JP2021507938A - アミジン及びチオフェン縮合されたシクロペンタジエニル配位子を含む金属錯体 - Google Patents
アミジン及びチオフェン縮合されたシクロペンタジエニル配位子を含む金属錯体 Download PDFInfo
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- JP2021507938A JP2021507938A JP2020554377A JP2020554377A JP2021507938A JP 2021507938 A JP2021507938 A JP 2021507938A JP 2020554377 A JP2020554377 A JP 2020554377A JP 2020554377 A JP2020554377 A JP 2020554377A JP 2021507938 A JP2021507938 A JP 2021507938A
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- 239000003446 ligand Substances 0.000 title claims abstract description 39
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims description 46
- 150000004696 coordination complex Chemical class 0.000 title claims description 36
- 229930192474 thiophene Natural products 0.000 title claims description 21
- 150000001409 amidines Chemical class 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 125000000129 anionic group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 88
- 229910052757 nitrogen Inorganic materials 0.000 claims description 63
- 239000000460 chlorine Substances 0.000 claims description 56
- 239000010936 titanium Substances 0.000 claims description 48
- 229910052719 titanium Inorganic materials 0.000 claims description 46
- 239000007795 chemical reaction product Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 13
- 229910052731 fluorine Chemical group 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 239000002516 radical scavenger Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000002466 imines Chemical class 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 7
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000011737 fluorine Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229910052752 metalloid Inorganic materials 0.000 claims description 2
- 150000002738 metalloids Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 166
- -1 alkyl C 6 Chemical compound 0.000 description 144
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 120
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 103
- 230000015572 biosynthetic process Effects 0.000 description 89
- 238000003786 synthesis reaction Methods 0.000 description 89
- 238000005481 NMR spectroscopy Methods 0.000 description 85
- 239000000203 mixture Substances 0.000 description 84
- 239000000243 solution Substances 0.000 description 79
- 125000001544 thienyl group Chemical group 0.000 description 68
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 67
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- 239000011734 sodium Substances 0.000 description 33
- 239000000284 extract Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000843 powder Substances 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000000725 suspension Substances 0.000 description 23
- 125000003963 dichloro group Chemical group Cl* 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 19
- 239000012074 organic phase Substances 0.000 description 19
- 239000003480 eluent Substances 0.000 description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 17
- 238000003818 flash chromatography Methods 0.000 description 17
- 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 16
- 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 16
- 239000011541 reaction mixture Substances 0.000 description 15
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 14
- 229940086542 triethylamine Drugs 0.000 description 13
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 12
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 12
- 150000001639 boron compounds Chemical class 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 239000007983 Tris buffer Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- WDIQDTMXPVOLTE-UHFFFAOYSA-N (2,6-difluorophenyl)-piperidin-1-ylmethanimine Chemical compound FC1=C(C(=CC=C1)F)C(=N)N1CCCCC1 WDIQDTMXPVOLTE-UHFFFAOYSA-N 0.000 description 7
