチルアルミノキサン−7(Akzo Nobel社, modified MAO-7, 7wt% Al Isopar溶液)36.4mMトルエン溶液8.24mLを反応器に投入した。その後、反応器の温度を145℃まで加熱した後、製造例1で合成した(2,3−ジヒドロ−2,2−ジメチル−7−ベンゾフラノキシ)(ペンタメチルシクロペンタジエニル)チタニウム(IV)ジクロライド(0.84mMトルエン溶液)1.19mLと0.65mLのトリフェニルメチリニウムテトラキスペンタフルオロフェニルボレート(99%、Boulder Scientific)4.65mMトルエン溶液を順に投入した後、エチレンで反応器内の圧力を30kg/cm2まで満たした後、連続的に供給して重合されるようにした。反応時間1分間最大温度169.6℃まで到達して、1分が経つと、10mLの10vol%塩酸水溶液を含有したエタノールを投入して重合を終了した後、1500mLのエタノールで1時間攪拌した後、反応生成物をろ過、分離した。回収された反応生成物を60℃の真空オーブンで8時間乾燥した結果、3.92gの重合体が得られた。重合体の溶融点は、111.1℃、メルトインデクスは、0.043、密度は、0.9135g/ccであって、ゲルクロマトグラフィーによる分析時、重量平均分子量(Mw)が186,500g/mol、分子量分布(Mw/Mn)が2.66であって、1−オクテンの含量が9.3重量%であった。
回分式重合装置を使用して、次のようにエチレンと1−オクテンとの共重合を行った。
十分に乾燥後窒素で置換させた200mL容量のステンレススチール反応器にシクロヘキサン83mLと1−オクテン10mLを入れた後、改良メチルアルミノキサン−7(Akzo Nobel社, modified MAO-7, 7wt% Al Isopar溶液)36.4mMトルエン溶液8.24mLを反応器に投入した。その後、反応器の温度を142.6℃まで加熱した後、製造例1で合成した(2,3−ジヒドロ−2,2−ジメチル−7−ベンゾフラノキシ)(ペンタメチルシクロペンタジエニル)チタニウム(IV)ジクロライド(0.84mMトルエン溶液)1.19mLと0.65mLのトリフェニルメチリニウムテトラキスペンタフルオロフェニルボレート(99%、Boulder Scientific)4.65mMトルエン溶液を順に投入した後、エチレンで反応器内の圧力を30kg/cm2まで満たした後、連続的に供給して重合されるようにした。反応時間1分間最大温度168.2℃まで到達して、1分が経つと、10mLの10vol%塩酸水溶液を含有したエタノールを投入して重合を終了した後、1500mLのエタノールで4時間攪拌した後、反応生成物をろ過、分離した。回収された反応生成物を60℃の真空オーブンで8時間乾燥した結果、3.82gの重合体が得られた。重合体の溶融点は、102.2℃、メルトインデクスは、0.327、密度は、0.9056g/ccであって、ゲルクロマトグラフィーによる分析時、重量平均分子量(Mw)が131,700g/mol、分子量分布(Mw/Mn)が2.92であって、1−オクテンの含量が12.9重量%であった。
Claims (11)
- 下記化学式1の遷移金属化合物。
[化1]
[化学式1]
式中、Mは、周期律表上、4族の遷移金属であり、
Cpは、Mとη5−結合できるシクロペンタジエニル環、またはシクロペンタジエニル環を含む融合環であって、前記シクロペンタジエニル環またはシクロペンタジエニル融合環は、(C1〜C20)アルキル基、(C6〜C30)アリール基、(C2〜C20)アルケニル基、(C6〜C30)アリール(C1〜C20)アルキル基でさらに置換できて、
R1及びR2は、互いに独立して、水素原子、(C1〜C20)アルキル基、(C3〜C20)シクロアルキル基、(C6〜C30)アリール基、(C1〜C20)アルキル(C6〜C30)アリール基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換シリル基、(C6〜C30)アリール基、(C6〜C30)アリール(C1〜C10)アルキル基、(C1〜C20)アルコキシ基、(C1〜C20)アルキル置換または(C6〜C20)アリール置換シロキシ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換アミノ基、C1〜C20)アルキル置換または(C6〜C30)アリール置換ホスフィド基、(C1〜C20)アルキル置換メルカプト基、または、ニトロ基であり、
R3及びR4は、互いに独立して、水素原子、(C1〜C20)アルキル基、(C3〜C20)シクロアルキル基、(C6〜C30)アリール基、(C1〜C20)アルキル(C6〜C30)アリール基、または、(C6〜C30)アリール(C1〜C20)アルキル基であって、
aは、1または2の整数であり、
nは、1または2の整数であって、
Xは、互いに独立して、ハロゲン原子、(C1〜C20)アルキル基、(C3〜C20)シクロアルキル基、(C6〜C30)アリール(C1〜C20)アルキル基、(C1〜C20)アルコキシ基、(C3〜C20)アルキルシロキシ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換アミノ基、(C1〜C20)アルキル置換または(C6〜C30)アリール置換ホスフィン基、及び(C1〜C20)アルキル置換メルカプト基からなる群から選択される。 - 前記Mは、チタニウム、ジルコニウム、またはハフニウムであることを特徴とする、請求項1に記載の遷移金属化合物。
- 前記Cpは、シクロペンタジエニルまたはペンタメチルシクロペンタジエニルであることを特徴とする、請求項1に記載の遷移金属化合物。
- Xは、塩素、メチル基、メトキシ基、イソプロポキシ基及びジメチルアミノ基からなる群から選択されることを特徴とする、請求項1に記載の遷移金属化合物。
- 請求項1〜4のいずれかの項に記載の遷移金属化合物と、
アルキルアルミノキサンまたは有機アルミニウム助触媒、ホウ素化合物助触媒、または、これらの混合物と、
を含むエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造用遷移金属触媒組成物。 - 前記アルキルアルミノキサンまたは有機アルミニウム助触媒は、メチルアルミノキサン、改良メチルアルミノキサン、テトライソブチルアルミノキサン、トリアルキルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、または、これらの混合物から選択されることを特徴とする、請求項5に記載のエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造用遷移金属触媒組成物。
- 前記遷移金属と前記助触媒の比率は、遷移金属(M):アルミニウムのモル比を基準に、1:50〜1:5,000の範囲であることを特徴とする、請求項5または6に記載のエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造用遷移金属触媒組成物。
- 前記ホウ素化合物助触媒は、N,N−ジメチルアニリニウムテトラキスペンタフルオロフェニルボレート、トリフェニルメチリニウムテトラキスペンタフルオロフェニルボレート、または、これらの混合物から選択されることを特徴とする、請求項5に記載のエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造用遷移金属触媒組成物。
- 前記遷移金属化合物と助触媒の比率が、遷移金属(M):ホウ素原子:アルミニウム原子のモル比を基準に、1:0.5〜5:10〜500の範囲であることを特徴とする、請求項5または8に記載のエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造用遷移金属触媒組成物。
- 請求項5に記載の遷移金属触媒組成物を用いたエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造方法であって、
前記エチレンと重合される共単量体は、プロピレン、1−ブテン、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−オクタデセン、 及び1−エイコセンから選択された1種以上であり、前記エチレンと前記α−オレフィンとの共重合体中のエチレンの含量は、60〜99重量%であることを特徴とする、エチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造方法 。 - 前記エチレン単量体の反応器内の圧力は、6〜150気圧であり、重合反応温度は、60〜250℃であることを特徴とする、請求項10に記載のエチレン単独重合体またはエチレンとα−オレフィンとの共重合体の製造方法 。
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