JP6974448B2 - ビス連結ホスファグアニジン第iv族金属錯体およびそれから製造されたオレフィン重合触媒 - Google Patents
ビス連結ホスファグアニジン第iv族金属錯体およびそれから製造されたオレフィン重合触媒 Download PDFInfo
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- JP6974448B2 JP6974448B2 JP2019515935A JP2019515935A JP6974448B2 JP 6974448 B2 JP6974448 B2 JP 6974448B2 JP 2019515935 A JP2019515935 A JP 2019515935A JP 2019515935 A JP2019515935 A JP 2019515935A JP 6974448 B2 JP6974448 B2 JP 6974448B2
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- 239000002685 polymerization catalyst Substances 0.000 title claims description 26
- XCXAQVZPLNXACA-UHFFFAOYSA-N phosphanylmethanimidamide Chemical group NC(P)=N XCXAQVZPLNXACA-UHFFFAOYSA-N 0.000 title description 26
- 150000001336 alkenes Chemical class 0.000 title description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 18
- 150000004696 coordination complex Chemical class 0.000 title description 6
- -1 phosphaguanidine compound Chemical class 0.000 claims description 130
- 239000003446 ligand Substances 0.000 claims description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 125000001072 heteroaryl group Chemical group 0.000 claims description 25
- 125000005842 heteroatom Chemical group 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- 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 10
- 150000004678 hydrides Chemical group 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 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 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002390 heteroarenes Chemical group 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 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 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 claims description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 283
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 204
- 238000005481 NMR spectroscopy Methods 0.000 description 115
- 239000000243 solution Substances 0.000 description 76
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 67
- 239000005977 Ethylene Substances 0.000 description 67
- 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 65
- 239000000203 mixture Substances 0.000 description 60
- 229920000642 polymer Polymers 0.000 description 51
- 239000003054 catalyst Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 49
- 238000006116 polymerization reaction Methods 0.000 description 45
- 239000004711 α-olefin Substances 0.000 description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- 239000007787 solid Substances 0.000 description 37
- 238000003756 stirring Methods 0.000 description 35
- 230000008569 process Effects 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 33
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 29
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 29
- 239000004810 polytetrafluoroethylene Substances 0.000 description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 28
- 239000012141 concentrate Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 25
- 239000008241 heterogeneous mixture Substances 0.000 description 25
- 239000000725 suspension Substances 0.000 description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 125000001183 hydrocarbyl group Chemical group 0.000 description 22
- 125000002947 alkylene group Chemical group 0.000 description 19
- 229920000573 polyethylene Polymers 0.000 description 19
- 239000002904 solvent Substances 0.000 description 17
- 239000004215 Carbon black (E152) Substances 0.000 description 16
- 230000004913 activation Effects 0.000 description 16
- 125000003636 chemical group Chemical group 0.000 description 16
- 229920000098 polyolefin Polymers 0.000 description 16
- 125000001424 substituent group Chemical group 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 14
- 238000007792 addition Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 229920001400 block copolymer Polymers 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 238000012546 transfer Methods 0.000 description 11
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 10
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 159000000003 magnesium salts Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 229910007926 ZrCl Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000003426 co-catalyst Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 150000004820 halides Chemical group 0.000 description 7
