JP2019530771A - チオグアニジン第iv族遷移金属触媒および重合系 - Google Patents
チオグアニジン第iv族遷移金属触媒および重合系 Download PDFInfo
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- JP2019530771A JP2019530771A JP2019515967A JP2019515967A JP2019530771A JP 2019530771 A JP2019530771 A JP 2019530771A JP 2019515967 A JP2019515967 A JP 2019515967A JP 2019515967 A JP2019515967 A JP 2019515967A JP 2019530771 A JP2019530771 A JP 2019530771A
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- thioguanidine
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- LBYVZRFDLNAPRC-UHFFFAOYSA-N 2-sulfanylguanidine Chemical group NC(=N)NS LBYVZRFDLNAPRC-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title abstract description 64
- 229910052723 transition metal Inorganic materials 0.000 title description 3
- 150000003624 transition metals Chemical class 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 95
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000005977 Ethylene Substances 0.000 claims abstract description 76
- 239000003446 ligand Substances 0.000 claims abstract description 66
- 239000004711 α-olefin Substances 0.000 claims abstract description 45
- 125000003118 aryl group Chemical group 0.000 claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 24
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- -1 n- butyl Chemical group 0.000 claims description 86
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 21
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 16
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000002685 polymerization catalyst Substances 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
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- 150000001805 chlorine compounds Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 7
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical group Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 claims 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 29
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
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- 125000001072 heteroaryl group Chemical group 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
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- 125000001424 substituent group Chemical group 0.000 description 12
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- 239000000178 monomer Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
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- 125000004429 atom Chemical group 0.000 description 7
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- 229910052717 sulfur Inorganic materials 0.000 description 7
- HOCSPSSSYYQGMQ-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)-3-[4-[(2,6-dimethylphenyl)carbamothioylamino]butyl]thiourea Chemical compound CC1=CC=CC(C)=C1NC(=S)NCCCCNC(=S)NC1=C(C)C=CC=C1C HOCSPSSSYYQGMQ-UHFFFAOYSA-N 0.000 description 6
- FXEJNAAFZARADY-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)-3-phenylthiourea Chemical compound CC1=CC=CC(C)=C1NC(=S)NC1=CC=CC=C1 FXEJNAAFZARADY-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
