JP2021519837A - オレフィン重合活性化剤 - Google Patents
オレフィン重合活性化剤 Download PDFInfo
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- JP2021519837A JP2021519837A JP2020552345A JP2020552345A JP2021519837A JP 2021519837 A JP2021519837 A JP 2021519837A JP 2020552345 A JP2020552345 A JP 2020552345A JP 2020552345 A JP2020552345 A JP 2020552345A JP 2021519837 A JP2021519837 A JP 2021519837A
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- alkyl
- halogen
- substituted
- independently
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- 239000012190 activator Substances 0.000 title claims abstract description 94
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 title claims description 40
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005977 Ethylene Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000003446 ligand Substances 0.000 claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 150000001450 anions Chemical class 0.000 claims abstract description 33
- 239000004711 α-olefin Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- -1 phenylphenoxy Chemical group 0.000 claims description 131
- 229920000642 polymer Polymers 0.000 claims description 69
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 239000004215 Carbon black (E152) Substances 0.000 claims description 36
- 229930195733 hydrocarbon Natural products 0.000 claims description 36
- 150000001768 cations Chemical class 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 125000003837 (C1-C20) alkyl group Chemical class 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 10
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052733 gallium Chemical group 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 7
- 238000010586 diagram Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 39
- YSRFHVJGXPIDGR-UHFFFAOYSA-N dimethylsilane titanium Chemical compound [Ti].C[SiH2]C YSRFHVJGXPIDGR-UHFFFAOYSA-N 0.000 description 36
- 125000004432 carbon atom Chemical group C* 0.000 description 33
- 150000003254 radicals Chemical group 0.000 description 31
- 239000000243 solution Substances 0.000 description 27
- 150000002500 ions Chemical class 0.000 description 25
- 125000005842 heteroatom Chemical group 0.000 description 23
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 23
- 239000002904 solvent Substances 0.000 description 21
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 150000001721 carbon Chemical group 0.000 description 13