- IFMWVBVPVXRZHE-UHFFFAOYSA-M chlorotitanium(3+);propan-2-olate Chemical compound [Cl-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-] IFMWVBVPVXRZHE-UHFFFAOYSA-M 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- ZXDCRXXSBDHEFS-UHFFFAOYSA-N 2-(2,6-dimethylphenyl)-3h-isoindol-1-imine Chemical compound CC1=CC=CC(C)=C1N1C(=N)C2=CC=CC=C2C1 ZXDCRXXSBDHEFS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 5
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- NBLTYPTZIVHODY-UHFFFAOYSA-M magnesium;1,3-ditert-butylbenzene-5-ide;bromide Chemical compound [Mg+2].[Br-].CC(C)(C)C1=C[C-]=CC(C(C)(C)C)=C1 NBLTYPTZIVHODY-UHFFFAOYSA-M 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 150000004291 polyenes Chemical class 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 5
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 5
- 150000003613 toluenes Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- GUWYGSXMGQDGGC-UHFFFAOYSA-N 2-bromo-3,4,5,6-tetramethyl-4H-cyclopenta[b]thiophene Chemical compound BrC1=C(C2=C(S1)C(=C(C2C)C)C)C GUWYGSXMGQDGGC-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002585 base Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UARDWXPTHFQYJK-UHFFFAOYSA-K trichlorotitanium(1+) Chemical compound Cl[Ti+](Cl)Cl UARDWXPTHFQYJK-UHFFFAOYSA-K 0.000 description 4
- KZKRRZFCAYOXQE-UHFFFAOYSA-N 1$l^{2}-azinane Chemical group C1CC[N]CC1 KZKRRZFCAYOXQE-UHFFFAOYSA-N 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YJBDELSSANQBHH-UHFFFAOYSA-N 2,3,5-trimethyl-4,5-dihydrocyclopenta[b]thiophen-6-one Chemical compound CC1=C(C2=C(S1)C(C(C2)C)=O)C YJBDELSSANQBHH-UHFFFAOYSA-N 0.000 description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- 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 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 150000001767 cationic compounds Chemical class 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000008282 halocarbons Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 150000002892 organic cations Chemical class 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- VTFCTROSJUESLK-UHFFFAOYSA-N 1,2,3-trimethyl-2,3-dihydro-1h-indene Chemical compound C1=CC=C2C(C)C(C)C(C)C2=C1 VTFCTROSJUESLK-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
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- 239000011777 magnesium Substances 0.000 description 1
- BXBLTKZWYAHPKM-UHFFFAOYSA-M magnesium;methanidyl(trimethyl)silane;chloride Chemical compound [Mg+2].[Cl-].C[Si](C)(C)[CH2-] BXBLTKZWYAHPKM-UHFFFAOYSA-M 0.000 description 1
- QGEFGPVWRJCFQP-UHFFFAOYSA-M magnesium;methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC=C1 QGEFGPVWRJCFQP-UHFFFAOYSA-M 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- BVUQKCCKUOSAEV-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=[C-]C=C1 BVUQKCCKUOSAEV-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- MAXITDLNHAIZJS-UHFFFAOYSA-N n'-piperidin-1-ylbenzenecarboximidamide Chemical compound C=1C=CC=CC=1C(/N)=N/N1CCCCC1 MAXITDLNHAIZJS-UHFFFAOYSA-N 0.000 description 1
- IOSLYUNCRQCACW-UHFFFAOYSA-N n,n-di(propan-2-yl)benzenecarboximidamide Chemical compound CC(C)N(C(C)C)C(=N)C1=CC=CC=C1 IOSLYUNCRQCACW-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 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
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- FLALGSYYVIWTFQ-UHFFFAOYSA-K propan-2-olate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CC(C)O[Ti+3] FLALGSYYVIWTFQ-UHFFFAOYSA-K 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940054334 silver cation Drugs 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XMRSTLBCBDIKFI-UHFFFAOYSA-N tetradeca-1,13-diene Chemical compound C=CCCCCCCCCCCC=C XMRSTLBCBDIKFI-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- LWRYDHOHXNQTSK-UHFFFAOYSA-N thiophene oxide Chemical compound O=S1C=CC=C1 LWRYDHOHXNQTSK-UHFFFAOYSA-N 0.000 description 1