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- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000004474 heteroalkylene group Chemical group 0.000 description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 5
- JKPYKHAVAXVNCK-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)-3-[5-[(2,6-dimethylphenyl)carbamothioylamino]pentyl]thiourea Chemical compound Cc1cccc(C)c1NC(=S)NCCCCCNC(=S)Nc1c(C)cccc1C JKPYKHAVAXVNCK-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 125000002993 cycloalkylene group Chemical group 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000004404 heteroalkyl group Chemical group 0.000 description 5
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- 125000003367 polycyclic group Chemical group 0.000 description 5
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- QBVVQITUKDCTBS-UHFFFAOYSA-N 1-butyl-3-(2,6-dimethylphenyl)thiourea Chemical compound CCCCNC(=S)NC1=C(C)C=CC=C1C QBVVQITUKDCTBS-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229910007950 ZrBN Inorganic materials 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 125000006376 (C3-C10) cycloalkyl group Chemical group 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
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- VAUAMEDMLANPBY-UHFFFAOYSA-N [Zr]CC1=CC=CC=C1 Chemical compound [Zr]CC1=CC=CC=C1 VAUAMEDMLANPBY-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004639 dihydroindenyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- GVOLZAKHRKGRRM-UHFFFAOYSA-N hafnium(4+) Chemical compound [Hf+4] GVOLZAKHRKGRRM-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000006588 heterocycloalkylene group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003427 indacenyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 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
- 125000004501 isothiazol-5-yl group Chemical group S1N=CC=C1* 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000003145 oxazol-4-yl group Chemical group O1C=NC(=C1)* 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000004523 tetrazol-1-yl group Chemical group N1(N=NN=C1)* 0.000 description 1
- 125000004299 tetrazol-5-yl group Chemical group [H]N1N=NC(*)=N1 0.000 description 1
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/64006—Bidentate ligand
- C08F4/64041—Monoanionic ligand
- C08F4/64044—NN
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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
- C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/64168—Tetra- or multi-dentate ligand
- C08F4/64186—Dianionic ligand
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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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
Description
本出願は、その全体が参照により本明細書に組み込まれる、2016年9月30日に出願された米国特許仮出願第62/402,210号に対する優先権を主張する。
本開示で使用される一般的な略語は、Me:メチル、Et:エチル、Ph:フェニル、Bn:ベンジル(−CH2−Ph)、THF:テトラヒドロフラン、Et2O:ジエチルエーテル、C6D6:重水素化ベンゼン、CDCl3:重水素化クロロホルム、DMSO−d6:重水素化ジメチルスルホキシド、MeI:ヨウ化メチル、MgSO4:硫酸マグネシウム、HfBn4:ハフニウム(IV)テトラベンジル、ZrBn4:ジルコニウム(IV)テトラベンジル、N2:窒素ガス、MMAO:変性メチルアルミノキサン、NMR:核磁気共鳴、DSC:示差走査熱量測定、mmol:ミリモル、mL:ミリリットル、M:モル、min:分、h:時間、d:日数、GPC:ゲル浸透クロマトグラフィー、Mw:重量平均分子量、Mn:数平均分子量を含み得る。
