JP7011652B2 - ホスファグアニジン第iv族金属オレフィン重合触媒 - Google Patents
ホスファグアニジン第iv族金属オレフィン重合触媒 Download PDFInfo
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- JP7011652B2 JP7011652B2 JP2019515985A JP2019515985A JP7011652B2 JP 7011652 B2 JP7011652 B2 JP 7011652B2 JP 2019515985 A JP2019515985 A JP 2019515985A JP 2019515985 A JP2019515985 A JP 2019515985A JP 7011652 B2 JP7011652 B2 JP 7011652B2
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- XCXAQVZPLNXACA-UHFFFAOYSA-N phosphanylmethanimidamide Chemical group NC(P)=N XCXAQVZPLNXACA-UHFFFAOYSA-N 0.000 title claims description 90
- 239000002685 polymerization catalyst Substances 0.000 title claims description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 15
- 150000001336 alkenes Chemical class 0.000 title description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 190
- -1 trimethylsilylmethylene, benzyl Chemical group 0.000 claims description 126
- 229910052757 nitrogen Inorganic materials 0.000 claims description 99
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 125000005842 heteroatom Chemical group 0.000 claims description 33
- 125000001072 heteroaryl group Chemical group 0.000 claims description 31
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 25
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- 229910052735 hafnium Chemical group 0.000 claims description 21
- 150000004678 hydrides Chemical class 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
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- 125000004404 heteroalkyl group Chemical group 0.000 claims description 10
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
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- 239000001301 oxygen Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010936 titanium Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
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- 150000002390 heteroarenes Chemical class 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 claims 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 773
- 238000005481 NMR spectroscopy Methods 0.000 description 532
- 239000000243 solution Substances 0.000 description 342
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 276
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 259
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- 238000006243 chemical reaction Methods 0.000 description 108
- 238000000034 method Methods 0.000 description 106
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 102
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 101
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 42