- 125000005607 tigloyl group Chemical group 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-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
- 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
- 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/045—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated conjugated hydrocarbons other than butadiene or isoprene
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- 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
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- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
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Abstract
Description
TCyLMZp (1)
(式中、
Mは、第4族の金属であり、
Zは、アニオン性配位子であり、
pは、1〜2、好ましくは2の数であり、
TCyは、式(2)
R1及びR2は、個別に、水素、ハロゲン、特にCl若しくはBr、C1〜C10−アルキル、C5〜C10−シクロアルキル、非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10−アリール、特にC1〜C4−アルキル又はC1〜C4−ジアルキルアミノ置換のフェニル及びSiR3、OR、NR2、SR、PR2(ここで、Rは、個別に、C1〜C10−アルキル、C5〜C10−シクロアルキル及び非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニルを意味する)の群から個別に選択され、特に、R1及びR2は、個別に、水素、ハロゲン、特にCl若しくはBr、C1〜C10−アルキル、C5〜C10−シクロアルキル、非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10−アリール、特にC1〜C4−アルキル又はC1〜C4−ジアルキルアミノ置換のフェニルの群から選択されるか、又は
R1及びR2は、それらが結合されているチオフェン環の2つの二重結合炭素原子と共に、非置換又はC1〜C4−アルキル置換の脂肪族C5〜C6−シクロアルケン環を形成し、
R3、R4及びR5は、個別に、水素、C1〜C4−アルキル、非置換又はC1〜C4−アルキル及び/若しくはハロゲン、特に塩素若しくはフッ素置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニル並びにSiR3、OR、NR2、SR、PR2(ここで、Rは、個別に、C1〜C10−アルキル、C5〜C10−シクロアルキル及び非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニルを意味する)の群から個別に選択され、好ましくは、R3、R4及びR5は、個別に、水素、C1〜C4−アルキル、非置換又はC1〜C4−アルキル及び/若しくはハロゲン、特に塩素若しくはフッ素置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニルの群から選択され、より好ましくは、基R3〜R5の少なくとも1つは、C1〜C4−アルキル、特にメチルを意味するべきである)
のチオフェン縮合されたシクロペンタジエニルタイプの配位子であり、及び
Lは、式(3)
Sub1は、非置換又はC1〜C4−アルキル置換及び/若しくはハロゲン、特に塩素若しくはフッ素置換のC6〜C10−芳香族置換基、特にフェニルであり、及び
Sub2は、第15族のヘテロ原子であって、それを通してSub2がイミンの炭素原子に結合される、ヘテロ原子を含む置換基であるか、又は
Sub1及びSub2は、それらが結合されているイミノ基と共に、式(3a)
アミジン環に縮合されたベンゾ環は、非置換であり得るか、又はさらなる置換基R7を含有し得、さらなる置換基R7は、個別に、水素、C1〜C4−アルキル及びハロゲンの群から選択される添え字「q」のものであり、それにより、qは、0〜4、好ましくは0〜2、最も好ましくは0の数であり、
Sub4は、第14族の原子であって、それを介してSub4がアミノ窒素原子N1に結合される、第14族の原子を含む脂肪族又は芳香族の環状又は直鎖状の置換基であり、好ましくは、Sub4は、非置換であるか、又はハロゲン、特にCl若しくはF及びC1〜C4−アルキルから選択される基からの1つ若しくは複数の置換基によって置換されるC6〜C10−芳香族環、好ましくはフェニルである)
の配位子を形成する)
のアミジネート配位子である)
の金属錯体を用いて達成される。
好ましい実施形態では、R1及びR2は、個別に、水素、C1〜C10−アルキル、C5〜C10−シクロアルキル及び非置換又はC1〜C10−アルキル置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニルの群から選択されるか、又はR1及びR2は、それらが結合されているチオフェン環の2つの二重結合炭素原子と共に、非置換又はC1〜C4−アルキル置換の脂肪族C5〜C6−シクロアルケン環を形成する。
好ましい実施形態では、第4族の金属Mは、チタン(Ti)、ジルコニウム(Zr)又はハフニウム(Hf)、最も好ましくはチタンである。
本明細書で使用するとき、「シクロペンタジエニルタイプの配位子」という用語は、それが慣用されている意味を広く包含し、すなわちπ型の結合を介して金属に結合され、通常、金属に対してη5−配位を取っている、5員の炭素環を有する置換された配位子を意味する。
nは、3〜4の数であり、及び
R6は、それぞれ個別に、添え字mのC1〜C4−アルキルを意味し、
mは、0〜4、好ましくは0〜2の数であり、且つR3、R4及びR5は、先に与えられた意味を有する)
のチオフェン縮合されたシクロペンタジエニルタイプの配位子である、式(1)の金属錯体である。
好ましい実施形態では、Zは、独立して、以下のものを意味する:ハロゲン原子、C1〜10アルキル基、C7〜20アラルキル基、C6〜20アリール基又はC1〜20炭化水素で置換されたアミノ基、C1〜20アルコシキ基、より好ましくはハロゲン原子及びC1〜10アルキル基、C7〜20アラルキル基、最も好ましくはCl、メチル、ベンジル、メチルトリメチルシリル。最も好ましいのは、Cl又はメチルである。pが1よりも大きい、すなわちp=2の場合、Zに与えられる意味は、独立している。p=2であり、両方のZが同一であることが好ましい。
そのような好ましいSub1の典型的な例は、式3によって表され、ここで、Sub1は、フェニル又は置換フェニル残基であり、好ましくは2,6−ジメチルフェニル、2,6−ジクロロフェニル又は2,6−ジフルオロフェニルである。
アミジン含有配位子(3a)は、イミンの窒素原子N2を介して金属Mと共有結合され、
アミジン環に縮合されたベンゾ環は、非置換であり得るか、又はさらなる置換基R7を含有し得、さらなる置換基R7は、個別に、水素、C1〜C4−アルキル及びハロゲンの群から選択される添え字「q」のものであり、それにより、qは、0〜4、好ましくは0〜2、最も好ましくは0の数であり、
