JP6441332B2 - ハロゲン化ビス−フェニルフェノキシ触媒を使用するポリオレフィンの分子量制御 - Google Patents
ハロゲン化ビス−フェニルフェノキシ触媒を使用するポリオレフィンの分子量制御 Download PDFInfo
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- JP6441332B2 JP6441332B2 JP2016524204A JP2016524204A JP6441332B2 JP 6441332 B2 JP6441332 B2 JP 6441332B2 JP 2016524204 A JP2016524204 A JP 2016524204A JP 2016524204 A JP2016524204 A JP 2016524204A JP 6441332 B2 JP6441332 B2 JP 6441332B2
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- olefin
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- hydrocarbyl
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- -1 bis-phenylphenoxy Chemical class 0.000 title claims description 121
- 239000003054 catalyst Substances 0.000 title claims description 61
- 229920000098 polyolefin Polymers 0.000 title description 5
- 238000004260 weight control Methods 0.000 title description 2
- 239000003446 ligand Substances 0.000 claims description 64
- 239000004711 α-olefin Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- 239000005977 Ethylene Substances 0.000 claims description 30
- 229920001519 homopolymer Polymers 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 27
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 23
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052735 hafnium Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 125000005647 linker group Chemical group 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 125000004607 1,2,3,4-tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 89
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 239000000203 mixture Substances 0.000 description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- 239000007787 solid Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000013058 crude material Substances 0.000 description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000012267 brine Substances 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- DVZWQGLVEOWFOU-UHFFFAOYSA-N C[Hf]C Chemical compound C[Hf]C DVZWQGLVEOWFOU-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000003818 flash chromatography Methods 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- YULPSMQVAPNEIB-UHFFFAOYSA-N 2,7-ditert-butyl-9-[2-(oxan-2-yloxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl]carbazole Chemical compound C1CCCOC1OC=1C(N2C3=CC(=CC=C3C3=CC=C(C=C32)C(C)(C)C)C(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=CC=1B1OC(C)(C)C(C)(C)O1 YULPSMQVAPNEIB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 3
- ZPKIIVSSIUVJSM-UHFFFAOYSA-N BrCCCOC1=C(C=C(C=C1I)F)F Chemical compound BrCCCOC1=C(C=C(C=C1I)F)F ZPKIIVSSIUVJSM-UHFFFAOYSA-N 0.000 description 3