- 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 41
- 238000006116 polymerization reaction Methods 0.000 description 38
- 239000012535 impurity Substances 0.000 description 33
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- 125000004432 carbon atom Chemical group C* 0.000 description 29
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 description 25
- 239000011734 sodium Substances 0.000 description 25
- 239000004711 α-olefin Substances 0.000 description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 24
- MDKCFLQDBWCQCV-UHFFFAOYSA-N benzyl isothiocyanate Chemical compound S=C=NCC1=CC=CC=C1 MDKCFLQDBWCQCV-UHFFFAOYSA-N 0.000 description 24
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 21
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 21
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 21
- 101710134784 Agnoprotein Proteins 0.000 description 20
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 20
- 239000003426 co-catalyst Substances 0.000 description 19
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- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 19
- 230000004913 activation Effects 0.000 description 18
- 125000002947 alkylene group Chemical group 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 17
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- 241000287219 Serinus canaria Species 0.000 description 16
- 150000001718 carbodiimides Chemical class 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 15
- 125000003636 chemical group Chemical group 0.000 description 15
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 13
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- 150000002540 isothiocyanates Chemical class 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 8
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 8
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 8
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- 150000003863 ammonium salts Chemical class 0.000 description 4
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
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- GSEWLHCVMFWKQO-UHFFFAOYSA-N hydrazinylidenemethanimine Chemical compound NN=C=N GSEWLHCVMFWKQO-UHFFFAOYSA-N 0.000 description 3
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- 238000010348 incorporation Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
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- 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 2
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- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
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- 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