Sub4は、第14族の原子であって、それを介してSub4がアミノ窒素原子N1に結合される、第14族の原子を含む脂肪族又は芳香族の環状又は直鎖状の置換基であり、好ましくは、Sub4は、非置換であるか、又はハロゲン、特にCl若しくはF及びC1〜C4−アルキル、特にメチルから選択される基からの1つ若しくは複数の置換基によって置換されるC6〜C10芳香族環、好ましくはフェニルである)
の配位子Lを有する、式(1)の金属錯体に関する。
(式中、Mは、Tiであり、
Zは、塩素、C1〜C4−アルキル及びC7〜20アラルキルからなる群から選択され、好ましくはメチル又はベンジルであり、
pは、2であり、
TCyは、R1及びR2が、他から独立して、水素、メチル、フェニル又はC1〜C4−アルキル置換のフェニルである、式(2)の配位子であり、
R3、R4及びR5は、他から独立して、水素、メチル、フルオロフェニル、i−プロピルフェニルであるか、又は
TCyは、m=0である、式(2a)の配位子である)
の金属錯体である。
本発明は、式(1)の金属錯体を製造するためのプロセスであって、式(3)
TCyMZp+1 (3)
の金属錯体は、式LHのアミジン又はそのハロゲン化水素酸塩LH・HZと反応され、ここで、Lは、請求項1〜6の少なくとも一項に記載の意味を有し、及びZは、ハロゲン、アラルキル又はアルコキシ、特にCl、ベンジル又はイソプロポキシルを意味する、プロセスにさらに関する。
a)本発明における式(1)の金属錯体、及び
b)活性化剤、及び
c)任意選択的に、捕捉剤
を含む触媒系もさらに提供する。
(C1)一般式BQ1Q2Q3で表されるホウ素化合物
(C2)一般式G(BQ1Q2Q3Q4)で表されるホウ素化合物
(C3)一般式(J−H)(BQ1Q2Q3Q4)で表されるホウ素化合物
(E1)一般式T1 aAlZ3−aで表されるオルガノアルミニウム化合物
(E2)一般式{−Al(T2)−O−}bで表される構造を有する環状アルミノキサン
(E3)一般式T3{−Al(T3)−O−}cAlT3 2で表される構造を有する直鎖状アルミノキサン
(ここで、T1、T2及びT3のそれぞれは、炭化水素基であり、すべてのT1、すべてのT2及びすべてのT3は、それぞれ同一であるか又は異なり得る。Zは、水素原子又はハロゲン原子を表し、すべてのZは、同一であるか又は異なり得る。「a」は、0<a≦3を満足する数を表し、「b」は、2以上の整数であり、「c」は、1以上の整数である。)
本発明は、少なくとも1つ、好ましくは少なくとも2つのオレフィン性モノマーを重合させることにより、ポリマーを重合させるためのプロセスをさらに提供し、それは、前記モノマーを式(1)の金属錯体と接触させることを含む。
オレフィン性モノマーとは、少なくとも1つの重合可能な二重結合を含む分子であると理解されたい。
サイズ排除クロマトグラフィー、IR検出器付き(SEC−IR)
装置:Freeslate Rapid GPCシステム
単一検出器付き(赤外検出器、IR4 Standalone、Polymer Char製)
カラム:PLGel Mixed−B 10μm(×3、300×7.5mmカラム)
較正:線状ポリスチレン(PS)標準を用いて較正
(分子量、約30〜3000kg/mol)
温度:140℃
流量:1.5mL/分
注入量:125μL
溶媒/溶離液:1,2,4−トリクロロベンゼン、0.4g/LのBHT安定剤添加
サンプルの調製:
約140℃で2時間かけて溶解
2〜0.5ミクロンの焼結ガラスフィルターを通して濾過
サンプル濃度:1.5mg/mL
NMR(1H、400MHz)。スペクトルは、Bruker Avance 400スペクトロメーターで測定。
一般
すべての操作は、アルゴン又は窒素の雰囲気下、標準的なSchlenkライン又はドライボックス法を使用して実施した。溶媒は、窒素を吹き込むことにより脱ガスし、適切な乾燥剤のカラムを通過させて乾燥させた。トルエンは、ナトリウム上でリフラックスさせ、蒸留した。重水素を含む溶媒は、カリウム上(C6D6)又はP2O5上(CDCl3及びCD2Cl2)で乾燥させ、減圧下で蒸留し、Teflonバルブアンプル中、窒素下で貯蔵した。NMRサンプルは、窒素下において、J.Young Teflonバルブ付きの5mmのWilmad 507−PPチューブ内で調製した。1H及び13C−{1H}スペクトルは、周囲温度で記録し、内部標準として残存プロチオ−溶媒(protio−solvent)(1H)又は溶媒(13C)の共鳴を用い、テトラメチルシラン(d=0ppm)に対して記録する。ケミカルシフトは、δ(ppm)で、カップリング定数は、Hzの単位で表した。
1.1. 配位子の合成
1.1.1. 4,5−ジメチル−4,5−ジヒドロ−6H−シクロペンタ[b]チオフェン−6−オンの合成。
1H NMR(CDCl3,400MHz):δ7.90−7.91(d,J=4.8Hz,1H),7.05−7.06(d,J=4.7Hz,1H),2.88−2.94(m,1H),2.53−2.59(m,1H),1.40−1.42(d,J=7.6Hz,3H),1.34−1.36(d,J=7.2Hz,3H)。
1H NMR(CDCl3,400MHz):δ7.08−7.09(d,J=4.4Hz,1H),7.00−7.01(d,J=4.1Hz,1H),3.07−3.13(m,1H),2.05(s,3H),1.97(s,3H),1.26−1.28(d,3H)。
1H NMR(CDCl3,400MHz):δ6.71(s,1H),2.76−2.82(m,1H),2.53(s,3H),2.38−2.44(m,1H),1.26−1.33(m,6H)。
1H NMR(CDCl3,400MHz):δ2.81−2.86(m,1H),2.47(s,3H),1.28−1.44(m,6H)。
1H NMR(CDCl3,400MHz):δ3.05−3.10(m,1H),2.40(s,3H),1.94(s,3H),1.91(s,3H),1.29−1.30(d,J=7.0Hz,3H)。
1H NMR(CDCl3,400MHz):δ3.01−3.07(m,1H),2.40(s,3H),2.17(s,3H),1.99(s,3H),1.94(s,3H),1.25−1.27(d,J=7.4Hz,3H)。
1H NMR(CDCl3,400MHz):δ2.39(s,3H),2.28(s,3H),2.15(s,3H),1.93(s,3H),1.37(s,3H),−0.08(s,9H)。
1H NMR(CDCl3,400MHz):δ7.96−7.98(m,1H),7.84−7.86(m,1H),7.24−7.38(m,2H),3.30−3.35(m,1H),2.32(s,3H),2.00(s,3H),1.33−1.35(d,J=7.1Hz,3H)。
1H NMR(CDCl3,400MHz):δ7.95−7.97(m,1H),7.69−7.71(m,1H),7.31−7.35(m,1H),7.13−7.17(m,1H),2.11(s,3H),2.02(s,3H),1.62(s,3H),−0.11(s,9H)。
1H NMR(CDCl3,400MHz):δ7.76(s,1H),2.86−2.92(m,1H),2.53−2.59(m,1H),1.31−1.48(m,6H)。
1H NMR(CDCl3,400MHz):δ6.92(s,1H),3.07−3.13(m,1H),1.97(s,3H),1.93(s,3H),1.30−1.32(d,J=7.6Hz,3H)。
1H NMR(CDCl3,400MHz):δ7.46(s,1H),2.81−2.87(dq,1H,J=6.9Hz,J=2.4Hz),2.46−2.53(dq,1H,J=7.5Hz,J=2.4Hz),2.24(s,3H),1.38(d,3H,J=6.9Hz),1.31(d,3H,J=7.5Hz)。
1H NMR(CDCl3,400MHz):δ2.82−2.87(m,1H),2.38−2.44(m,1H),2.19(s,3H),1.37(s,3H,J=7.1Hz),1.29(d,3H,J=7.5Hz)。
1H NMR(CDCl3,400MHz):δ3.03−3.08(m,1H),2.19(s,3H),1.95(s,3H),1.90(s,3H),1.24(d,3H,J=7.9Hz)。
1H NMR(CDCl3,400MHz):δ7.37−7.47(m,4H),7.25−7.28(m,1H),3.08−3.14(m,1H),2.35(s,3H),2.02(s,3H),1.96(s,3H),1.30(d,3H,J=7.6Hz)。
1H NMR(CDCl3,400MHz):δ7.33(s,1H),7.29(s,2H),3.09−3.12(m,1H),2.34(s,3H),2.01(s,3H),1.95(s,3H),1.33−1.35(m,21H)。