- PITYNBOSIPMCLH-UHFFFAOYSA-N Fc1ccc(OCCCOc2c(F)cc(F)cc2I)c(I)c1 Chemical compound Fc1ccc(OCCCOc2c(F)cc(F)cc2I)c(I)c1 PITYNBOSIPMCLH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- IQZRYLWTCFMYIP-UHFFFAOYSA-N 1-(3-bromopropoxy)-4-fluoro-2-iodobenzene Chemical compound FC1=CC=C(OCCCBr)C(I)=C1 IQZRYLWTCFMYIP-UHFFFAOYSA-N 0.000 description 2
- 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- AIJQYPOGTRNCHQ-UHFFFAOYSA-N 4-fluoro-2-iodo-6-methylphenol Chemical compound CC1=CC(F)=CC(I)=C1O AIJQYPOGTRNCHQ-UHFFFAOYSA-N 0.000 description 2
- FTTVHYAABUMDNX-UHFFFAOYSA-N 4-fluoro-2-iodophenol Chemical compound OC1=CC=C(F)C=C1I FTTVHYAABUMDNX-UHFFFAOYSA-N 0.000 description 2
- JJRQFJGUSLIDNM-UHFFFAOYSA-N 5-fluoro-2-[3-(4-fluoro-2-iodophenoxy)propoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(F)=CC(I)=C1OCCCOC1=CC=C(F)C=C1I JJRQFJGUSLIDNM-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- UGVVIPAIDGTTNN-UHFFFAOYSA-N C[Zr]C Chemical compound C[Zr]C UGVVIPAIDGTTNN-UHFFFAOYSA-N 0.000 description 2
- RFZOLBWUILFYIZ-UHFFFAOYSA-N Cc1cc(F)cc(I)c1OCCCOc1c(F)cc(F)cc1I Chemical compound Cc1cc(F)cc(I)c1OCCCOc1c(F)cc(F)cc1I RFZOLBWUILFYIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 241000183024 Populus tremula Species 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- ACXNSKYDNPWWAG-UHFFFAOYSA-N 1,2-ditert-butyl-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(C(C)(C)C)C(C(C)(C)C)=C3NC2=C1 ACXNSKYDNPWWAG-UHFFFAOYSA-N 0.000 description 1
- MDMTWWABYVCEOM-UHFFFAOYSA-N 1,5-dichloro-2-[3-(2,4-dichloro-6-iodophenoxy)propoxy]-3-iodobenzene Chemical compound IC1=CC(Cl)=CC(Cl)=C1OCCCOC1=C(Cl)C=C(Cl)C=C1I MDMTWWABYVCEOM-UHFFFAOYSA-N 0.000 description 1
- DNTJGBIQTKFVRH-UHFFFAOYSA-N 2,4-difluoro-6-iodophenol Chemical compound OC1=C(F)C=C(F)C=C1I DNTJGBIQTKFVRH-UHFFFAOYSA-N 0.000 description 1
- IMLFTFFRHKAQCM-UHFFFAOYSA-N 2,7-ditert-butyl-9-[2-(oxan-2-yloxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl]carbazole Chemical compound C12=CC(C(C)(C)C)=CC=C2C2=CC=C(C(C)(C)C)C=C2N1C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OC1CCCCO1 IMLFTFFRHKAQCM-UHFFFAOYSA-N 0.000 description 1
- OPPJMEZERJEHPN-UHFFFAOYSA-N 2-(2,7-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(2,7-ditert-butylcarbazol-9-yl)-2-(3-fluoro-5-methylphenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-fluoro-3-methylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(=CC(=C1)F)C2=CC(=CC(C2(O)OCCCOC3=C(C=C(C=C3C)F)C4=C(C(=CC(=C4)C(C)(C)CC(C)(C)C)N5C6=C(C=CC(=C6)C(C)(C)C)C7=C5C=C(C=C7)C(C)(C)C)O)N8C9=C(C=CC(=C9)C(C)(C)C)C1=C8C=C(C=C1)C(C)(C)C)C(C)(C)CC(C)(C)C OPPJMEZERJEHPN-UHFFFAOYSA-N 0.000 description 1
- NMXLXQGHBSPIDR-UHFFFAOYSA-N 2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCCO1 NMXLXQGHBSPIDR-UHFFFAOYSA-N 0.000 description 1