前述の定義を考慮して、本出願の具体的な実施形態をこれから説明する。本開示は、異なる形態で具体化されてもよく、記載された任意の具体的な実施形態に限定されると解釈されるべきではないことを理解されたい。むしろ、実施形態は、この開示が徹底的かつ完全であり、本主題の範囲を当業者に十分に伝えるように提供される。
本開示の実施形態によるエチレン−コ−アルキレンコポリマーなどのポリオレフィン組成物は、触媒量の前述の組成物のうちの少なくとも1つの存在下で、エチレンと1つ以上のオレフィンモノマーとの反応生成物を含み、これは、重合条件下ならびに任意に1つ以上の共触媒および/または捕捉剤の存在下で、少なくとも1つのチオグアニジン錯体を含む。
本発明によるポリオレフィン組成物を製造するために、任意の従来の重合プロセスを用いてもよい。そのような従来の重合プロセスとしては、溶液重合法、粒子形成重合法、および1つ以上の従来の反応器を使用するそれらの組み合わせ、例えばループ反応器、等温反応器、流動床反応器、撹拌槽反応器、バッチ式反応器の並列、直列、および/またはそれらの任意の組み合わせが挙げられるが、これらに限定されない。
エチレンと1−オクテンとのバッチ共重合
本明細書の実施形態による様々な触媒の有効性を決定するために、エチレンと1−オクテンとを触媒C1、C2、C3、C4、およびC5の存在下でバッチ共重合した。
Claims (43)
- 式(I)による少なくとも1つのチオグアニジン錯体を含む組成物であって、
Mが、Ti、Zr、またはHfから選択される金属中心であり、
aが、1または2であり、
前記少なくとも1つのチオグアニジン錯体の各基Qが、前記金属中心に結合した二座チオグアニジン配位子であり、前記チオグアニジン配位子が、式(Ia)または式(Ib)を有し、
前記少なくとも1つのチオグアニジン錯体中の各基Z1が、アルキレン基から、独立して選択され、
a=2である場合、2つの基Qの基R3が、少なくとも1つの共有結合によって互いに任意に結合しており、
各Xが、前記金属中心に共有結合または配位結合しており、かつ、アルキル基、ハライド、またはアミドから、独立して選択される、組成物。 - aが、1であり、前記少なくとも1つのチオグアニジン錯体が、式(IIa)または式(IIb)を有し、
- 式(IIa)のR1ならびに式(IIa)および(IIb)のR3が、式
式中、A1およびA2が独立して、水素または(C1−C10)アルキル基である、請求項2に記載の組成物。 - A1およびA2が、独立して、水素またはメチルである、請求項3に記載の組成物。
- A1およびA2の両方がメチルである、請求項3に記載の組成物。
- R2が、(C1−C10)アルキル基である、請求項2に記載の組成物。
- R2が、メチルである、請求項2に記載の組成物。
- 全ての基Xが、同一である、請求項2に記載の組成物。
- 各Xが、前記金属中心に配位したベンジル基である、請求項2に記載の組成物。
- 各Xが、塩化物である、請求項2に記載の組成物。
- 前記少なくとも1つのチオグアニジン錯体が、化合物C1を含む、請求項2に記載の組成物。
- aが、2であり、前記少なくとも1つのチオグアニジン錯体が、式(IIIa)、式(IIIb)、または式(IIIc)を有し、
- 各R1が、フェニルまたは(C1−C10)アルキル基から、独立して選択される、請求項12に記載の組成物。
- 各R1が、フェニルまたは(C1−C4)アルキル基から、独立して選択される、請求項12に記載の組成物。
- 各R1が、フェニルまたはn−ブチルから、独立して選択される、請求項12に記載の組成物。
- 各R1が、フェニルであるか、または各R1が、n−ブチルである、請求項12に記載の組成物。
- 各R2が、(C1−C10)アルキル基である、請求項12に記載の組成物。
- 各R2が、メチルである、請求項12に記載の組成物。
- 各R3が独立して、式
式中、A1およびA2が、独立して、(C1−C10)アルキル基である、請求項12に記載の組成物。 - A1およびA2の両方がメチルである、請求項19に記載の組成物。
- 各Xが、前記金属中心に配位したベンジル基である、請求項12に記載の組成物。
- 各Xが、塩化物である、請求項12に記載の組成物。
- 両方の基Qが、同一であり、全ての基Xが、同一である、請求項12に記載の組成物。
- 前記少なくとも1つのチオグアニジン錯体が、化合物C2もしくはC3、またはそれらの組み合わせから選択される、請求項12に記載の組成物。
- aが、2であり、
2つの基QのR3が、架橋基Z2として互いに結合しており、
前記少なくとも1つのチオグアニジン錯体が、式(IVa)、式(IVb)、または式(IVc)を有し、
- Z2が、−(CH2)n−であり、nが、4〜10である、請求項25に記載の組成物。
- Z2が、−(CH2)n−であり、nが、4または5である、請求項25に記載の組成物。
- 各R2が、(C1−C10)アルキル基である、請求項25に記載の組成物。
- 各R2が、メチルである、請求項25に記載の組成物。
- 各R1が独立して、式
式中、A1およびA2が独立して、(C1−C10)アルキル基である、請求項25に記載の組成物。 - A1およびA2の両方がメチルである、請求項30に記載の組成物。
- 各Xが、前記金属中心に配位したベンジル基である、請求項25に記載の組成物。
- 各Xが、塩化物である、請求項25に記載の組成物。
- 全ての基R1が、同一であり、全ての基R2が、同一であり、全ての基Xが、同一である、請求項25に記載の組成物。
- 前記少なくとも1つのチオグアニジン錯体が、化合物C4、C5、C6、もしくはC7、またはそれらの組み合わせから選択される、請求項25に記載の組成物。
- 触媒量の請求項1に記載の組成物の存在下で、エチレンとα−オレフィンコモノマーとを共重合するように構成された、重合触媒系。
- 前記組成物が、化合物C1、C2、C3、C4、C5、C6、C7、またはそれらの組み合わせから選択される少なくとも1つのチオグアニジン錯体を含む、請求項36に記載の重合触媒系。
- 前記α−オレフィンコモノマーが、少なくとも1つのC3−C12α−オレフィンを含む、請求項36に記載の重合系から製造されるエチレン−コ−アルキレンコポリマー。
- 前記組成物が、化合物C1、C2、C3、C4、C5、C6、C7、またはそれらの組み合わせから選択される少なくとも1つのチオグアニジン錯体を含む、請求項38に記載のエチレン−コ−アルキレンコポリマー。
- 前記α−オレフィンコモノマーが、1−オクテンである、請求項38に記載のエチレン−コ−アルキレンコポリマー。
- 触媒量の請求項1に記載の組成物の存在下で、エチレン−コ−アルキレンコポリマーを形成するために、エチレンとα−オレフィンコモノマーとを反応させることであって、前記α−オレフィンコモノマーが、少なくとも1つのC3−C12α−オレフィンを含む、重合方法。
- 前記組成物が、化合物C1、C2、C3、C4、C5、C6、C7、またはそれらの組み合わせから選択される少なくとも1つのチオグアニジン錯体を含む、請求項41に記載の重合方法。
- 前記α−オレフィンコモノマーが、1−オクテンである、請求項42に記載の重合方法。
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