1H NMR(CDCl3,400MHz):δ7.35−7.40(m,2H),7.27−7.29(m,1H),7.18−7.22(m,1H),3.09−3.17(m,2H),2.05(s,3H),2.04(s,3H),1.98(s,3H),1.32(d,3H,J=7.4Hz),1.18(d,3H,J=6.9Hz),1.17(d,3H,J=6.9Hz)。
1H NMR(CDCl3,400MHz):δ2.99−3.05(m,1H),2.80−2.86(m,1H),2.18(s,3H),1.96(s,3H),1.91(s,3H),1.89−1.93(m,2H),1.82−1.84(m,2H),1.72−1.74(m,1H),1.37−1.43(m,4H),1.21−1.30(m,1H),1.24(d,3H,J=7.6Hz)。
1H NMR(CDCl3,400MHz):δ2.95−3.01(m,1H),2.72(m,2H),2.53−2.54(m,2H),1.95(s,3H),1.90(s,3H),1.17−1.25(m,9H)。
1H NMR(CDCl3,400MHz):δ2.99−3.03(m,1H),2.73−2.81(m,2H),2.56−2.65(m,2H),1.96(s,3H),1.91(s,3H),1.84−1.89(m,3H),1.21−1.27(m,4H)。
1H NMR(CDCl3,400MHz):δ7.32−7.34(m,1H),7.20−7.21(m,2H),7.07−7.09(m,1H),3.34(sept,J=6.9Hz,1H),3.11−3.17(m,1H),2.40(s,3H),2.17(s,3H),1.94(s,3H),1.40−1.41(d,J=6.9Hz,6H),1.27−1.29(d,J=7.5Hz,3H)。
1H NMR(400MHz,CDCl3):δ6.74(s,1H,B),6.69(s,1H,A),3.33(d,1H,J=17.1Hz,J=6.0Hz,B),3.16(dd,1H,J=17.2Hz,J=6.8Hz,A),2.90(quind,1H,J=7.3Hz,J=2.8Hz,A),2.67(dd,1H,J=17.7Hz,J=2.9Hz,B),2.54(s,3H,A),2.44−2.52(m,1H(A)+H(B)+3H(B)),1.28(d,3H(A)+3H(B))。
1H NMR(400MHz,CDCl3):δ3.11(dd,1H,J=17.5Hz,J=6.9Hz),2.92(quind,1H,J=7.3Hz,J=2.6Hz),2.43−2.48(m,1H),2.46(s,3H),1.29(d,3H,J=7.4Hz)。
1H NMR(400MHz,CDCl3):δ3.05(dd,1H,J=17.2Hz,J=6.8Hz),2.86(quind,1H,J=7.3Hz,J=2.6Hz),2.36−2.41(m,1H),2.37(s,3H),2.02(s,3H),1.25(d,3H,J=7.5Hz)。
1H NMR(CDCl3,400MHz):δ2.98(s,2H),2.38(s,3H),2.08(s,3H),2.02(s,3H),1.98(s,3H)。
1H NMR(CDCl3,400MHz):δ7.51−7.57(m,2H),7.40−7.47(m,2H),7.28−7.34(m,1H),3.21(s,2H),2.39(s,3H),2.24(s,3H),2.13(s,3H)。
1H NMR(CDCl3,400MHz):δ7.46−7.55(m,2H),7.07−7.16(m,2H),3.20(s,2H),2.40(s,3H),2.21(s,3H),2.13(s,3H)。
1H NMR(CDCl3,400MHz):δ2.90−3.01(m,3H),2.36(s,3H),2.07(s,3H),2.02(s,3H),1.21(d,J=7.0Hz,6H)。
トリクロリド錯体を調製するための一般的手順。
1H NMR(CD2Cl2,400MHz):δ2.70−2.93(m,4H),2.59(s,3H),2.57(s,3H),2.45(s,3H),1.33(s,3H),1.30(s,3H)。
1H NMR(CD2Cl2,400MHz):δ2.78−3.02(m,4H),2.64(s,3H),2.58(s,3H),2.44(s,3H),1.88−1.94(m,4H)。
1H NMR(CD2Cl2,400MHz):δ7.45−7.55(m,5H),2.74(s,3H),2.63(s,3H),2.50(s,3H),2.48(s,3H)。
1H NMR(CD2Cl2,400MHz):δ7.54(m,1H),7.37(m,2H),2.76(s,3H),2.64(s,3H),2.54(s,3H),2.49(s,3H),1.39(s,18H)。
1H NMR(CD2Cl2,400MHz):δ2.97−3.04(m,1H),2.69(s,3H),2.58(s,3H),2.43(s,3H),2.40(s,3H),1.96−2.01(m,2H),1.85−1.88(m,2H),1.75−1.78(m,1H),1.27−1.51(m,5H)。
1H NMR(CD2Cl2,400MHz):δ7.45−7.46(m,2H),7.24−7.39(m,2H),3.00−3.30(br.s,1H),2.72(s,3H),2.62(br.s,3H),2.50(s,3H),2.26(s,3H),1.18(d,3H,J=6.6Hz)。
1H NMR(CDCl3,400MHz):δ7.71−7.72(d,J=5.3Hz,1H),7.17−7.18(d,J=5.3Hz,1H),2.64(s,3H),2.63(s,3H),2.48(s,3H)。
1H NMR(CDCl3,400MHz):δ7.51(d,J=7.3Hz,1H),7.39−7.48(m,2H),7.26−7.36(m,1H),2.54−2.69(m,4H),2.39(s,3H),2.37(s,3H),2.10(s,3H),1.11(d,J=6.9Hz,3H),1.08(d,J=6.9Hz,3H)。
1H NMR(CD2Cl2,400MHz):δ2.67(s,3H),2.56(s,3H),2.51(s,3H),2.45(s,3H),2.38(s,3H)。
1H NMR(CD2Cl2,400MHz):δ8.09−8.11(m,1H),7.84−7.86(m,1H),7.52−7.57(m,2H),2.82(s,3H),2.64(s,3H),2.52(s,3H)。
1H NMR(CDCl3,400MHz):δ2.74(s,3H),2.57(s,3H),2.55(s,3H),2.43(s,3H)。
1H NMR(トリス−イソプロポキシ錯体,C6D6,400MHz):δ6.60(s,1H),4.56−4.65(sept,J=6.1Hz,3H),2.43(s,3H),2.09(s,3H),1.98(s,3H),1.13−1.16(m,18H)。
1H NMR(トリクロリド錯体,CD2Cl2,400MHz):δ7.63(s,1H),2.75(s,3H),2.61(s,3H),2.45(s,3H)。
1H NMR(CDCl3,400MHz):δ6.65(s,1H),2.54(s,3H),2.50(s,3H),2.48(s,3H),2.24(s,3H)
1H NMR(CDCl3,400MHz):δ7.74(d,J=7.2Hz,2H),7.51(t,J=7.6Hz,2H),7.37−7.47(m,1H),6.77(s,1H),2.79(s,3H),2.50(s,3H),2.30(s,3H)。
1H NMR(CDCl3,400MHz):δ7.72(dd,J=8.1,5.7Hz,2H),7.20(t,J=8.5Hz,2H),6.77(s,1H),2.76(s,3H),2.50(s,3H),2.30(s,3H)。
1H NMR(CDCl3,400MHz):δ6.70(s,1H),3.46(sept,J=6.8Hz,1H),2.52(s,3H),2.47(s,3H),2.23(s,3H),1.53(d,J=6.9Hz,3H),1.18(d,J=7.0Hz,3H)。
非環状アミジネート配位子を繋ぎ止めるための一般的な手順:
200mLのトルエン中の金属前駆体の溶液に対して、1当量のアミジネート及び5当量のトリメチルアミンを室温で添加した。そのようにして得られた混合物を室温で一晩撹拌してから、蒸発乾固させた。その残分を200mLのトルエン中に溶解させ、そのようにして得られた混合物を、セライトのパッドを通して濾過した。その濾液を濃縮して20mLとし、150mLのペンタンを添加した。そのようにして得られた懸濁液を冷却して−30℃とし、濾過し、その沈殿物を、2×50mLの冷ペンタンを用いて洗浄し、次いで真空中で乾燥させた。そのようにして得られた粉体をペンタン:ヘキサン混合物(1:5)から−30℃で再結晶させた。