- QTLLJEKQHSHZBV-UHFFFAOYSA-N 2-[2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy]oxane Chemical compound IC1=CC(C(C)(C)CC(C)(C)C)=CC=C1OC1OCCCC1 QTLLJEKQHSHZBV-UHFFFAOYSA-N 0.000 description 1
- AVACKPMKMKQZIL-UHFFFAOYSA-N 2-[3-(2,4-difluoro-6-iodophenoxy)propoxy]-1,5-difluoro-3-iodobenzene Chemical compound IC1=CC(F)=CC(F)=C1OCCCOC1=C(F)C=C(F)C=C1I AVACKPMKMKQZIL-UHFFFAOYSA-N 0.000 description 1
- HNKYVRUWHVIXRI-UHFFFAOYSA-N 2-fluoro-6-phenyl-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound FC1=C(C(=CC(=C1)C(C)(CC(C)(C)C)C)C1=CC=CC=C1)O HNKYVRUWHVIXRI-UHFFFAOYSA-N 0.000 description 1
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 1
- YGIUULANRZOBSB-UHFFFAOYSA-N 4-fluoro-1-[3-(4-fluoro-2-iodophenoxy)propoxy]-2-iodobenzene Chemical compound IC1=CC(F)=CC=C1OCCCOC1=CC=C(F)C=C1I YGIUULANRZOBSB-UHFFFAOYSA-N 0.000 description 1
- NRZLMVMAZOJHAP-UHFFFAOYSA-N 5-fluoro-2-[3-(4-fluoro-2-iodo-6-methylphenoxy)propoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(F)=CC(I)=C1OCCCOC1=C(C)C=C(F)C=C1I NRZLMVMAZOJHAP-UHFFFAOYSA-N 0.000 description 1
- JYNMSEHISHIDHO-UHFFFAOYSA-N 6-(2,7-ditert-butylcarbazol-9-yl)-3-[3-[2-[3-(2,7-ditert-butylcarbazol-9-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]-4-fluorophenoxy]propoxy]-2-(3-fluorophenyl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC(=C(C(=C1)N2C3=C(C=CC(=C3)C(C)(C)C)C4=C2C=C(C=C4)C(C)(C)C)O)C5=C(C=CC(=C5)F)OCCCOC6=C(C(=C(C=C6C(C)(C)CC(C)(C)C)N7C8=C(C=CC(=C8)C(C)(C)C)C9=C7C=C(C=C9)C(C)(C)C)O)C1=CC(=CC=C1)F JYNMSEHISHIDHO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JZVJYPZEYAYLGN-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC=CC(=C1)F)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC=CC(=C1)F)O JZVJYPZEYAYLGN-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003289 ascorbyl group Chemical group [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229940045348 brown mixture Drugs 0.000 description 1
- 238000006758 bulk electrolysis reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000593 indol-1-yl group Chemical group [H]C1=C([H])C([H])=C2N([*])C([H])=C([H])C2=C1[H] 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000004254 isoquinolin-1-yl group Chemical group [H]C1=C([H])C2=C([H])C([H])=C([H])C([H])=C2C(*)=N1 0.000 description 1
- 125000004552 isoquinolin-4-yl group Chemical group C1=NC=C(C2=CC=CC=C12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- 125000004549 quinolin-4-yl group Chemical group N1=CC=C(C2=CC=CC=C12)* 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DHHKPEUQJIEKOA-UHFFFAOYSA-N tert-butyl 2-[6-(nitromethyl)-6-bicyclo[3.2.0]hept-3-enyl]acetate Chemical compound C1C=CC2C(CC(=O)OC(C)(C)C)(C[N+]([O-])=O)CC21 DHHKPEUQJIEKOA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Crystallography & Structural Chemistry (AREA)