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 239000012266 salt solution Substances 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
- 150000004819 silanols Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- SCABQASLNUQUKD-UHFFFAOYSA-N silylium Chemical class [SiH3+] SCABQASLNUQUKD-UHFFFAOYSA-N 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
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- LZPMJIKOSBZRCP-UHFFFAOYSA-M sodium hypochlorous acid chlorate Chemical compound Cl(=O)(=O)[O-].[Na+].ClO LZPMJIKOSBZRCP-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 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
- 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
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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Description
本出願は、その全体が参照により本明細書に援用される、2016年9月30日出願の米国仮特許出願第62/402,554号に対する優先権を主張する。
式Iは、その構造的骨格の一部としてグアニジン部分を1つ有し、金属-配位子錯体、前触媒、プロ触媒、重合触媒、またはホスファグアニジン錯体と称され得る。ホスファグアニジン部分の一般構造は、本開示内の他の配位子および他のホスファグアニジン金属錯体に見出すことができる。本開示を通して、多くのホスファグアニジン配位子およびホスファグアニジン金属錯体が、そのような一般式Iを用いて例示および記載されている。
式I、II、またはIIIの金属-配位子錯体を含むプロ触媒は、活性化助触媒にそれを接触させること、もしくはそれを組み合わせることによって、または金属系オレフィン重合反応で使用するための当該技術分野で既知のものなどの活性化技術を使用することによって、触媒的に活性になる。本明細書に使用するのに好適な活性化助触媒としては、アルキルアルミニウム、ポリマーまたはオリゴマーアルモキサン(アルミノキサンとしても知られる)、中性ルイス酸、および非ポリマー、非配位、イオン形成化合物(酸化条件下でのそのような化合物の使用を含む)が挙げられる。好適な活性化技術は、バルク電気分解である。前述の活性化助触媒および技術のうちの1つ以上の組み合わせもまた企図される。「アルキルアルミニウム」という用語は、モノアルキルアルミニウムジヒドリドもしくはモノアルキルアルミニウムジハロゲン化物、ジアルキルアルミニウムヒドリドもしくはジアルキルアルミニウムハロゲン化物、またはトリアルキルアルミニウムを意味する。アルミノキサンおよびそれらの調製は、例えば、米国特許(USPN)第6,103,657号で知られている。好ましいポリマーまたはオリゴマーアルモキサンの例は、メチルアルモキサン、トリイソブチルアルミニウム変性メチルアルモキサン、およびイソブチルアルモキサンである。
本触媒から生成されるポリオレフィン組成物は、重合条件下で1つ以上の助触媒および/または捕捉剤の存在下で、1つ以上のオレフィンモノマーと本開示に従ったオレフィン重合触媒系との反応生成物を含む。
本発明に従ったポリオレフィン組成物を生成するために、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、例えば、並列式、直列式、および/またはそれらの任意の組み合わせの、ループ反応器、等温反応器、流動床反応器、撹拌槽反応器、バッチ式反応器などの、1つ以上の従来の反応器を使用する溶液重合プロセス、粒子形成重合プロセス、およびそれらの組み合わせが挙げられるが、これらに限定されない。
窒素を充填した12℃のグローブボックス中で、ホスファグアニジン(39.4mg、0.0933mmol、1.00当量)とC6D6(0.50mL)との透明な黄金色の溶液に、ZrBn4(42.3mg、0.0933mmol、1.00当量)とC6D6(0.42mL)との溶液を素早く滴下する方式で添加した。1時間撹拌(300rpm)した後、アリコートを取り出したところ、NMRは完全な変換を示した。黄金色の溶液を、脱酸素した無水ヘキサン(10mL)で希釈し、濃縮し、ヘキサン(5mL)に懸濁し、濃縮し、このプロセスをもう一度繰り返して残留C6D6およびトルエンを除去し、ヘキサン(5mL)に懸濁し、次いで得られた黄金色の混合物を0.45μmのサブミクロンPTFEフィルターを通して濾過し、ヘキサンですすぎ(3x2mL)、濃縮して、暗金褐色の粘稠な泡沫としてジルコニウム金属-配位子錯体MCI-34(50.0mg、0.0553mmol、59%、純度87%)を得た。1H-NMRおよび31P-NMRによるNMRは、生成物が、純度およそ87%であることを示した。
1H NMR(500MHz、クロロホルム-d)δ7.38-7.26(m,5H),4.33(s,2H),1.14(s,9H)。13C NMR(126MHz、クロロホルム-d)δ140.73,138.79,128.53,127.86,127.48,55.29,50.86,31.16。