1H NMR(CD2Cl2,400MHz):δ7.87−7.89(m,1H),7.69−7.71(m,1H),7.30−7.41(m,3H),6.96−7.00(m,2H),3.29−3.42(m,2H),3.09−3.19(m,2H),2.48(s,3H),2.23(s,3H),2.21(s,3H),1.49−1.63(m,6H)。
19F NMR(CD2Cl2,376MHz):δ−111.15(m,1F),−111.22(m,1F)。
1H NMR(CD2Cl2,400MHz):δ7.34−7.41(m,1H),6.97−7.01(m,2H),3.65−3.67(m,2H),3.19−3.21(m,2H),2.33(s,3H),2.32(s,3H),2.22(s,3H),2.13(s,3H),2.13(s,3H)。
19F NMR(CD2Cl2,376MHz):δ−111.39(m,1F),−111.48(m,1F)。
1H NMR(CD2Cl2,400MHz):δ7.30−7.37(m,1H),7.11(s,1H),6.93−6.97(m,2H),3.66−3.77(m,2H),3.18−3.21(m,2H),2.43(s,3H),2.22(s,3H),2.11(s,3H),1.63−1.76(m,4H),1.54−1.59(m,2H)。
19F NMR(CD2Cl2,376MHz):δ−110.03(m,1F),−110.12(m,1F)。
1H NMR(CDCl3,400MHz):δ7.29−7.37(m,1H),6.92−6.98(m,2H),3.65−3.76(m,2H),3.18−3.20(m,2H),2.43(s,3H),2.38(s,3H),2.19(s,3H),2.07(s,3H),1.63−1.75(m,4H),1.54−1.59(m,2H)。
19F NMR(CDCl3,376MHz):δ−110.24(m)。
1H NMR(CD2Cl2,400MHz):δ7.39(m,1H),7.28(d,1H,J=4.9Hz),6.92−7.02(m,3H),3.63(br.s,2H),3.20(br.s,2H),2.23(s,6H),2.18(s,3H),1.68(br.s,4H),1.57(br.s,2H)。
1H NMR(CD2Cl2,400MHz):δ7.28−7.41(m,3H),7.11−7.15(m,1H),6.98(m,3H),3.67(br.s,2H),3.18(m,2H),2.73(sept,1H,J=6.9Hz),2.29(s,3H),2.18(s,3H),1.94(s,3H),1.83(s,3H),1.66(br.s,4H),1.55(br.s,2H),1.10(d,3H,J=6.9Hz),1.04(d,3H,J=6.9Hz)
1H NMR(CD2Cl2,400MHz):δ7.35(m,1H),7.29(d,2H,J=8.9Hz),7.03(s,1H),6.91−7.00(m,2H),6.67(d,2H,J=8.9Hz),3.68(br.s,2H),3.18(m,2H),2.97(s,6H),2.29(s,3H),2.18(s,3H),2.10(s,3H),1.67(br.s,4H),1.55(br.s,2H)
1H NMR(CDCl3,400MHz):δ7.34−7.37(m,3H),7.23−7.30(m,1H),7.13(s,1H),6.87−6.91(m,2H),3.57−3.70(m,2H),3.13−3.16(m,2H),2.28(s,3H),2.17(s,3H),2.07(s,3H),1.50−1.67(m,6H),1.31(s,18H)。
19F NMR(C6D6,376MHz):δ−110.31(m,1F),−110.66(m,1F)。
1H NMR(CDCl3,400MHz):δ7.28−7.34(m,2H),7.08−7.55(br.s,2H),6.90−6.95(m,2H),3.60−3.73(m,2H),3.15−3.18(m,2H),2.35(s,3H),2.26(s,3H),2.02(s,3H),1.95(s,3H),1.53−1.69(m,6H),1.31(s,18H)。
19F NMR(C6D6,376MHz):δ−110.31(m,1F),−110.66(m,1F)。
1H NMR(CD2Cl2,400MHz):δ7.34−7.47(m,2H),7.16(d,2H,J=8.4Hz),6.99(m,1H),6.70(d,2H,J=8.4Hz),3.69(br.s,2H),3.19(br.s,2H),2.98(s,6H),2.32(s,3H),2.26(s,3H),2.03(s,3H),1.98(s,3H),1.67(br.s,4H),1.56(br.s,2H)
1H NMR(C6D6,400MHz):δ7.31(d,2H,J=8.1Hz),7.02(d,2H,J=8.1Hz),6.46−6.58(m,3H),3.70(br.s,2H),2.90(br.s,2H),2.26(s,3H),2.20(s,3H),2.16(s,3H),1.97(s,3H),1.75(s,3H),1.40(br.s,2H),1.16(br.s,4H),0.65(s,3H),0.60(s,3H)。
収率:52%。
1H NMR(CD2Cl2,400MHz):δ7.37(m,1H),6.99(m,2H),3.67(m,2H),3.20(m,2H),2.55−2.68(m,4H),2.26(s,3H),2.13(s,3H),2.11(s,3H),1.68(br.s,4H),1.56(br.s,2H),1.24(s,3H),1.21(s,3H)。
収率:62%。
1H NMR(CD2Cl2,400MHz):δ7.40(m,1H),6.89(m,2H),3.65(br.s,2H),3.14(br.s,2H),2.80−2.90(m,1H),2.54−2.68(m,2H),2.45−2.48(m,1H),2.29(s,3H),2.14(s,3H),1.78(s,3H),1.65(br.s,4H),1.45(br.s,2H)。
収率:75%。
1H NMR(CD2Cl2,400MHz):δ7.35−7.44(m,6H),6.98(m,2H),3.66(br.s,2H),3.20(br.s,2H),2.40(s,3H),2.36(s,3H),2.21(s,3H),2.14(s,3H),1.64(br.s,4H),1.55(br.s,2H)。
収率:64%。
1H NMR(CD2Cl2,400MHz):δ7.43(t,1H,J4=1.7Hz),7.37(m,1H),7.29(s,1H),7.28(s,1H),6.99(m,2H),3.58−3.71(m,2H),3.20(m,2H),2.41(s,3H),2.40(s,3H),2.20(s,3H),2.15(s,3H),1.65(br.s,4H),1.56(br.s,2H),1.36(s,18H)。
収率:82%。
1H NMR(CD2Cl2,400MHz):δ7.34−7.43(m,3H),7.14−7.26(m,2H),7.00(m,2H),3.78(br.s,2H),3.12−3.33(m,3H),3.29(br.s,3H),2.24(br.s,3H),2.15(br.s,3H),2.08(br.s,3H),1.68−1.73(m,4H),1.58(br.s,2H),1.14(d,6H,J=6.6Hz)。
収率:77%。
1H NMR(CD2Cl2,400MHz):δ7.38(m,1H),6.96−7.03(m,2H),3.71(br.s,2H),3.20(br.s,2H),2.85(ddd,1H,J1=11.4Hz,J2=8.0Hz,J3=3.5Hz),2.35(s,3H),2.24(s,3H),2.20(s,3H),2.09(s,3H),1.78−1.89(m,4H),1.67−1.73(m,5H),1.56(br.s,2H),1.39(m,3H),1.30(m,2H)。
環状アミジネート配位子を繋ぎ止めるための一般的な手順:
70mLのトルエン中の金属前駆体の溶液に対して、アミジネート配位子(1当量)及びトリメチルアミン(5当量)を室温で添加した。その混合物を室温で一晩撹拌してから、蒸発乾固させた。その残分を150mLのトルエン中に溶解させ、そのようにして得られた混合物を、Celiteのパッドを通して濾過した。次いで、その濾液を蒸発させて、15mLとし、結晶化の観点から−30℃で100mLのヘキサンを添加した。それらの結晶を濾過により単離し、2×50mLのヘキサンを用いて洗浄してから、真空中で乾燥させた。