- 238000010828 elution Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003426 co-catalyst Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 125000003636 chemical group Chemical group 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- DVZWQGLVEOWFOU-UHFFFAOYSA-N C[Hf]C Chemical compound C[Hf]C DVZWQGLVEOWFOU-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 229920006124 polyolefin elastomer Polymers 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- DPSOUODMTOWXTB-UHFFFAOYSA-N CC1=C(C)C(C)([Ti])C(C)=C1C Chemical compound CC1=C(C)C(C)([Ti])C(C)=C1C DPSOUODMTOWXTB-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 102000018779 Replication Protein C Human genes 0.000 description 5
- 108010027647 Replication Protein C Proteins 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 125000002619 bicyclic group Chemical group 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- XZNOAVNRSFURIR-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol Chemical compound FC(F)(F)C(O)(C(F)(F)F)C(F)(F)F XZNOAVNRSFURIR-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- DWOZNANUEDYIOF-UHFFFAOYSA-L 4-ditert-butylphosphanyl-n,n-dimethylaniline;dichloropalladium Chemical compound Cl[Pd]Cl.CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1.CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1 DWOZNANUEDYIOF-UHFFFAOYSA-L 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000004404 heteroalkyl group Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SFPQWMKUAVIGIX-UHFFFAOYSA-N C1=CC=C2C([Ti])C=CC2=C1 Chemical compound C1=CC=C2C([Ti])C=CC2=C1 SFPQWMKUAVIGIX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 125000000743 hydrocarbylene group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000010354 integration Effects 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
- 125000002950 monocyclic group Chemical group 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ODMWVMRTMJXBPA-UHFFFAOYSA-N C1C=CC=C2C([Ti])CCC21 Chemical compound C1C=CC=C2C([Ti])CCC21 ODMWVMRTMJXBPA-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O phenylazanium Chemical class [NH3+]C1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000006747 (C2-C10) heterocycloalkyl group Chemical group 0.000 description 1
- 125000006529 (C3-C6) alkyl group Chemical group 0.000 description 1
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- 125000004523 tetrazol-1-yl group Chemical group N1(N=NN=C1)* 0.000 description 1
- 125000004299 tetrazol-5-yl group Chemical group [H]N1N=NC(*)=N1 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
- LGWZGBCKVDSYPH-UHFFFAOYSA-N triacontane Chemical compound [CH2]CCCCCCCCCCCCCCCCCCCCCCCCCCCCC LGWZGBCKVDSYPH-UHFFFAOYSA-N 0.000 description 1
- OLTHARGIAFTREU-UHFFFAOYSA-N triacontane Natural products CCCCCCCCCCCCCCCCCCCCC(C)CCCCCCCC OLTHARGIAFTREU-UHFFFAOYSA-N 0.000 description 1