カルボジイミドは、異性体の混合物として存在する。アスタリスク(*)は、少量の異性体および/または互変異性体を表す。
1H NMR(500MHz、クロロホルム-d)δ8.08(dq,J=8.4,0.9Hz,1H),7.88(ddt,J=8.1,1.3,0.6Hz,1H),7.81(dd,J=8.1,1.2Hz,1H),7.57(ddd,J=8.4,6.8,1.4Hz,1H),7.53-7.48(m,2H),7.45(dd,J=8.1,7.0Hz,1H),4.77(s,2H),0.93(s,9H)。13C NMR(126MHz、クロロホルム-d)δ140.89,134.89,133.82,131.17,128.64,128.41,126.37,126.26,125.86,125.34,123.85,55.24,48.79,30.95。C16H18N2[M+H]+のHRMS(ESI)計算値239.1504、実測値239.1558。
1H NMR(500MHz、クロロホルム-d)δ8.15(dd,J=8.4,1.4Hz,1H),7.88-7.84(m,1H),7.74(d,J=8.2Hz,1H),7.62(dd,J=7.0,1.3Hz,1H),7.54-7.47(m,2H),7.47-7.43(m,1H),5.06(s,2H),4.03(s,1H),2.38(s,3H),1.42(s,9H)。13C NMR(126MHz、クロロホルム-d)δ148.57,137.76,133.58,131.55,128.45,126.66,125.57,125.47,125.27,124.44,123.96,52.97,52.58,28.94,15.48。C17H22N2S[M+H]+のHRMS(ESI)計算値287.2、実測値287.2。
1H NMR(500MHz、クロロホルム-d)δ7.98(d,J=8.3Hz,1H),7.87-7.83(m,1H),7.79(d,J=8.1Hz,1H),7.55-7.46(m,2H),7.46-7.37(m,2H),6.17(s,1H),5.90(s,1H),5.12(s,2H),1.27(s,9H)。13C NMR(126MHz、クロロホルム-d)δ180.81,133.89,132.64,131.30,128.90,128.81,126.80,126.74,126.10,125.42,123.47,52.89,48.07,29.48。C16H20N2S[M+H]+のHRMS(ESI)計算値273.1381、実測値273.1811。
1H NMR(500MHz、クロロホルム-d)δ7.36-7.25(m,5H),6.23(s,1H),5.82(s,1H),4.60(s,2H),4.17(s,1H),1.15(d,J=6.5Hz,6H)。13C NMR(126MHz、クロロホルム-d)δ180.61,136.99,127.87,127.57,48.35,46.22,22.52。
1H NMR(400MHz、クロロホルム-d)δ7.39-7.33(m,3H),7.30(d,J=7.8Hz,2H),7.22(t,J=7.1Hz,1H),4.52(br s,2H),3.97(br s,1H),2.38(s,3H),1.18(d,J=6.3Hz,6H)。13C NMR(101MHz、クロロホルム-d)δ151.32,141.04,128.24,127.39,126.46,52.22,45.01,23.49,14.46。
1H NMR(500MHz、クロロホルム-d)δ7.35(tdd,J=7.8,6.3,1.7Hz,8H),7.32-7.23(m,2H),4.59(s,4H),4.53-4.21(m,1H),2.42(s,3H)。13C NMR(126MHz、クロロホルム-d)δ152.61,140.20,128.41,127.60,126.83,52.81,50.37,14.40。C16H18N2S[M+H]+のLRMS(ESI)計算値271.1、実測値271.1。
1H NMR(500MHz,DMSO-d6)δ7.95(s,2H),7.36-7.20(m,10H),4.69(s,4H)。13C NMR(126MHz,DMSO-d6)δ183.46,139.71,128.70,127.68,127.28,47.57。
1H NMR(500MHz,DMSO-d6)δ7.87(s,1H),7.48(s,1H),7.33-7.17(m,9H),4.64(s,2H),3.62(s,2H),2.81(t,J=7.4Hz,2H)。13C NMR(126MHz,DMSO-d6)δ183.33,139.77,129.12,128.78,128.68,127.69,127.24,126.55,47.33,45.58,35.27。C16H18N2S[M+H]+のLCMS(ESI)計算値271.1、実測値271.1。
1H NMR(500MHz、クロロホルム-d)δ7.44-7.20(m,5H),6.34(d,J=146.5Hz,1H),5.92(s,1H),4.59(s,2H),3.21(s,2H),0.83(s,9H)。13C NMR(126MHz、クロロホルム-d)δ182.09,136.87,128.97,127.98,127.47,56.09(48.36*),31.69,27.26。C13H20N2S[M+H]+のMS-ESI計算値237.1、実測値237.1。
1H NMR(400MHz、クロロホルム-d)δ7.44-7.26(m,4H),7.10(d,J=1.5Hz,1H),7.08(s,1H),7.03(d,J=6.5Hz,1H),7.01(d,J=6.5Hz,1H),4.53(s,3H),2.96(hept,J=6.9Hz,2H),2.43(s,3H),1.20(d,J=6.9Hz,6H),1.13(d,J=6.9Hz,6H)。13C NMR(101MHz、クロロホルム-d)δ144.22,139.42,138.78,128.57,127.54,127.42,123.09,123.02,47.10,28.13,23.40,23.35,13.74。C21H28N2S[M+H]+のLRMS(ESI)計算値341.2、実測値341.2。