- 125000004474 heteroalkylene group Chemical group 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 125000000743 hydrocarbylene group Chemical group 0.000 description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 125000002950 monocyclic group Chemical group 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 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 7
- 238000006467 substitution reaction Methods 0.000 description 7
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 125000002619 bicyclic group Chemical group 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- 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 6
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
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- 125000002993 cycloalkylene group Chemical group 0.000 description 5
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 5
- 125000004404 heteroalkyl group Chemical group 0.000 description 5
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
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- 238000010348 incorporation Methods 0.000 description 5
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- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- MDKCFLQDBWCQCV-UHFFFAOYSA-N benzyl isothiocyanate Chemical compound S=C=NCC1=CC=CC=C1 MDKCFLQDBWCQCV-UHFFFAOYSA-N 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
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- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229910021482 group 13 metal Inorganic materials 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
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- 229910052710 silicon Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- QXALIERKYGCHHA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)borane Chemical compound BC1=C(F)C(F)=C(F)C(F)=C1F QXALIERKYGCHHA-UHFFFAOYSA-N 0.000 description 3
- 125000000008 (C1-C10) 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RKLVWHIHYXVTMM-UHFFFAOYSA-N B.C1CCCCC1PC1CCCCC1 Chemical compound B.C1CCCCC1PC1CCCCC1 RKLVWHIHYXVTMM-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YWOIGJHGVURSBN-UHFFFAOYSA-N NP(=N)N.[Hf] Chemical compound NP(=N)N.[Hf] YWOIGJHGVURSBN-UHFFFAOYSA-N 0.000 description 3
- FRSXKXAHHPTBJV-UHFFFAOYSA-N NP(=N)N.[Zr] Chemical compound NP(=N)N.[Zr] FRSXKXAHHPTBJV-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 3
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- 238000012685 gas phase polymerization Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 150000002540 isothiocyanates Chemical class 0.000 description 3
- 150000007527 lewis bases Chemical group 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
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- 238000007613 slurry method Methods 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- 125000006736 (C6-C20) aryl 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
- LBYVZRFDLNAPRC-UHFFFAOYSA-N 2-sulfanylguanidine Chemical compound NC(=N)NS LBYVZRFDLNAPRC-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAADZYUXQLUXFX-UHFFFAOYSA-N N-phenylmethylthioformamide Natural products S=CNCC1=CC=CC=C1 QAADZYUXQLUXFX-UHFFFAOYSA-N 0.000 description 2
- SHMHIUCQSFMZQE-UHFFFAOYSA-N P(N)(N)=N Chemical compound P(N)(N)=N SHMHIUCQSFMZQE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
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- 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
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- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
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- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZKEFILOOQGVKNY-UHFFFAOYSA-N triphenylphosphane;dihydrobromide Chemical compound Br.Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZKEFILOOQGVKNY-UHFFFAOYSA-N 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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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62/402,541号に対する優先権を主張する。
以下に示すように、式Iは、その構造骨格の一部として少なくとも2つのホスファグアニジン部分および遷移金属中心を有する。ホスファグアニジン部分の一般構造は、この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。