- 229940062627 tribasic potassium phosphate Drugs 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
Description
本出願は、2018年3月30日出願の米国仮特許出願第62/650,412号に対する優先権を主張し、参照によりその全体が本明細書に組み込まれる。
ポリマー材料などの媒体の電気絶縁効率は、媒体の電気抵抗および媒体の電気損失を考慮して評価することができる。電気損失は、電場の存在下で、絶縁媒体が電気的に絶縁する効率を低下させる。抵抗は、電力または電気損失に逆相関するため、絶縁媒体の抵抗は、交流(AC)システムと直流(DC)システムとの両方で可能な限り高くする必要がある。
触媒系としては、プロ触媒を挙げることができる。プロ触媒は、式(I)のアニオンおよび対カチオンを有する金属活性化剤に錯体を接触させるか、または金属活性化剤と錯体を組み合わせることによって、触媒的に活性になることができる。プロ触媒は、チタン(Ti)金属−配位子錯体、ジルコニウム(Zr)金属−配位子錯体、またはハフニウム(Hf)金属−配位子錯体などの、第IV属金属(CASに従った第IVB族、またはIUPAC命名規則に従った第4族)−配位子錯体から選択することができる。プロ触媒の非限定的な例としては、触媒、プロ触媒、またはエチレン系ポリマーを重合するための触媒活性化合物が挙げられ、US8372927、WO2010/022228、WO2011/102989、US6953764、US6900321、WO2017/173080、US7650930、US6777509、WO99/41294、US6869904、またはWO2007/136496のうちの1つ以上に開示されており、これらの文書はすべて、参照によりその全体が本明細書に組み込まれる。
前の段落に記載される触媒系は、オレフィン、主にエチレンおよびプロピレンの重合に利用される。いくつかの実施形態では、重合スキーム中に単一種類のオレフィンまたはα−オレフィンのみが存在し、ホモポリマーを生成する。しかしながら、追加のα−オレフィンを重合手順に組み込んでもよい。追加のα−オレフィンコモノマーは、典型的には、20個以下の炭素原子を有する。例えば、α−オレフィンコモノマーは、3〜10個の炭素原子、または3〜8個の炭素原子を有し得る。例示的なα−オレフィンコモノマーとしては、プロピレン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン、4−メチル−1−ペンテン、5−エチリデン−2−ノルボルネン、および5−ビニル−2−ノルボルネンが挙げられるが、これらに限定されない。例えば、1つ以上のα−オレフィンコモノマーは、プロピレン、1−ブテン、1−ヘキセン、および1−オクテンからなる群から、または代替的に1−ヘキセンおよび1−オクテンからなる群から選択され得る。
バッチ式反応器の実験は、1ガロンの連続撹拌槽反応器で実施する。Isopar−E炭化水素溶媒、水素、および適切な量のオクテンコモノマーを反応器に充填した後、特定の温度に加熱し、エチレンと共に450psiに加圧する。反応器が圧力下にあるときに、プロ触媒、イオン性金属活性化剤錯体、溶媒、およびトリエチルアルミニウム捕捉剤を含む触媒カクテルを添加することによって、重合を開始する。反応器の温度および圧力を維持しながら、重合を10分間進行させる。反応が完了した後、ポリマーを収集し、真空オーブンで一晩乾燥させた後分析する。
未希釈の1−オクテン(11mL)を、撹拌棒を備えた40mLバイアルに添加する。それ自体が磁気撹拌プレート上に位置するポリウレタン絶縁ブロックに、バイアルを置く。撹拌溶液に活性化剤を添加する。撹拌溶液にプロ触媒の溶液を添加する。バイアルをすぐにセプタムスクリューキャップの蓋でキャップし、プローブの先端が1−オクテン溶液に浸るように温度計プローブをバイアルに挿入する。温度計プローブをデジタルレコーダに接続し、時間および温度を5秒間隔で記録する。バイアル内の溶液を継続的に撹拌し、10分間監視する。
原材料(エチレン、1−オクテン)およびプロセス溶媒(ExxonMobil Corporationから商標ISOPAR Eで市販されている狭い沸点範囲の高純度イソパラフィン溶媒)を分子ふるいで精製した後、反応環境に導入する。高純度グレードの、さらなる精製が必要ない水素を、加圧シリンダに供給する。反応器モノマー供給(エチレン)ストリームを、機械的圧縮機を介して525psigの反応圧力より高い圧力まで加圧する。機械的容積式ポンプを介して、溶媒およびコモノマー(1ーオクテン)供給物を525psigよりも高い反応圧力まで加圧する。不純物捕捉剤として、AkzoNobelから市販のトリエチルアルミニウムを使用する。個々の触媒成分(プロ触媒/活性化剤/捕捉剤)を、精製溶媒(ISOPAR E)で特定の成分濃度までバッチ式に手動で希釈し、525psigよりも高い反応圧力まで加圧する。活性化剤は、プロ触媒に対して1.2モルで使用する。すべての反応供給流は、マスフローメータで測定し、コンピュータ自動バルブ制御システムで独立して制御する。
前述の手順に従って、バッチ式反応器内で重合を実行した。各々式(I)に従ったアニオン構造およびビス(フェニルフェノキシ)第IV属金属−配位子錯体を有する活性化剤1、5〜9での、助触媒効率および得られたポリマーの特徴を評価した。