1H NMR(500MHz、クロロホルム-d)δ8.42(s,1H),7.33(t,J=7.7Hz,1H),7.26-7.17(m,6H),5.54(t,J=5.8Hz,1H),4.82(d,J=5.7Hz,2H),3.20(hept,J=6.8Hz,2H),1.21(d,J=6.9Hz,6H),1.13(d,J=6.9Hz,6H)。13C NMR(126MHz、クロロホルム-d)δ181.44,147.81,137.57,129.94,129.79,128.58,127.64,127.61,124.49,49.01,28.56,24.70,23.07。C20H26N2S[M+H]+のLRMS(ESI)計算値327.2、実測値327.2。
1H NMR(500MHz、クロロホルム-d)δ8.13(s,1H),7.35-7.23(m,5H),6.89(s,1H),6.81(d,J=1.6Hz,2H),6.33(t,J=5.5Hz,1H),4.87(d,J=5.5Hz,2H),2.28(s,6H)。13C NMR(126MHz、クロロホルム-d)δ180.79,140.08,137.42,135.77,129.07,128.72,127.66,127.57,122.87,49.34,21.23。
1H NMR(400MHz、クロロホルム-d)δ7.44-7.20(m,5H),6.65(s,1H),6.53(s,2H),4.74(s,1H),4.50(s,2H),2.31-2.27(br s,3H),2.26-2.25(br s,6H)。
1H NMR(500MHz、ベンゼン-d6)δ7.45(dddd,J=10.3,5.6,2.6,1.4Hz,6H),7.20-7.15(m,2H),7.06-6.96(m,7H),5.01(d,J=4.8Hz,2H),3.84(s,1H),2.10(d,J=2.9Hz,6H),1.87(p,J=3.0Hz,3H),1.56-1.44(m,6H)。13C NMR(126MHz、ベンゼン-d6)δ154.83(d,J=34.0Hz),142.81,134.63(d,J=14.2Hz),134.04(d,J=19.8Hz),129.05,128.80(d,J=6.7Hz),127.95,127.38,125.84,55.68(d,J=36.4Hz),52.71,41.64,36.54,29.66。31P NMR(202MHz、ベンゼン-d6)δ-15.75。
1H NMR(500MHz、クロロホルム-d)δ7.42-7.24(m,5H),5.96(t,J=5.3Hz,1H),5.94-5.84(m,1H),4.77(d,J=5.3Hz,2H),2.15-2.05(m,5H),1.97(dd,J=7.1,2.9Hz,8H),1.71-1.57(m,9H)。13C NMR(126MHz、クロロホルム-d)δ181.08,137.37,128.88,127.75,127.44,54.10,49.61,42.31,35.97,29.34。C18H24N2S[M+H]+のHRMS(ESI)計算値301.1733、実測値301.1815。
1H NMR(400MHz、クロロホルム-d)δ7.41-7.15(m,5H),4.61(s,2H),3.89(s,1H),2.35(s,3H),2.09(d,J=6.6Hz,6H),1.99(d,J=3.0Hz,3H),1.67(q,J=5.2,4.0Hz,6H)。13C NMR(101MHz、クロロホルム-d)δ147.93,142.37,128.03,127.06,125.86,54.84,53.15,41.92,36.65,29.70,15.53。C19H26N2S[M+H]+のHRMS(ESI)計算値315.1890、実測値315.1974。
1H NMR(500MHz、クロロホルム-d)δ7.39-7.27(m,5H),6.16(s,1H),5.79(s,1H),4.61(s,2H),3.84(s,1H),1.94(dq,J=12.6,4.0Hz,2H),1.64(dt,J=13.8,3.9Hz,2H),1.56(dq,J=12.2,4.0Hz,1H),1.37-1.27(m,2H),1.14(tt,J=15.3,7.6Hz,3H)。13C NMR(126MHz、クロロホルム-d)δ180.54,136.88,128.92,127.92,127.54,52.96,48.38,32.69,25.31,24.51。
1H NMR(500MHz、クロロホルム-d)δ7.34(dt,J=14.8,7.6Hz,4H),7.23(t,J=7.3Hz,1H),4.49(d,J=79.8Hz,2H),4.04(s,1H),3.64(m,1H),2.38(s,3H),2.09-1.80(m,2H),1.72(dt,J=13.4,4.1Hz,2H),1.62(dt,J=13.0,4.0Hz,1H),1.37(q,J=12.5Hz,2H),1.20(q,J=12.2Hz,3H)。13C NMR(126MHz、クロロホルム-d)δ150.83,141.74,128.23,127.35,126.42,54.16,50.70,34.61,25.81,24.92,14.44。C15H22N2S[M+H]+のHRMS(ESI)計算値263.1577、実測値263.1655。
1H NMR(500MHz、クロロホルム-d)δ7.38-7.24(m,6H),4.35(s,2H),3.15(dp,J=8.3,3.8Hz,1H),1.72(ddt,J=56.9,13.0,4.0Hz,6H),1.55-1.48(m,1H),1.31-1.09(m,6H)。13C NMR(126MHz、クロロホルム-d)δ140.72,138.70,128.55,127.68,127.43,55.68,50.72,34.68,25.37,24.48。C14H18N2[M+H]+のHRMS(ESI)計算値215.1543、実測値215.1536。