Description
本出願は、2013年6月28日に出願した米国特許仮出願第61/840,624号の利益を主張し、その全体が参照として本明細書に組み込まれる。
本明細書下記に示される化学名及び式構造を有する一連の触媒を使用して、エチレン/1−オクテン共重合を実施する。
この実施例7は、試料触媒の調製を例示する。当業者は、同様及び類似した方法を実施して、本発明の使用に適した他の触媒を調製できることを理解する。各生成物の確認には、1H NMR及び19F NMRを実施する。
(a)ステップ1:2−(3−ブロモプロポキシ)−1,5−ジフルオロ−3−ヨードベンゼンの調製
(b)ステップ2:1,5−ジフルオロ−2−(3−(4−フルオロ−2−ヨードフェノキシ)プロポキシ)−3−ヨードベンゼンの調製
(c)ステップ3:3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−2′−(3−((3′−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−フルオロ−2′−ヒドロキシ−5′−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−イル)オキシ)プロポキシ)−3′,5′−ジフルオロ−5−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−オールの調製
(d)ステップ4:金属配位子錯体の形成
触媒4を以下のようにして調製する。
(a)ステップ1:2,7−ジ−tert−ブチル−9−(2−((テトラヒドロ−2H−ピラン−2−イル)オキシ)−5−(2,4,4−トリメチルペンタン−2−イル)フェニル)−9H−カルバゾールの調製
(b)ステップ2:2,7−ジ−tert−ブチル−9−(2−((テトラヒドロ−2H−ピラン−2−イル)オキシ)−3−(4,4,5,5−テトラメチル−1,3,2−ジオキサボロラン−2−イル)−5−(2,4,4−トリメチルペンタン−2−イル)フェニル)−9H−カルバゾールの調製
(c)ステップ3:6′,6″−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3′−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−オール)の調製
(d)ステップ4:金属配位子錯体の形成
(a)ステップ1:3−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−2′−(3−((3′−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−フルオロ−2′−ヒドロキシ−5′−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−イル)オキシ)プロポキシ)−3′,5′−ジフルオロ−5−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−オールの調製
(b)ステップ2:金属配位子錯体の形成
(a)ステップ1:1−(3−ブロモプロポキシ)−4−フルオロ−2−ヨードベンゼンの調製
(b)ステップ2:5−フルオロ−2−(3−(4−フルオロ−2−ヨードフェノキシ)プロポキシ)−1−ヨード−3−メチルベンゼンの調製
(c)ステップ3:3−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−2′−(3−((3′−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−フルオロ−2′−ヒドロキシ−5′−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−イル)オキシ)プロポキシ)−5′−フルオロ−3′−メトキシ−5−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−オールの調製
(d)ステップ3:金属配位子錯体の形成
(a)ステップ1:2−(3−(2,4−ジフルオロ−6−ヨードフェノキシ)プロポキシ)−5−フルオロ−1−ヨード−3−メチルベンゼンの調製
(b)ステップ2:3−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−2′−(3−((3′−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3,5−ジヒドロ−2′−ヒドロキシ−5′−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−イル)オキシ)プロポキシ)−5′−フルオロ−3′−メトキシ−5−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−オールの調製
(c)ステップ3:金属配位子錯体の形成
(a)ステップ1:2′,2″−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(2,7−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5′−フルオロ−3′−メチル−5−(2,4,4−トリメチルペンタン−2−イル)−[1,1′−ビフェニル]−2−オール)の調製
(b)ステップ2:金属配位子錯体の形成
(a)ステップ1:配位子の調製
(b)ステップ2:金属配位子錯体の形成
触媒9のフルオロ類縁体の調製:
(a)ステップ1:配位子の調製
(b)ステップ2:金属配位子錯体の形成
本発明は、以下の態様を含む。
[1]
オレフィンホモポリマーまたはコポリマーを調製する方法であって、前記方法は、