式Iの金属−配位子錯体の前述の実施形態を含むプロ触媒は、それを活性化共触媒に接触させるか、もしくはそれを活性化共触媒と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に使用するための当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活性にされる。本発明で使用するのに好適な活性化共触媒は、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(酸化条件下でそのような化合物の使用を含む)を含む。好適な活性化技術は、バルク電気分解である。前述の活性化共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。用語「アルキルアルミニウム」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ライド、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ライド、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、米国特許番号(USPN)米国特許第6,103,657号で知られている。ポリマーアルモキサン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。
本触媒から製造されるポリオレフィン組成物は、重合条件下ならびに1つ以上の共触媒および/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よるオレフィン重合触媒系との反応生成物を含む。
本開示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、溶液重合プロセス、粒子形成重合プロセス、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。
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)。
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(brs、2H)、3.97(brs、1H)、2.38(s、3H)、1.18(d、J=6.3Hz、6H)。
1H NMR(500MHz、クロロホルム−d)δ7.36(d、J=5.5Hz、3H)、7.33−7.27(m、2H)、7.04−6.98(m、2H)、6.87(t、J=7.5Hz、1H)、4.74−4.46(m、3H)、2.45−2.34(m、3H)、2.12(s、6H)。
1H NMR(500MHz、クロロホルム−d)δ7.65(s、1H)、7.32−7.27(m、2H)、7.26−7.22(m、3H)、7.16(dd、J=8.5、6.5Hz、1H)、7.10(d、J=7.5Hz、2H)、5.72−5.54(m、1H)、4.85(d、J=5.4Hz、2H)、2.26(s、6H)。
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)。
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)。
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)。
1H NMR(400MHz、ベンゼン−d6)δ7.46−7.40(m、2H)、7.30−7.22(m、10H)、7.22−7.16(m、4H)、7.16−7.13(m、4H)、7.13−7.10(m、8H)、7.05(ddt、J=10.7、6.1、2.2Hz、4H)、6.89(dd、J=5.0、2.0Hz、1H)、6.72−6.63(m、10H)、6.56(td、J=7.4、1.7Hz、1H)、4.63(d、J=2.1Hz、4H)、0.96(s、6H)。
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)反応器のアレイから構成されていた。各セルは、およそ5mLの内部作動液容量を有するガラスインサートを装備していた。各セルは、独立した圧力制御を有しており、800rpmで連続的に撹拌した。特記しない限り、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、連鎖シャトリング剤溶液、および触媒溶液)をロボットシリンジで添加した。ガス状試薬(すなわち、エチレン、H2)を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、通気させた。
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ィー(Sym−RAD−GPC)での分析によって決定した。300万分率(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の濃度で1,2,4−トリクロロベンゼン(TCB)中に160℃で120分間加熱することによってポリマー試料を溶解した。次いで、250μLの一定分量の試料を注入する直前に、各試料を1mg/mLに希釈した。160℃で2.0mL/分の流速で、2つのPolymer Labs PLgel 10μm MIXED−Bカラム(300×10mm)をGPCに装備した。試料検出は、濃度モードにおいてPolyChar IR4検出器を使用して行った。この温度でTCB中のポリスチレン(PS)およびポリエチレン(PE)についての既知のMark−Houwink係数を使用して、ホモポリエチレン(PE)に調整された見掛け単位を用いて、狭ポリスチレン(PS)標準の従来の較正を利用した。
HT−GPC分析用の試料のランニングは、IR分析に先行した。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シリコンウエハを利用した。このプロセスでは、試料が供された全ての追加の熱は160℃であり、持続時間は210分以下であり、試料を再加熱して磁気GPCスターラーバーを取り外すと共に、J−KEM Scientific加熱式ロボットシェーカー上でガラス棒スターラーバーで振盪しなければならなかった。次いで、Tecan MiniPrep 75堆積ステーションを使用して加熱しながら試料を堆積させ、1,2,4−トリクロロベンゼンを窒素パージ下の160℃でウエハの堆積されたウェルから蒸発させた。1−オクテンの分析は、NEXUS 670 E.S.P.FT−IRを使用してHTシリコンウエハで行った。
バッチ反応器重合は、2LのParr(商標)バッチ反応器中で実施した。反応器は、電気加熱マントルによって加熱され、冷却水を含有する内部蛇行冷却コイルによって冷却される。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。反応器の底部には、反応器の内容物を触媒死滅溶液(典型的には5mLのIrgafos/Irganox/トルエン混合物)を予め充填したステンレス鋼製ダンプポットに排出するダンプバルブが装着されている。ダンプポットを30ガロンのブローダウンタンクに通気し、ポットおよびタンクの両方を窒素でパージした。重合または触媒補給のために使用された全ての溶媒は、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過させた。1−オクテンおよびIsoparEを2つのカラムに通過させ、第1のカラムはA2アルミナを含有し、第2のカラムはQ5を含有していた。エチレンを2つのカラムに通過させ、第1のカラムはA2O4アルミナおよび4Aモル篩を含有し、第2のカラムはQ5反応物を含有していた。移動に使用されたN2は、A2O4アルミナ、4Aモル篩、およびQ5を含有する単一のカラムに通過させた。
活性およびMw以上に、新しい触媒の連鎖移動能力を理解することは、Dowにおける新しいポリオレフィン触媒ファミリーの開発のための1つの重要な局面である。触媒の連鎖移動能力は、分子量の低下およびシャトリング触媒に予想されるPDIの狭小化を観察するために連鎖シャトリング剤(CSA)のレベルを変えるキャンペーンを実行することによって最初に評価される。良好な連鎖シャトル剤である可能性がある触媒によって生成されたポリマーの分子量は、より劣悪なシャトリング触媒によって生成されたポリマー分子量よりもCSAの添加に対してより敏感である。メイヨー式(式1)は、連鎖移動剤が存在しない場合に、連鎖移動剤が天然の数平均鎖長
本願発明には以下の態様が含まれる。
項1.
式Iのホスファグアニジン化合物を含む金属−配位子錯体であって、
R1、R5、R6、およびR10は、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独立して選択される同じまたは異なる部分を含み、
R2、R3、R7、およびR8は、脂肪族部分、芳香族部分、またはヘテロ芳香族部分から独立して選択される同じまたは異なる部分を含み、
R4およびR9は独立して、孤立電子対またはヘテロ原子から選択され、
Mは、チタン、ジルコニウム、またはハフニウムから選択され、各Xは独立して、脂肪族部分、芳香族部分、NRN 2部分、またはハライド部分から選択され、RNは、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、
各点線は、任意で架橋結合を定義する、金属−配位子錯体。
項2.