1H NMR(500MHz、ベンゼン-d6)δ3.00(t,J=6.1Hz,2H),2.19(t,J=6.1Hz,2H),1.95(s,6H),1.19(s,9H)。13C NMR(126MHz、ベンゼン-d6)δ139.66,59.93,54.10,44.76,44.30,30.88。
1H NMR(500MHz、クロロホルム-d)δ5.21(s,1H),5.05(s,1H),3.16(q,J=5.4Hz,2H),2.36(dd,J=6.1,5.3Hz,2H),2.19(s,6H),1.29(s,9H)。13C NMR(126MHz、クロロホルム-d)δ158.49,59.54,49.89,45.21,38.09,29.49。C9H22N3O[M+H]+のHRMS(ESI)計算値188.2、実測値188.2。
1H NMR(400MHz、ベンゼン-d6)δ3.12(td,J=6.8,1.3Hz,2H),2.14(t,J=6.9Hz,2H),1.98(s,6H),1.54(pd,J=6.8,1.2Hz,2H),1.14(s,9H)。13C NMR(101MHz、ベンゼン-d6)δ139.64,56.49,54.22,45.10,44.47,31.11,29.62。
1H NMR(500MHz、クロロホルム-d)δ5.23(s,1H),5.07(s,1H),3.13(q,J=6.2Hz,2H),2.28(t,J=6.7Hz,2H),2.16(s,5H),1.57(p,J=6.6Hz,2H),1.28(s,8H)。13C NMR(126MHz、クロロホルム-d)δ158.45,57.28,49.88,45.35,39.18,29.50,27.66。C10H23N3O[M+H]+のHRMS(ESI)計算値202.1875、実測値202.1965。
ポリオレフィン触媒スクリーニングは、ハイスループット並列重合反応器(PPR)システムで行った。PPRシステムは、不活性雰囲気のグローブボックス内の48個の単一セル(6×8マトリックス)反応器のアレイで構成した。各セルは、およそ5mLの内部作業液体容量を有するガラスインサートを備えていた。各セルは独立した圧力制御を有し、800rpmで連続的に撹拌した。特に明記しない限り、触媒溶液はトルエン中で調製した。全ての液体(すなわち溶媒、1-オクテン、および触媒溶液)は、自動シリンジを介して添加した。ガス状試薬(すなわち、エチレン、H2)は、ガス注入口を介して添加した。各実験の前に、反応器を80℃に加熱し、エチレンでパージし、排気した。
分子量データは、ハイブリッドSymyx/Dow構築ロボット支援希釈高温ゲル浸透クロマトグラファー(Sym-RAD-GPC)での分析によって決定した。百万分の300(ppm)のブチル化ヒドロキシルトルエン(BHT)によって安定化された、10mg/mLの濃度の1,2,4-トリクロロベンゼン(TCB)中で、ポリマー試料を120分間160℃で加熱することによって溶解した。次いで、試料の250μLアリコートを注入する直前に、各試料を1mg/mLに希釈した。GPCは、160℃で2.0mL/分の流速の2つのPolymer Labs PLgel 10μm MIXED-Bカラム(300×10mm)を備えていた。試料検出は、PolyChar IR4検出器を濃度モードで使用して行った。この温度で、TCB中のポリスチレン(PS)およびホモポリエチレン(PE)の既知のMark-Houwink係数を使用して、PEに調整された見かけの単位を用いて、光散乱較正用(narrow)PS基準物質の従来の較正を利用した。
IR分析より前に、HT-GPC分析用の試料の実験を行った。試料の1-オクテン組み込みの堆積および分析には、48ウェルHTシリコンウェハを利用した。このプロセスでは、試料に施した全ての追加の加熱は、160℃で210分以下の持続時間であり、試料は、再加熱して磁気GPC撹拌棒を取り外し、同様にJ-KEM Scientific加熱式自動シェーカーでガラスロッド撹拌棒を用いて振盪しなければならなかった。次いで、Tecan MiniPrep75堆積ステーションを使用して加熱しながら試料を堆積し、160℃の窒素パージ下で、堆積したウェハのウェルから1,2,4-トリクロロベンゼンを蒸発させた。1-オクテンの分析は、NEXUS670E.S.P.FT-IRを使用してHTシリコンウェハ上で行った。
バッチ式反応器重合は、2Lまたは4LのParr(商標)バッチ式反応器で実行した。反応器は、電気加熱マントルによって加熱し、冷却水を含有する内部蛇管冷却コイルによって冷却した。反応器および加熱/冷却システムの両方を、Camile(商標)TGプロセスコンピューターによって制御および監視した。反応器の底部に、触媒失活剤溶液(catalyst kill solution)(典型的には5mLのIrgafos/Irganox/トルエン混合物)で予め満たしたステンレス鋼製のダンプポットに反応器の内容物を空ける、ダンプバルブを取り付ける。ポットとタンクの両方を窒素でパージして、ダンプポットを30ガロンのブロータンクと通気させた。重合または触媒補給のために使用した全ての溶媒は、重合に影響を及ぼし得るあらゆる不純物を除去するために溶媒精製カラムを通した。1-オクテンおよびIsoparEは、A2アルミナを含有する第1のカラム、Q5反応物を含有する第2のカラムの2つのカラムを通過させた。エチレンは、A204アルミナおよび
本願発明には以下の態様が含まれる。
項1.
式Iに従ったホスファグアニジン錯体であって、
R1およびR5が、水素化物、脂肪族、ヘテロ脂肪族、芳香族、およびヘテロ芳香族部分から選択された同じかまたは異なる部分を含み、
R2およびR4が、脂肪族部分、ヘテロ脂肪族部分、芳香族部分、またはヘテロ芳香族部分から選択された同じかまたは異なる部分を含み、
R3が、孤立電子対またはヘテロ原子を含み、
Mが、チタン、ジルコニウム、またはハフニウムから選択され、Xが、脂肪族部分、芳香族部分、NRN 2部分、またはハロゲン化物部分から選択され、RNが、アルキル、アリール、またはヘテロアリール部分から選択され、
各点線が、任意選択的に架橋結合を定義する、ホスファグアニジン錯体。
項2.