エチレン、アルファ−オレフィン、またはこれらの組み合わせと、下記式の触媒量の金属配位子錯体触媒であって、
式中、Mは、チタン、ジルコニウム、またはハフニウムであり、それぞれ独立して、+2、+3、または+4のホルマール酸化状態であり、
nは、0〜3の整数であり、nが0の場合、Xは不在であり、
各Xは、独立して、中性、一価アニオン性、もしくは二価アニオン性である単座配位配位子であるか、または2つのXは、一緒になって、中性、一価アニオン性、もしくは二価アニオン性である二座配位配位子を形成し、
X及びnは、金属配位子錯体が中性になるように選択され、
各Z部分は、独立して、O、S、N(C 1 −C 40 )ヒドロカルビル、またはP(C 1 −C 40 )ヒドロカルビルであり、
Lは、(C 1 −C 40 )ヒドロカルビレンまたは(C 1 −C 40 )ヘテロヒドロカルビレンであるが、Z部分を連結している2〜8炭素原子のリンカー主鎖を含む部分を有することが条件であり、そのような2〜8原子のリンカーの各原子は、独立して、炭素原子またはヘテロ原子であり、各ヘテロ原子は、独立して、O、S、S(O)、S(O) 2 、Si(R C ) 2 、Ge(R C ) 2 、P(R P )、またはN(R N )であり、
R 1a 、R 1b 、またはその両方は、ハロゲン原子であり、
R 2a 、R 3a 、R 4a 、R 2b 、R 3b 、R 4b 、R 6c 、R 7c 、R 8c 、R 6d 、R 7d 、及びR 8d は、独立して、水素原子、(C 1 −C 40 )ヒドロカルビル、(C 1 −C 40 )ヘテロヒドロカルビル、Si(R C ) 3 、Ge(R C ) 3 、P(R P ) 2 、N(R N ) 2 、OR C 、SR C 、NO 2 、CN、F 3 C、F 3 CO、RCS(O)−、RCS(O) 2 −、(RC) 2 C=N−、RCC(O)O−、RCOC(O)−、RCC(O)N(R)−、(RC)2NC(O)−、またはハロゲン原子であり、各R 5c 及びR 5d は、独立して、(C 6 −C 40 )アリールまたは(C 1 −C 40 )ヘテロアリールであり、アリール、ヘテロアリール、ヒドロカルビル、ヘテロヒドロカルビル、ヒドロカルビレン、及びヘテロヒドロカルビレン基のそれぞれは、独立して、非置換であるか、または1つ以上の置換基R S で置換されており、各R S は、独立して、ハロゲン原子、ポリフルオロ置換、ペルフルオロ置換、非置換(C 1 −C 18 )アルキル、F 3 C−、FCH 2 O−、F 2 HCO−、F 3 CO−、R 3 Si−、R 3 Ge−、RO−、RS−、RS(O)−、RS(O) 2 −、R 2 P−、R 2 N−、R 2 C=N−、NC−、RC(O)O−、ROC(O)−、RC(O)N(R)−、もしくはR 2 NC(O)−であり、またはR S のうちの2つは、一緒になって、非置換(C 1 −C 18 )アルキレンを形成し、各Rは、独立して非置換(C 1 −C 18 )アルキルである、金属配位子錯体触媒とを、
エチレンホモポリマー、アルファ−オレフィンホモポリマー、またはエチレン/アルファ−オレフィンコポリマーが形成されるような条件下で接触させることを含み、
R 1a もR 1b もハロゲン原子ではないこと以外は同一である触媒による同一の条件下で調製された、それ以外は同一のエチレンホモポリマー、アルファ−オレフィンホモポリマー、またはエチレン/アルファ−オレフィンコポリマーと比較したとき、少なくとも20パーセント低減されている重量平均分子量を有する、前記方法。
[2]
R 1a 、R 1b 、またはその両方が、フッ素、塩素、ヨウ素、及びこれらの組み合わせから選択されるハロゲン原子である、[1]に記載の前記方法。
[3]
R 5c 及びR 5d が、独立して、1,2,3,4−テトラヒドロナフチル、アントラセニル、1,2,3,4−テトラヒドロアントラセニル、1,2,3,4,5,6,7,8−オクタヒドロアントラセニル、フェナントレニル、1,2,3,4,5,6,7,8−オクタヒドロフェナントレニル、2,6−ジメチルフェニル、2,6−ジイソプロピルフェニル、3,5−ジ(第三級−ブチル)フェニル、3,5−ジフェニルフェニル、1−ナフチル、2−メチル−1−ナフチル、2−ナフチル、1,2,3,4−テトラ−ヒドロナフサ−5−イル、1,2,3,4−テトラヒドロナフサ−6−イル、アントラセン−9−イル、1,2,3,4−テトラヒドロアントラセン−9−イル、1,2,3,4,5,6,7,8−オクタヒドロアントラセン−9−イル、1,2,3,4,5,6,7,8−オクタヒドロフェナントレン−9−イル、インドリル、インドリニル、キノリニル、1,2,3,4−テトラヒドロキノリニル、イソキノリニル、1,2,3,4−テトラヒドロイソキノリニル、カルバゾリル、1,2,3,4−テトラヒドロカルバゾリル、1,2,3,4,5,6,7,8−オクタヒドロカルバゾリル、3,6−ジ(第三級−ブチル)−カルバゾール−9−イル、3,6−ジ(第三級−オクチル)−カルバゾール−9−イル、3,6−ジフェニルカルバゾール−9−イル、3,6−ビス(2,4,6−トリメチルフェニル)−カルバゾール−9−イル、2,7−ジ(第三級−ブチル)−カルバゾール−9−イル、2,7−ジ(第三級−オクチル)−カルバゾール−9−イル、2,7−ジフェニルカルバゾール−9−イル、及び2,7−ビス(2,4,6−トリメチルフェニル)−カルバゾール−9−イルから独立して選択される、[1]または[2]に記載の前記方法。
[4]
前記アルファ−オレフィンが、3〜12個の炭素を有する直鎖アルファオレフィン、5〜16個の炭素を有する分岐鎖アルファ−オレフィン、及びこれらの組み合わせからなる群から選択される、[1]〜[3]のいずれか一項に記載の前記方法。
[5]
前記重量平均分子量が少なくとも20パーセント低減される、[1]〜[4]のいずれか一項に記載の前記方法。
Claims (3)
- オレフィンホモポリマーまたはコポリマーを調製する方法であって、前記方法は、
エチレン、アルファ−オレフィン、またはこれらの組み合わせと、下記式の触媒量の金属配位子錯体触媒であって、