1H NMR(CD2Cl2,400MHz):δ7.65−7.67(m,1H),7.58−7.61(m,1H),7.47−7.54(m,2H),7.20−7.24(m,1H),7.15−7.17(m,2H),4.69−4.85(m,2H),2.37(s,3H),2.29(s,3H),2.28(s,3H),2.24(s,3H),2.20(s,3H),2.04(s,3H),1.87(s,3H)。
1H NMR(CD2Cl2,400MHz):δ7.84−7.86(m,1H),7.57−7.61(m,1H),7.48−7.52(m,2H),7.21−7.23(m,1H),7.15−7.17(m,2H),7.09(s,1H),4.75(s,2H),2.37(s,3H),2.35(s,3H),2.33(s,3H),2.05(s,3H),2.00(s,3H)。
1H NMR(CDCl3,400MHz):δ7.73−7.75(m,1H),7.55−7.59(m,1H),7.46−7.50(m,2H),7.14−7.21(m,3H),4.74(s,2H),2.35(s,3H),2.35(s,3H),2.33(s,3H),2.26(s,3H),1.98(s,3H),1.97(s,3H)。
1H NMR(CD2Cl2,400MHz):δ7.76(d,1H,J=7.5Hz),7.61(m,1H),7.49−7.54(m,2H),7.17−7.25(m,4H),6.89(d,1H,J=4.5Hz),4.77(m,2H),2.34(s,3H),2.31(s,3H),2.16(s,3H),2.09(s,3H),2.07(s,3H)。
1H NMR(CD2Cl2,400MHz):δ7.81(d,1H,J=7.5Hz),7.59−7.62(m,1H),7.42−7.54(m,2H),7.35−7.42(m,3H),7.12−7.29(m,4H),4.75(m,2H),2.70(sept,1H,J=6.9Hz),2.34(s,3H),2.27(s,3H),2.16(s,3H),2.13(s,3H),1.80(s,3H),1.75(s,3H),1.09(d,3H,J=6.9Hz),1.02(d,3H,J=6.9Hz)
1H NMR(CD2Cl2,400MHz):δ7.76(d,1H,J=7.7Hz),7.59(m,1H),7.41−7.52(m,3H),7.32(d,2H,J=8.8Hz),7.23(m,2H),7.00(s,1H),6.71(d,2H,J=8.8Hz),4.74(m,2H),2.99(s,6H),2.32(s,3H),2.22(s,3H),2.18(s,3H),2.10(s,3H),1.95(s,3H)。
1H NMR(CDCl3,400MHz):δ7.75−7.77(m,1H),7.53−7.57(m,1H),7.41−7.47(m,2H),7.36−7.39(m,3H),7.08−7.19(m,4H),4.63−4.75(m,2H),2.33(s,3H),2.17(s,3H),2.11(s,3H),2.08(s,3H),1.96(s,3H),1.31(s,18H)。
1H NMR(CD2Cl2,400MHz):δ7.72(d,1H,J=7.5Hz),7.59(m,1H),7.52(d,1H,J=7.5Hz),7.47(t,1H,J=7.5Hz),7.41(t,1H,J4=1.8Hz),7.11−7.26(m,5H),4.67−4.82(m,2H),2.36(s,3H),2.25(s,3H),2.16(s,3H),2.06(s,3H),1.94(s,3H),1.87(s,3H),1.33(s,18H)。
1H NMR(CD2Cl2,400MHz):δ7.46−7.60(m,4H),7.28(m,2H),7.13(m,1H),4.70(s,2H),2.55−2.68(m,4H),2.26(s,6H),2.15(s,3H),2.13(s,3H),2.11(s,3H),1.20(s,3H),1.19(s,3H)。
収率:67%。
1H NMR(CD2Cl2,400MHz):δ7.67(m,1H),7.59(m,1H),7.49−7.54(m,2H),7.15−7.24(m,3H),4.68−4.86(m,2H),2.83−2.88(m,1H),2.59−2.69(m,2H),2.47−2.48(m,1H),2.38(s,3H),2.29(s,3H),2.26(s,3H),2.04(s,3H),1.87(s,3H),1.79(br.s,4H)。
収率:45%。
1H NMR(CD2Cl2,400MHz):δ7.73(d,1H,J=7.6Hz),7.51−7.58(m,2H),7.29−7.42(m,6H),7.15−7.22(m,3H),4.70−4.85(m,2H),2.37(s,3H),2.37(s,3H),2.36(s,3H),2.31(s,3H),2.05(s,3H),1.98(s,3H)。
収率:52%。
1H NMR(CD2Cl2,400MHz):δ7.76(d,1H,J=7.9Hz),7.50−7.56(m,2H),7.39−7.45(m,2H),7.14−7.24(m,5H),4.70−4.84(m,2H),2.39(s,3H),2.37(s,3H),2.36(s,3H),2.30(s,3H),2.06(s,3H),1.96(s,3H),1.31(s,18H)。
収率:60%。
1H NMR(CD2Cl2,400MHz):δ7.75(d,1H,J=7.7Hz),7.59(m,1H),7.51(m,2H),7.15−7.24(m,3H),4.69−4.83(m,2H),2.77(m,1H),2.36(s,3H),2.30(s,3H),2.29(s,3H),2.23(s,3H),2.00(s,3H),1.94(s,3H),1.78−1.86(m,2H),1.69(br.s,2H),1.54−1.55(m,1H),1.18−1.39(m,5H)。
環状アミジネート配位子を繋ぎ止めるための一般的な手順:
70mLのトルエン中の金属前駆体の溶液に対して、アミジネート配位子(1当量)及びトリメチルアミン(5当量)を室温で添加した。その混合物を室温で一晩撹拌してから、蒸発乾固させた。その残分を150mLのトルエン中に溶解させ、そのようにして得られた混合物を、Celiteのパッドを通して濾過した。次いで、その濾液を蒸発させて15mLとし、結晶化の観点から−30℃で100mLのヘキサンを添加した。それらの結晶を濾過により単離し、2×50mLのヘキサンを用いて洗浄してから、真空中で乾燥させた。
収率:1.96g(86%)。
1H NMR(CDCl3,400MHz):δ7.64(d,J=7.7Hz,1H),7.53−7.60(m,1H),7.42−7.50(m,2H),7.35(tt,J=8.5,6.1Hz,1H),7.05(t,J=8.4Hz,2H),6.15(s,1H),4.93(d,J=17.4Hz,1H),4.81(d,J=17.3Hz,1H),2.17(s,3H),2.07(s,3H),2.04(s,3H),1.98(s,3H)。
収率:2.10g(83%)。
1H NMR(CDCl3,400MHz):δ7.51(d,J=7.4Hz,3H),7.40(d,J=8.2Hz,2H),7.31−7.37(m,1H),7.17−7.31(m,4H),6.81−6.97(m,2H),6.31(s,1H),4.85(d,J=17.4Hz,1H),4.72(d,J=17.5Hz,1H),2.47(s,3H),2.12(m,6H)。
1H NMR(CDCl3,400MHz):δ7.51−7.57(m,1H),7.41−7.49(m,4H),7.34−7.41(m,1H),7.19−7.29(m,2H),6.94(t,J=8.8Hz,3H),4.86(d,J=17.5Hz,1H),4.71(d,J=17.5Hz,1H),2.44(s,3H),2.13(s,3H),2.09(s,3H)。
収率:616mg(78%)。
1H NMR(CDCl3,400MHz):δ7.62−7.67(m,1H),7.53−7.58(m,1H),7.42−7.48(m,2H),7.27−7.36(m,1H),6.97−7.08(m,2H),6.26(s,1H),4.97(d,J=17.3Hz,1H),4.70(d,J=17.4Hz,1H),2.92(sept,J=6.9Hz,1H),2.24(s,3H),2.04(s,3H),1.93(s,3H),1.02(d,J=6.9Hz,3H),0.89(d,J=6.9Hz,3H)。