Xが、メチル、トリメチルシリルメチレン、ベンジル、クロロ、またはNMe2部分から選択され、R2およびR4が、非置換フェニル環、置換フェニル環、置換シクロヘキシル基、または非置換シクロヘキシル基から選択された同じかまたは異なる部分を含み、R3が、孤立電子対、または酸素、硫黄、窒素、ホウ素、もしくはそれらの組み合わせから選択されたヘテロ原子を含み、R1およびR5が、水素化物、アルキル、メチル、エチル、イソ-プロピル、シクロヘキシルtert-ブチル、アダマンチル、ネオペンチル、フェネチル、ベンジル、置換または非置換フェニル部分から独立して選択される、項1に記載のホスファグアニジン錯体。
項3.
前記ホスファグアニジン錯体が、式IIの構造を含み、
項4.
前記ホスファグアニジン錯体が、式IIIの構造を含み、
項5.
項1~4のいずれか一項に記載のホスファグアニジン錯体を含む、重合触媒系。
項6.
前記重合触媒系が、連鎖移動剤を含む、項1~5に記載の重合触媒系。
項7.
前記重合触媒系中の前記連鎖移動剤が、ジエチル亜鉛である、項1~6に記載の重合触媒系。
項8.
項5~7に記載の重合触媒から生成された、エチレンホモポリマー。
項9.
項5~7に記載の重合触媒から生成された、α-オレフィンホモポリマーであって、前記α-オレフィンが、C3-C12部分で構成されている、α-オレフィンホモポリマー。
項10.
前記α-オレフィンが、1-オクテンである、項9に記載のα-オレフィンホモポリマー。
項11.
項5~7に記載の重合触媒から生成された、エチレン/α-オレフィンコポリマーであって、前記α-オレフィンが、少なくとも1つのC3-C12α-オレフィンコモノマーを含む、エチレン/α-オレフィンコポリマー。
項12.
前記α-オレフィンが、1-オクテンである、項11に記載のエチレン/α-オレフィンコポリマー。
Claims (7)
- Xが、メチル、トリメチルシリルメチレン、ベンジル、またはクロロから選択され、R2およびR4が、非置換フェニル環、置換フェニル環、置換シクロヘキシル基、または非置換シクロヘキシル基から選択された同じかまたは異なる部分を含み、R3が、孤立電子対、または酸素、硫黄、窒素、ホウ素、もしくはそれらの組み合わせから選択されたヘテロ原子を含み、R1およびR5が、水素化物、アルキル、メチル、エチル、イソ-プロピル、シクロヘキシルtert-ブチル、アダマンチル、ネオペンチル、フェネチル、ベンジル、置換または非置換フェニル部分から独立して選択される、請求項1に記載のホスファグアニジン錯体。
- 前記ホスファグアニジン錯体が、式IIの構造を含み、
- 前記ホスファグアニジン錯体が、式IIIの構造を含み、
- 請求項1~4のいずれか一項に記載のホスファグアニジン錯体を含む、重合触媒系。
- 前記重合触媒系が、連鎖移動剤を含む、請求項5に記載の重合触媒系。
- 前記重合触媒系中の前記連鎖移動剤が、ジエチル亜鉛である、請求項6に記載の重合触媒系。
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JP2003509518A (ja) | 1998-08-04 | 2003-03-11 | イーストマン ケミカル カンパニー | 改良された色及び接着特性を有する高分子量で主として無定形のポリマーの合成方法 |
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KR20190060809A (ko) | 2019-06-03 |
CN109963886A (zh) | 2019-07-02 |
EP3519470A1 (en) | 2019-08-07 |
BR112019005993B1 (pt) | 2022-10-11 |
EP3519470B1 (en) | 2020-10-21 |
WO2018064493A1 (en) | 2018-04-05 |
CN109963886B (zh) | 2023-01-06 |
KR102606000B1 (ko) | 2023-11-27 |
US20200031960A1 (en) | 2020-01-30 |
ES2845147T3 (es) | 2021-07-26 |
US11066495B2 (en) | 2021-07-20 |
BR112019005993A2 (pt) | 2019-06-25 |
JP2019534866A (ja) | 2019-12-05 |
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