式中、Mは、チタン、ジルコニウム、またはハフニウムであり、それぞれ独立して、+2、+3、または+4のホルマール酸化状態であり、
nは、0〜3の整数であり、nが0の場合、Xは不在であり、
各Xは、独立して、中性、一価アニオン性、もしくは二価アニオン性である単座配位配位子であるか、または2つのXは、一緒になって、中性、一価アニオン性、もしくは二価アニオン性である二座配位配位子を形成し、
X及びnは、金属配位子錯体が中性になるように選択され、
各Z部分は、独立して、O、S、N(C1−C40)ヒドロカルビル、またはP(C1−C40)ヒドロカルビルであり、
Lは、(C1−C40)ヒドロカルビレンまたは(C1−C40)ヘテロヒドロカルビレンであるが、Z部分を連結している2〜8炭素原子のリンカー主鎖を含む部分を有することが条件であり、そのような2〜8原子のリンカーの各原子は、独立して、炭素原子またはヘテロ原子であり、各ヘテロ原子は、独立して、O、S、S(O)、S(O)2、Si(RC)2、Ge(RC)2、P(RP)、またはN(RN)であり、独立して、各RCは非置換(C1−C18)ヒドロカルビルであり、または2つのRCは、一緒になって、(C2−C 19 )アルキレンを形成し、各RPは、非置換(C1−C18)ヒドロカルビルであり、各RNは、非置換(C1−C18)ヒドロカルビル、水素原子、または不在であり、
R1a、R1b、またはその両方は、ハロゲン原子であり、
R2a、R3a、R4a、R2b、R3b、R4b、R6c、R7c、R8c、R6d、R7d、及びR8dは、独立して、水素原子、(C1−C40)ヒドロカルビル、(C1−C40)ヘテロヒドロカルビル、Si(RC)3、Ge(RC)3、P(RP)2、N(RN)2、ORC、SRC、NO2、CN、F3C、F3CO、RCS(O)−、RCS(O)2−、(RC)2C=N−、RCC(O)O−、RCOC(O)−、RCC(O)N(R)−、(RC)2NC(O)−、またはハロゲン原子であり、
R5c及びR5dは、独立して、1,2,3,4−テトラヒドロナフチル、アントラセニル、1,2,3,4−テトラヒドロアントラセニル、1,2,3,4,5,6,7,8−オクタヒドロアントラセニル、フェナントレニル、1,2,3,4,5,6,7,8−オクタヒドロフェナントレニル、2,6−ジメチルフェニル、2,6−ジイソプロピルフェニル、3,5−ジ(第三級−ブチル)フェニル、3,5−ジフェニルフェニル、1−ナフチル、2−メチル−1−ナフチル、2−ナフチル、1,2,3,4−テトラ−ヒドロナフサ−5−イル、1,2,3,4−テトラヒドロナフサ−6−イル、アントラセン−9−イル、1,2,3,4−テトラヒドロアントラセン−9−イル、1,2,3,4,5,6,7,8−オクタヒドロアントラセン−9−イル、1,2,3,4,5,6,7,8−オクタヒドロフェナントレン−9−イル、インドリル、インドリニル、キノリニル、1,2,3,4−テトラヒドロキノリニル、イソキノリニル、1,2,3,4−テトラヒドロイソキノリニル、カルバゾリル、1,2,3,4−テトラヒドロカルバゾリル、1,2,3,4,5,6,7,8−オクタヒドロカルバゾリル、2,7−ジ(第三級−ブチル)−カルバゾール−9−イル、2,7−ジ(第三級−オクチル)−カルバゾール−9−イル、2,7−ジフェニルカルバゾール−9−イル、又は2,7−ビス(2,4,6−トリメチルフェニル)−カルバゾール−9−イルから選択され、
エチレンホモポリマー、アルファ−オレフィンホモポリマー、またはエチレン/アルファ−オレフィンコポリマーが形成されるような条件下で接触させることを含み、
R1aもR1bもハロゲン原子ではないこと以外は同一である触媒による同一の条件下で調製された、それ以外は同一のエチレンホモポリマー、アルファ−オレフィンホモポリマー、またはエチレン/アルファ−オレフィンコポリマーと比較したとき、少なくとも20パーセント低減されている重量平均分子量を有する、前記方法。 - R1a、R1b、またはその両方が、フッ素、塩素、ヨウ素、又はこれらの組み合わせから選択されるハロゲン原子である、請求項1に記載の前記方法。
- 前記アルファ−オレフィンが、3〜12個の炭素を有する直鎖アルファオレフィン、5〜16個の炭素を有する分岐鎖アルファ−オレフィン、及びこれらの組み合わせからなる群から選択される、請求項1または2に記載の前記方法。
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ES2934177T3 (es) | 2023-02-17 |
EP3013871B1 (en) | 2022-10-19 |
WO2014210333A1 (en) | 2014-12-31 |
KR102218415B1 (ko) | 2021-02-22 |
JP6813556B2 (ja) | 2021-01-13 |
JP2016524024A (ja) | 2016-08-12 |
EP3925989A1 (en) | 2021-12-22 |
CN105283474A (zh) | 2016-01-27 |
US20170158790A1 (en) | 2017-06-08 |
JP2019049003A (ja) | 2019-03-28 |
US9605098B2 (en) | 2017-03-28 |
SG10201802443VA (en) | 2018-05-30 |
SG11201510689SA (en) | 2016-01-28 |
BR112015030912A8 (pt) | 2020-01-28 |
KR20160037890A (ko) | 2016-04-06 |
BR112015030912A2 (pt) | 2017-07-25 |
BR112015030912B1 (pt) | 2021-08-03 |
US20160108156A1 (en) | 2016-04-21 |
US10144791B2 (en) | 2018-12-04 |
EP3013871A1 (en) | 2016-05-04 |
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