市販の結晶化溶出分別装置(CEF)(Polymer Char、Spain)を使用して、高温熱勾配相互作用クロマトグラフィー(TGIC)測定を行った(Congら、Macromolecules、2011、44(8)、3062〜3072)。HYPERCARBカラム(100X4.6mm、部品#35005〜104646、Thermo Scientific)を分離に使用した。27ミクロンのガラスビーズ(カタログ#GL01918/20〜27μm、MO−SCI Specialty Products,LLC(Rolla,MO,USA))を充填した「8cm×0.48cm(内径3/16インチ)」のステンレス鋼カラムを、IR検出器の前、CEF機器のトップオーブンに設置した。実験パラメータは次の通りである:トップオーブン/輸送ライン/針温度150℃、溶解温度160℃、溶解撹拌設定2、試料充填容量0.400mL、ポンプ安定化時間15秒、洗浄カラムのポンプ流量0.500mL/分、カラム充填のポンプ流量0.300mL/分、安定化温度150℃、安定化時間(カラム充填前)3.0分、安定化時間(カラム充填後)1.0分、SF(可溶性画分)時間3.0分、150℃〜30℃の冷却速度3.00℃/分、冷却プロセス中の流量0.01mL/分、30℃〜160℃の加熱速度2.00℃/分、等温時間160℃で10分間、溶出流量0.500mL/分、および注入ループサイズ140マイクロリットル。
ポリマー試料と同じ実験条件下で、溶媒ブランク(純粋溶媒注入)を実施した。ポリマー試料のデータ処理は、較正の加熱速度から計算した、各検出器チャネルの溶媒ブランクの減算、較正プロセスで説明されている温度外挿、較正プロセスから決定した遅延容量を用いた温度の補正、および溶出温度軸の30℃〜160℃の範囲への調節を含む。
Claims (12)
- オレフィンを重合するプロセスであって、触媒系の存在下で、エチレンと(C3−C40)アルファ−オレフィンコモノマーとを接触させて、エチレン系ポリマーを生成することを含み、前記触媒系が、プロ触媒と、イオン性金属活性化剤錯体とを含み、前記イオン性金属活性化剤錯体が、アニオンおよび対カチオンを含み、前記アニオンが、式(I)に従った構造を有し、
Mが、アルミニウム、ホウ素、またはガリウムであり、
nが2、3、または4であり、
各Rが独立して、式(II)を有するラジカル、および式(III)を有するラジカルからなる群から選択され、
各R11、R12、R13、R21、R22、R23、R24、およびR25が独立して、(C1−C40)アルキル、(C6−C40)アリール、−ORC、−O−、−SRC、−H、または−Fから選択され、Rが、式(III)に従ったラジカルであるとき、R21、R22、R23、R24、またはR25のうちの少なくとも1つが、ハロゲン置換(C1−C40)アルキル、ハロゲン置換(C6−C40)アリール、または−Fであるが、
ただし、
各Rが式(II)に従ったラジカルであり、Yが炭素であるとき、R11、R12、もしくはR13のうちの少なくとも1つが、ハロゲン置換(C1−C40)アルキル、ハロゲン置換(C6−C40)アリール、もしくは−Fであるか、あるいは
Mがアルミニウムであり、nが4であり、各Rが式(II)に従ったラジカルであり、各Yが炭素であるとき、
各Rのうちの各R11、R12、およびR13が、ハロゲン置換(C1−C40)アルキル、ハロゲン置換(C6−C40)アリール、もしくは−Fであるか、または
各RのうちのR11、R12、およびR13のハロゲン原子の総数が、少なくとも6であることを条件とし、
各Xが、ハロゲン置換(C1−C20)アルキル、(C1−C20)アルキル、ハロゲン置換(C6−C40)アリール、(C6−C40)アリール、トリフラート、または−S(O)3RCから独立して選択された単座配位子であり、
任意選択的に、式(I)の2つの基Rが、共有結合しており、
各RCが独立して、(C1−C30)ヒドロカルビル、または−Hである、プロセス。 - 前記プロ触媒が、ビス(フェニルフェノキシ)金属−配位子錯体である、請求項1に記載の重合プロセス。
- nが4であり、各Rが独立して、−C(H)(CF3)2、−C6F5、または−C(CF3)3である、請求項1または請求項2に記載の重合プロセス。
- nが3であり、Xが、−OH、トリフラート(−OTf)、メチル、またはハロゲンから選択される、請求項1または請求項2に記載の重合プロセス。
- nが4であり、4つの基Rのうちの3つが、−C(CF3)3であり、4つの基Rのうちの1つが、−C6F5である、請求項1または請求項2に記載の重合プロセス。
- 前記対カチオンが、正の1(+1)の形式的変化を有する、請求項1〜5のいずれか一項に記載の重合プロセス。
- 前記対カチオンが、+N(H)RN 3であり、式中、各RNが、(C1−C20)アルキル、または(C6−C20)アリールから選択される、請求項1〜6のいずれか一項に記載の重合プロセス。
- 前記対カチオンが、+N(H)RN 3であり、式中、少なくとも2つのRNが、(C10−C20)アルキルから選択される、請求項6に記載の重合プロセス。
- 前記対カチオンが、+C(C6H5)3である、請求項1〜6のいずれか一項に記載の重合プロセス。
- 前記対カチオンが、+C(C6H4RC)3であり、式中、RCが、(C1−C20)アルキルである、請求項1〜6のいずれか一項に記載の重合プロセス。
- 2つの基Rが、共有結合しており、前記アニオンが、式(IV)に従った構造を有し、
MおよびXが、式(I)で定義されたとおりであり、
nが1、または2であり、
Lが、共有結合している前記2つの基Rを表し、
各Lが独立して、(C2−C40)アルキレン、(C2−C40)ヘテロアルキレン、またはまたは−(Si(RC)2−O)z−Si(RC)2−から選択され、zが、0、1、2、または3であり、RCが独立して、(C1−C30)ヒドロカルビルまたは−Hであり、
nが1のとき、Xが、ハロゲン、ハロゲン化−(C1−C20)アルキル、またはトリフラートから独立して選択された単座配位子である、請求項1に記載の重合プロセス。 - 高沸点完全飽和炭化水素溶液中に、200マイクロモルの濃度のイオン性金属活性化剤錯体および20ミリモルの水を有する、高沸点完全飽和炭化水素溶液中の前記イオン性金属活性化剤錯体が、炭化水素導電率試験によって測定すると、0.1以下の誘電正接パーセントを有する、請求項1〜11のいずれか一項に記載の重合プロセス。
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