各R1、R5、R6、およびR10が独立して、水素化物、メチル、エチル、イソ−プロピル、シクロヘキシル、tert−ブチル、ネオペンチル、フェネチル、ベンジル、アダマンチル、フェニル、2,6−ジ−イソ−プロピルフェニル、または2,6−ジメチルフェニルから選択される、項1に記載の金属−配位子錯体。
項3.
各R2、R3、R7、およびR8が独立して、エチル、シクロヘキシル、フェニル、または4−メトキシフェニルから選択される、項1または2に記載の金属−配位子錯体。
項4.
各R4およびR9が独立して、孤立電子対、酸素、窒素、硫黄、またはボラン基から選択される、項1〜3に記載の金属−配位子錯体。
項5.
各R4およびR9が孤立電子対である、項1〜3に記載の金属−配位子錯体。
項6.
各Xが独立して、メチル、トリメチルシリルメチル(−CH2SiMe3)、ベンジル、クロロ、またはジメチルアミド(NMe2)基から選択される同じまたは異なる部分を含む、項1〜4に記載の金属−配位子錯体。
項7.
Mがジルコニウムである、項1〜6に記載の金属−配位子錯体。
項8.
Mがハフニウムである、項1〜6に記載の金属−配位子錯体。
項9.
項1〜8に記載の金属−配位子錯体を含む重合触媒系であって、連鎖移動剤を含む、重合触媒系。
項10.
前記連鎖移動剤がジエチル亜鉛である、項9に記載の重合触媒系。
項11.
項9および10に記載の重合触媒系から製造された、エチレンホモポリマー。
項12.
項9および10に記載の重合触媒系から製造された、α−オレフィンホモポリマー。
項13.
前記α−オレフィンが1−オクテンである、項12に記載のα−オレフィンホモポリマー。
項14.
項9および10に記載の重合触媒系から製造されたエチレン/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15.
前記α−オレフィンが1−オクテンである、項14に記載のエチレン/α−オレフィンコポリマー。
Claims (10)
- 式Iのホスファグアニジン化合物を含む金属−配位子錯体であって、
R1、R5、R6、およびR10は、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独立して選択される同じまたは異なる部分を含み、
R2、R3、R7、およびR8は、脂肪族部分、芳香族部分、またはヘテロ芳香族部分から独立して選択される同じまたは異なる部分を含み、
R4およびR9は独立して、孤立電子対またはヘテロ原子から選択され、
Mは、チタン、ジルコニウム、またはハフニウムから選択され、各Xは独立して、脂肪族部分、芳香族部分、NRN 2部分、またはハライド部分から選択され、RNは、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、
各点線は、任意で架橋結合を定義する、金属−配位子錯体。 - 各R1、R5、R6、およびR10が独立して、水素化物、メチル、エチル、イソ−プロピル、シクロヘキシル、tert−ブチル、ネオペンチル、フェネチル、ベンジル、アダマンチル、フェニル、2,6−ジ−イソ−プロピルフェニル、または2,6−ジメチルフェニルから選択される、請求項1に記載の金属−配位子錯体。
- 各R2、R3、R7、およびR8が独立して、エチル、シクロヘキシル、フェニル、または4−メトキシフェニルから選択される、請求項1または2に記載の金属−配位子錯体。
- 各R4およびR9が独立して、孤立電子対、酸素、窒素、硫黄、またはボラン基から選択される、請求項1〜3に記載の金属−配位子錯体。
- 各R4およびR9が孤立電子対である、請求項1〜3に記載の金属−配位子錯体。
- 各Xが独立して、メチル、トリメチルシリルメチル(−CH2SiMe3)、ベンジル、クロロ、またはジメチルアミド(NMe2)基から選択される同じまたは異なる部分を含む、請求項1〜4に記載の金属−配位子錯体。
- Mがジルコニウムである、請求項1〜6に記載の金属−配位子錯体。
- Mがハフニウムである、請求項1〜6に記載の金属−配位子錯体。
- 請求項1〜8に記載の金属−配位子錯体を含む重合触媒系であって、連鎖移動剤を含む、重合触媒系。
- 前記連鎖移動剤がジエチル亜鉛である、請求項9に記載の重合触媒系。
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