JP7051827B2 - 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
- Publication number
- JP7051827B2 JP7051827B2 JP2019515967A JP2019515967A JP7051827B2 JP 7051827 B2 JP7051827 B2 JP 7051827B2 JP 2019515967 A JP2019515967 A JP 2019515967A JP 2019515967 A JP2019515967 A JP 2019515967A JP 7051827 B2 JP7051827 B2 JP 7051827B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- groups
- thioguanidine
- item
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LBYVZRFDLNAPRC-UHFFFAOYSA-N 2-sulfanylguanidine Chemical group NC(=N)NS LBYVZRFDLNAPRC-UHFFFAOYSA-N 0.000 title claims description 121
- 238000006116 polymerization reaction Methods 0.000 title claims description 53
- 239000003054 catalyst Substances 0.000 title description 57
- 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 description 109
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 67
- 239000005977 Ethylene Substances 0.000 claims description 67
- 239000003446 ligand Substances 0.000 claims description 67
- 239000004711 α-olefin Substances 0.000 claims description 49
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 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 description 2
- -1 polyethylene Polymers 0.000 description 78
- 238000005481 NMR spectroscopy Methods 0.000 description 49
- 229920000642 polymer Polymers 0.000 description 42
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 26
- 239000000243 solution Substances 0.000 description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 229920000573 polyethylene Polymers 0.000 description 18
- 125000005842 heteroatom Chemical group 0.000 description 17
- 125000000743 hydrocarbylene group Chemical group 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 125000003636 chemical group Chemical group 0.000 description 16
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 16
- 238000006467 substitution reaction Methods 0.000 description 16
- 239000000725 suspension Substances 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229920000098 polyolefin Polymers 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002184 metal Chemical class 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 11
- 229920001400 block copolymer Polymers 0.000 description 10
- 125000001072 heteroaryl group Chemical group 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 125000002619 bicyclic group Chemical group 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 125000004474 heteroalkylene group Chemical group 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 125000002950 monocyclic group Chemical group 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002685 polymerization catalyst Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000012043 crude product Substances 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
- 125000000524 functional group Chemical group 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 125000002993 cycloalkylene group Chemical group 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 125000004404 heteroalkyl group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 4
- 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
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000945 filler Substances 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
- 150000007527 lewis bases Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000007613 slurry method Methods 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- 125000006651 (C3-C20) 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
- UULUECCNPPJFBU-UHFFFAOYSA-N 2-isothiocyanato-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1N=C=S UULUECCNPPJFBU-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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
- 235000019502 Orange oil Nutrition 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical group [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000010502 orange oil Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 125000006747 (C2-C10) heterocycloalkyl group Chemical group 0.000 description 1
- DYEQHQNRKZJUCT-UHFFFAOYSA-N 1,2-dimethylidenecyclohexane Chemical compound C=C1CCCCC1=C DYEQHQNRKZJUCT-UHFFFAOYSA-N 0.000 description 1
- XBJHZEUYCYYCLK-UHFFFAOYSA-N 1,2-dimethylidenecyclopentane Chemical compound C=C1CCCC1=C XBJHZEUYCYYCLK-UHFFFAOYSA-N 0.000 description 1
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 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 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- WEOIMVGRKQBCKD-UHFFFAOYSA-N 2,3-dimethylidenebicyclo[2.2.2]octane Chemical compound C1CC2CCC1C(=C)C2=C WEOIMVGRKQBCKD-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MSIPIPSIPFSYRF-UHFFFAOYSA-N 3,4-dimethylbicyclo[2.2.1]heptane Chemical compound C1CC2(C)C(C)CC1C2 MSIPIPSIPFSYRF-UHFFFAOYSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical class [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005700 Putrescine Substances 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
- 229910007950 ZrBN Inorganic materials 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
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 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
- 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
- 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
- 238000005485 electric heating Methods 0.000 description 1
- 239000003623 enhancer Substances 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
- 230000020169 heat generation Effects 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
- 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
- 238000001802 infusion Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 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
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds 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
- 230000000877 morphologic effect Effects 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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012766 organic filler Substances 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
- 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
- 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
- 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
- 238000003786 synthesis reaction Methods 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
- 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
- 239000012808 vapor phase Substances 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- 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)
- Polymerization Catalysts (AREA)
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。
本願発明には以下の態様が含まれる。
項1.
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。
項2.
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、
項3.
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、項2に記載の組成物。
項4.
A1およびA2が、独立して、水素またはメチルである、項3に記載の組成物。
項5.