ジエチルエーテル(20mL/mmol)中にジクロリド錯体を懸濁させた。その反応混合物を冷却して−30℃とし、それに続けてMeMgBr(2.2当量)を添加した。この混合物を室温で一晩撹拌してから、蒸発乾固させた。その残分にn−ヘキサン(10L/mmol)を添加し、そのようにして得られた懸濁液を、Celite503パッドを通して濾過した。その濾液を蒸発乾固させると、ジメチルチタン錯体が得られた。必要に応じて、その反応生成物を−30℃でn−ペンタン/n−ヘキサンから再結晶させた。それぞれのメチル化合物は、Mの添字で示している。
ダブルインターミグ及びバッフルを備えた2リットルのバッチ式オートクレーブ中でバッチ式共重合を実施した。反応温度は、90±3℃(表1、2、3及び4に示したデータ)及び120±3℃(表5における反応)に設定し、Lauda Thermostatにより調節した。フィードストリーム(溶媒及びモノマー)は、各種の吸着媒体と接触させて、当業者に公知である、触媒を失活させる不純物、例えば水、酸素及び極性化合物を除去することにより精製した。重合時、エチレン及びプロピレンモノマーは、その反応器のガスキャップに連続的にフィードした。背圧バルブにより、反応器の圧力を一定に保った。
Claims (15)
- 式(1)
TCyLMZp (1)
(式中、
Mは、第4族の金属であり、
Zは、アニオン性配位子であり、
pは、1〜2、好ましくは2の数であり、
TCyは、式(2)
R1及びR2は、個別に、水素、ハロゲン、C1〜C10アルキル、C5〜C10シクロアルキル及び非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10アリール、特にC1〜C4−アルキル置換のフェニル並びにSiR3、OR、NR2、SR、PR2(ここで、Rは、個別に、C1〜C10−アルキル、C5〜C10−シクロアルキル及び非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニルを意味する)の群から選択されるか、又は
R1及びR2は、それらが結合されているチオフェン環の2つの二重結合炭素原子と共に、非置換又はC1〜C4−アルキル置換の脂肪族C5〜C6−シクロアルケン環を形成し、
R3、R4及びR5は、個別に、水素、C1〜C4アルキル、非置換又はC1〜C4−アルキル及び/若しくはハロゲン、特に塩素若しくはフッ素置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニル並びにSiR3、OR、NR2、SR、PR2(ここで、Rは、個別に、C1〜C10−アルキル、C5〜C10−シクロアルキル及び非置換又はC1〜C10−アルキル若しくはC1〜C4−ジアルキルアミノ置換のC6〜C10−アリール、特にC1〜C4−アルキル置換のフェニルを意味する)の群から選択される)
のチオフェン縮合されたシクロペンタジエニルタイプの配位子であり、及び
Lは、式(3)
Sub1は、非置換又はC1〜C4−アルキル及び/若しくはハロゲン、特に塩素若しくはフッ素置換のC6〜C10−芳香族置換基、特にフェニルであり、及び
Sub2は、第15族のヘテロ原子であって、それを通してSub2がイミンの炭素原子に結合される、ヘテロ原子を含む置換基であるか、又は
Sub1及びSub2は、それらが結合されているイミノ基と共に、式(3a)
アミジン環に縮合されたベンゾ環は、非置換であり得るか、又はさらなる置換基R7を含有し得、前記さらなる置換基R7は、個別に、水素、C1〜C4−アルキル及びハロゲンの群から選択される添え字「q」のものであり、それにより、qは、0〜4、好ましくは0〜2、最も好ましくは0の数であり、
Sub4は、第14族の原子であって、それを介してSub4がアミノ窒素原子N1に結合される、第14族の原子を含む脂肪族又は芳香族の環状又は直鎖状の置換基であり、好ましくは、Sub4は、非置換であるか、又はハロゲン、特にCl若しくはF及びC1〜C4−アルキルから選択される基からの1つ若しくは複数の置換基によって置換されるC6〜C10芳香族環、好ましくはフェニルである)
の配位子を形成する)
のアミジネート配位子である)
の金属錯体。 - Mは、チタンである、請求項1に記載の金属錯体。
- Zは、独立して、ハロゲン原子、C1〜10アルキル基、C7〜20アラルキル基、C6〜20アリール基又はC1〜20炭化水素で置換されたアミノ基を意味する、請求項1又は2に記載の金属錯体。
- Mは、Tiであり、
Zは、塩素及びC1〜C4−アルキルからなる群から選択され、及び
pは、2である、請求項1〜3のいずれか一項に記載の式(1)の金属錯体。 - Sub1は、フェニル又はC1〜C4−アルキル及び/若しくはCl置換のフェニル残基であり、及びSub2は、式−NR8R9のアミノ基であり、ここで、R8及びR9は、個別に、脂肪族ヒドロカルビル、ハロゲン化脂肪族ヒドロカルビル、芳香族ヒドロカルビル、ハロゲン化芳香族ヒドロカルボニル残基の群から選択され、それにより、R8は、任意選択的に、R5又はSub1と共に複素環構造を形成する、請求項1〜4のいずれか一項に記載の金属錯体。
- TCyは、式(2a)
nは、3〜4の数であり、及び
R6は、各添え字mについて、個別に、C1〜C4−アルキルを意味し、
mは、0〜4、好ましくは0〜2の数である)
のチオフェン縮合されたシクロペンタジエニル配位子である、請求項1〜5のいずれか一項に記載の式(1)の金属錯体。 - 前記式(1)は、式3a)
前記アミジン含有配位子(3a)は、前記イミンの窒素原子N2を介して前記金属Mと共有結合され、
前記アミジン環に縮合された前記ベンゾ環は、非置換であり得るか、又はさらなる置換基R7を含有し得、前記さらなる置換基R7は、個別に、水素、C1〜C4−アルキル及びハロゲンの群から選択される添え字「q」のものであり、それにより、qは、0〜4、好ましくは0〜2、最も好ましくは0の数であり、
Sub4は、第14族の原子であって、それを介してSub4が前記アミノ窒素原子N1に結合される、第14族の原子を含む脂肪族又は芳香族の環状又は直鎖状の置換基であり、好ましくは、Sub4は、非置換であるか、又はハロゲン、特にCl若しくはF及びC1〜C4−アルキルから選択される基からの1つ若しくは複数の置換基によって置換されるC6〜C10芳香族環、好ましくはフェニルである)
の配位子Lを有する、請求項1〜6のいずれか一項に記載の式(1)の金属錯体。 - 請求項1〜7のいずれか一項に規定の式(1)の金属錯体を製造するためのプロセスであって、式(3)
TCyMZp+1 (3)
の金属錯体は、式LHのアミジン又はそのハロゲン化水素酸塩LH・HZと反応され、ここで、Lは、請求項1〜6のいずれか一項に規定の意味を有し、及びZは、ハロゲン、特にCl、Br又はFを意味する、プロセス。 - a)請求項1〜7のいずれか一項に規定の式(1)の金属錯体、
b)活性化剤、及び
c)任意選択的に、捕捉剤
を含む触媒系。 - 前記捕捉剤c)は、第1〜13族の金属若しくはメタロイドのヒドロカルビル又は第15族若しくは第16族の原子を含有する少なくとも1つの立体障害のある化合物とのその反応生成物である、請求項9に記載の触媒系。
- 前記活性化剤b)は、ボラン、ホウ酸塩又はオルガノアルミニウム化合物(E)、好ましくはアルキルアルミノキサンである、請求項9又は10に記載の触媒系。
- 少なくとも1つのオレフィン性モノマーを重合させることによってポリマーを調製するためのプロセスであって、前記モノマーを、請求項1〜7のいずれか一項に規定の金属錯体又は請求項9〜11のいずれか一項に規定の触媒系と接触させることを含むプロセス。
- エチレン及び少なくともC3〜C12−α−オレフィンは、オレフィン性モノマーとして使用される、請求項12に記載のプロセス。
- エチレン、少なくとも1つのC3〜12アルファオレフィン並びに好ましくは5−メチレン−2−ノルボルネン、5−エチリデン−2−ノルボルネン、5−ビニルノルボルネン、2,5−ノルボルナジエン、ジシクロ−ペンタジエン及びビニルシクロヘキセンからなる群、特に5−エチリデン−2−ノルボルネン及び5−ビニルノルボルネンからなる群から選択される少なくとも1つの非共役ジエンは、オレフィン性モノマーとして使用される、請求項12又は13に記載のプロセス。
- 請求項1に規定の金属錯体又は請求項9に規定の触媒系を用いて得ることが可能なポリマー。
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