A1およびA2の両方がメチルである、項3に記載の組成物。
項6.
R2が、(C1-C10)アルキル基である、項2に記載の組成物。
項7.
R2が、メチルである、項2に記載の組成物。
項8.
全ての基Xが、同一である、項2に記載の組成物。
項9.
各Xが、前記金属中心に配位したベンジル基である、項2に記載の組成物。
項10.
各Xが、塩化物である、項2に記載の組成物。
項11.
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、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、
項13.
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、項12に記載の組成物。
項14.
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、項12に記載の組成物。
項15.
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、項12に記載の組成物。
項16.
各R1が、フェニルであるか、または各R1が、n-ブチルである、項12に記載の組成物。
項17.
各R2が、(C1-C10)アルキル基である、項12に記載の組成物。
項18.
各R2が、メチルである、項12に記載の組成物。
項19.
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、項12に記載の組成物。
項20.
A1およびA2の両方がメチルである、項19に記載の組成物。
項21.
各Xが、前記金属中心に配位したベンジル基である、項12に記載の組成物。
項22.
各Xが、塩化物である、項12に記載の組成物。
項23.
両方の基Qが、同一であり、全ての基Xが、同一である、項12に記載の組成物。
項24.
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、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、
項26.
Z2が、-(CH2)n-であり、nが、4~10である、項25に記載の組成物。
項27.
Z2が、-(CH2)n-であり、nが、4または5である、項25に記載の組成物。
項28.
各R2が、(C1-C10)アルキル基である、項25に記載の組成物。
項29.
各R2が、メチルである、項25に記載の組成物。
項30.
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、項25に記載の組成物。
項31.
A1およびA2の両方がメチルである、項30に記載の組成物。
項32.
各Xが、前記金属中心に配位したベンジル基である、項25に記載の組成物。
項33.
各Xが、塩化物である、項25に記載の組成物。
項34.
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、項25に記載の組成物。
項35.
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、項25に記載の組成物。
触媒量の項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。
項37.
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、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、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。
項39.
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、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、項38に記載のエチレン-コ-アルキレンコポリマー。
項41.
触媒量の項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。
項42.
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、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、項42に記載の重合方法。
Claims (15)
- 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M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が独立して、アルキレン基から選択され、
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結合していても、または結合していなくてもよく、
各Xが、前記金属中心Mに共有結合または配位結合しており、かつ独立して、アルキル基、ハライド、またはアミドから選択される、組成物。 - 各R1が独立して、フェニルまたは(C1-C10)アルキル基から選択される、請求項5に記載の組成物。
- Z2が、-(CH2)n-であり、nが、4~10である、請求項9に記載の組成物。
- 重合方法であって、
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反応させて、エチレン-コ-アルキレンコポリマーを形成することを含み、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、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14に記載の重合方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662402210P | 2016-09-30 | 2016-09-30 | |
US62/402,210 | 2016-09-30 | ||
PCT/US2017/051535 WO2018063813A1 (en) | 2016-09-30 | 2017-09-14 | Thioguanidine group iv transition metal catalysts and polymerization systems |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2019530771A JP2019530771A (ja) | 2019-10-24 |
JP7051827B2 true JP7051827B2 (ja) | 2022-04-11 |
Family
ID=60083415
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019515967A Active JP7051827B2 (ja) | 2016-09-30 | 2017-09-14 | チオグアニジン第iv族遷移金属触媒および重合系 |
Country Status (8)
Country | Link |
---|---|
US (1) | US10647799B2 (ja) |
EP (1) | EP3519463B1 (ja) |
JP (1) | JP7051827B2 (ja) |
KR (1) | KR102448251B1 (ja) |
CN (1) | CN109843949B (ja) |
BR (1) | BR112019006302B1 (ja) |
ES (1) | ES2848316T3 (ja) |
WO (1) | WO2018063813A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112019005911B1 (pt) * | 2016-09-30 | 2022-10-11 | Dow Global Technologies Llc | Composição e método de polimerização |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4003712A (en) | 1970-07-29 | 1977-01-18 | Union Carbide Corporation | Fluidized bed reactor |
US3709853A (en) | 1971-04-29 | 1973-01-09 | Union Carbide Corp | Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts |
US4011382A (en) | 1975-03-10 | 1977-03-08 | Union Carbide Corporation | Preparation of low and medium density ethylene polymer in fluid bed reactor |
US4302566A (en) | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Preparation of ethylene copolymers in fluid bed reactor |
US4543399A (en) | 1982-03-24 | 1985-09-24 | Union Carbide Corporation | Fluidized bed reaction systems |
US4613484A (en) | 1984-11-30 | 1986-09-23 | Phillips Petroleum Company | Loop reactor settling leg system for separation of solid polymers and liquid diluent |
FR2618786B1 (fr) | 1987-07-31 | 1989-12-01 | Bp Chimie Sa | Procede de polymerisation d'olefines en phase gazeuse dans un reacteur a lit fluidise |
US5352749A (en) | 1992-03-19 | 1994-10-04 | Exxon Chemical Patents, Inc. | Process for polymerizing monomers in fluidized beds |
ZA943399B (en) | 1993-05-20 | 1995-11-17 | Bp Chem Int Ltd | Polymerisation process |
DE10130229A1 (de) | 2001-06-22 | 2003-01-02 | Celanese Ventures Gmbh | Non-Metallocene, Verfahren zur Herstellung von diesen und deren Verwendung zur Polymerisation von Olefinen |
DE10251513A1 (de) | 2002-11-04 | 2004-05-19 | Basf Ag | Übergangsmetallkatalysatoren für (Co)Polymerisation von olefinischen Monomeren |
EP1749842A1 (en) * | 2005-08-03 | 2007-02-07 | Total Petrochemicals Research Feluy | Transition metal complexes supported on activating fluorinated support |
EP2003125A1 (en) * | 2007-06-14 | 2008-12-17 | Total Petrochemicals Research Feluy | New tridentate ligand compounds with imino furan units, method for manufacturing said compounds, and their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins |
KR101854480B1 (ko) * | 2010-02-19 | 2018-05-03 | 다우 글로벌 테크놀로지스 엘엘씨 | 올레핀 단량체의 중합 방법 및 이를 위한 촉매 |
-
2017
- 2017-09-14 KR KR1020197011023A patent/KR102448251B1/ko active IP Right Grant
- 2017-09-14 JP JP2019515967A patent/JP7051827B2/ja active Active
- 2017-09-14 WO PCT/US2017/051535 patent/WO2018063813A1/en unknown
- 2017-09-14 EP EP17784062.6A patent/EP3519463B1/en active Active
- 2017-09-14 US US16/333,071 patent/US10647799B2/en active Active
- 2017-09-14 BR BR112019006302-1A patent/BR112019006302B1/pt active IP Right Grant
- 2017-09-14 ES ES17784062T patent/ES2848316T3/es active Active
- 2017-09-14 CN CN201780060254.4A patent/CN109843949B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
JP2019530771A (ja) | 2019-10-24 |
CN109843949A (zh) | 2019-06-04 |
WO2018063813A8 (en) | 2018-08-23 |
US20190263949A1 (en) | 2019-08-29 |
WO2018063813A1 (en) | 2018-04-05 |
KR20190064598A (ko) | 2019-06-10 |
EP3519463B1 (en) | 2020-12-23 |
US10647799B2 (en) | 2020-05-12 |
BR112019006302B1 (pt) | 2022-10-18 |
KR102448251B1 (ko) | 2022-09-28 |
ES2848316T3 (es) | 2021-08-06 |
EP3519463A1 (en) | 2019-08-07 |
CN109843949B (zh) | 2021-08-10 |
BR112019006302A2 (pt) | 2019-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108779204B (zh) | 烯烃聚合催化剂体系和其使用方法 | |
JP6916809B2 (ja) | オレフィン重合触媒系及びその使用方法 | |
JP2020535263A (ja) | 溶解性を改善させるために金属上に2つのメチレントリアルキルシリコン配位子を有するビスフェニルフェノキシポリオレフィン触媒 | |
CN108779205B (zh) | 烯烃聚合催化剂 | |
JP7053589B2 (ja) | チオ尿素第4族遷移金属触媒および重合系 | |
JP7051827B2 (ja) | チオグアニジン第iv族遷移金属触媒および重合系 | |
JP6974448B2 (ja) | 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 | |
JP2020535298A (ja) | 溶解性を改善させるために金属上にメチレントリアルキルシリコン配位子を有するビスフェニルフェノキシポリオレフィン触媒 | |
CN111164110A (zh) | 在金属上具有烷氧基或酰胺基配体的用于改进溶解度的双-苯基-苯氧基聚烯烃催化剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190523 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20190527 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20190826 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200907 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210714 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210803 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20211028 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220308 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220330 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7051827 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |