JP2022542254A - チーグラー・ナッタ触媒および水素化触媒を使用する溶液プロセスにおけるエチレンの重合 - Google Patents
チーグラー・ナッタ触媒および水素化触媒を使用する溶液プロセスにおけるエチレンの重合 Download PDFInfo
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- JP2022542254A JP2022542254A JP2022504156A JP2022504156A JP2022542254A JP 2022542254 A JP2022542254 A JP 2022542254A JP 2022504156 A JP2022504156 A JP 2022504156A JP 2022504156 A JP2022504156 A JP 2022504156A JP 2022542254 A JP2022542254 A JP 2022542254A
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- Prior art keywords
- procatalyst
- heterogeneous
- catalyst
- catalyst system
- titanium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 14
- 230000008569 process Effects 0.000 title claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title description 19
- 239000005977 Ethylene Substances 0.000 title description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 72
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 alkylaluminum alkoxides Chemical class 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 239000004711 α-olefin Substances 0.000 claims description 15
- 150000001805 chlorine compounds Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 31
- 239000002904 solvent Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- 150000002901 organomagnesium compounds Chemical class 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000002002 slurry Substances 0.000 description 16
- 239000003446 ligand Substances 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 12
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000003550 marker Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical group Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen 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
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- CZQIDPLTQBOKMO-UHFFFAOYSA-L butylcyclopentane;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCC[C]1[CH][CH][CH][CH]1.CCCC[C]1[CH][CH][CH][CH]1 CZQIDPLTQBOKMO-UHFFFAOYSA-L 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- YQZMEUFOYRWASB-UHFFFAOYSA-L dichlorotitanium;ethylcyclopentane Chemical compound Cl[Ti]Cl.CC[C]1[CH][CH][CH][CH]1.CC[C]1[CH][CH][CH][CH]1 YQZMEUFOYRWASB-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002734 organomagnesium group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- NMXLXQGHBSPIDR-UHFFFAOYSA-N 2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCCO1 NMXLXQGHBSPIDR-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- SPXDYPYJHCSREL-UHFFFAOYSA-N CCC(C)[Mg]C(C)CC Chemical compound CCC(C)[Mg]C(C)CC SPXDYPYJHCSREL-UHFFFAOYSA-N 0.000 description 1
- HYLHFOVZFADXNK-UHFFFAOYSA-N CCCCCC[Mg]CC Chemical compound CCCCCC[Mg]CC HYLHFOVZFADXNK-UHFFFAOYSA-N 0.000 description 1
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical compound CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 1
- MDCNUULPPQFEAB-UHFFFAOYSA-N CCCC[Mg]C(C)C Chemical compound CCCC[Mg]C(C)C MDCNUULPPQFEAB-UHFFFAOYSA-N 0.000 description 1
- MVECFARLYQAUNR-UHFFFAOYSA-N CCCC[Mg]CC Chemical compound CCCC[Mg]CC MVECFARLYQAUNR-UHFFFAOYSA-N 0.000 description 1
- ODHFJIDDBSDWNU-UHFFFAOYSA-N CCCC[Mg]CCCC Chemical compound CCCC[Mg]CCCC ODHFJIDDBSDWNU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HAEBMOGKTDSWHJ-UHFFFAOYSA-L [Cl-].[Cl-].CC1(C=CC=C1)[Ti+2]C1(C=CC=C1)C Chemical group [Cl-].[Cl-].CC1(C=CC=C1)[Ti+2]C1(C=CC=C1)C HAEBMOGKTDSWHJ-UHFFFAOYSA-L 0.000 description 1
- DGXOWMLKUUUVMZ-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Ti+3]C Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3]C DGXOWMLKUUUVMZ-UHFFFAOYSA-K 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012550 audit Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 description 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IFMWVBVPVXRZHE-UHFFFAOYSA-M chlorotitanium(3+);propan-2-olate Chemical compound [Cl-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-] IFMWVBVPVXRZHE-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Chemical group 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000000743 hydrocarbylene group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 150000007527 lewis bases Chemical group 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- WCFJMDWWJOCLSJ-UHFFFAOYSA-N magnesium;methanidylbenzene Chemical compound [Mg+2].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 WCFJMDWWJOCLSJ-UHFFFAOYSA-N 0.000 description 1
- KMYFNYFIPIGQQZ-UHFFFAOYSA-N magnesium;octane Chemical compound [Mg+2].CCCCCCC[CH2-].CCCCCCC[CH2-] KMYFNYFIPIGQQZ-UHFFFAOYSA-N 0.000 description 1
- DQZLQYHGCKLKGU-UHFFFAOYSA-N magnesium;propane Chemical compound [Mg+2].C[CH-]C.C[CH-]C DQZLQYHGCKLKGU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 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
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LXWBMENBONGPSB-UHFFFAOYSA-J oxolane;tetrachlorotitanium Chemical compound C1CCOC1.C1CCOC1.Cl[Ti](Cl)(Cl)Cl LXWBMENBONGPSB-UHFFFAOYSA-J 0.000 description 1
- MIDYWIPTCYRMQF-UHFFFAOYSA-K oxolane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].C1CCOC1.C1CCOC1.C1CCOC1 MIDYWIPTCYRMQF-UHFFFAOYSA-K 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- LTEDQKPGOZDGRZ-UHFFFAOYSA-L propan-2-olate;titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl.CC(C)[O-].CC(C)[O-] LTEDQKPGOZDGRZ-UHFFFAOYSA-L 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 1
- VSEOIQRHQSIHRZ-UHFFFAOYSA-L titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl VSEOIQRHQSIHRZ-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
本出願は、2019年7月31日に出願された、米国仮特許出願第62/881,004号に対する優先権を主張し、その開示全体が参照により本明細書に組み込まれる。
いくつかの実施形態では、触媒系は、助触媒をさらに含み得る。本開示による不均一系プロ触媒は、助触媒と組み合わされて、チーグラー・ナッタ触媒を形成し得る。不均一系プロ触媒を含むチーグラー・ナッタ触媒は、オレフィン重合反応のチーグラー・ナッタ型プロ触媒を活性化するための当技術分野で既知である任意の技術によって、触媒的に活性にすることができる。限定することを意図するものではないが、1つの例では、不均一系プロ触媒は、プロ触媒を活性化助触媒に接触させるか、またはプロ触媒を活性化助触媒と組み合わせることによって、触媒的に活性にすることができる。本明細書で使用するのに好適な活性化助触媒は、ポリマーまたはオリゴマーのアルモキサン(アルミノキサンとしても既知)を含むアルキルアルミニウムを含む。前述の活性化助触媒のうちの1つ以上の組み合わせもまた企図される。「アルキルアルミニウム」という用語は、モノアルキルアルミニウムジヒドリドもしくはモノアルキルアルミニウムジハライド、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。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としては、メチルアルモキサン、トリイソブチルアルミニウム修飾メチルアルモキサン、およびイソブチルアルモキサンを挙げることができる。いくつかの実施形態では、助触媒は、アルミニウムのアルキル、アルミニウムのハロアルキル、ハロゲン化アルキルアルミニウム、およびこれらの混合物から選択され得る。いくつかの実施形態では、助触媒は、トリエチルアルミニウム、トリメチルアルミニウム、トリ-n-ブチルアルミニウム、トリイソブチルアルミニウム、トリ-n-ヘキシルアルミニウム、トリ-n-オクチルアルミニウム、ジエチルアルミニウムクロリド、MAO、MMAO、ジエチルアルミニウムエトキシド、およびこれらの混合物から選択され得る。
1つ以上の実施形態では、触媒系は、不均一系プロ触媒、水素化プロ触媒、および任意選択的に、炭化水素溶媒中の助触媒を混合することによって調製される。次いで、触媒系は、重合プロセスで使用することができる。
MgCl2支持体の比表面積は、ブルナウアー、エメット、テラー(BET)表面積法によって測定する。MicromeriticsによるTristar 3020表面積分析器を使用する。溶媒を除去するために、30mLの量のMgCl2スラリーを濾過し、次いで、30mLのヘキサン中に再スラリー化する。得られたスラリーを不活性雰囲気下で再度濾過し、追加のヘキサンで洗浄する。このプロセスを1回繰り返して、MgCl2のフィルタケーキを得る。残留溶媒を真空下でフィルタケーキから除去する。フィルタケーキは、MicromeriticsによるVac Prep 061で、0.5インチ(1.27cm)の試料チューブおよび不活性試料保護用に設計されたTransealストッパーを使用して、真空乾燥させたMgCl2の試料0.2gを不活性雰囲気下でTransealストッパー付きのチューブに投入することによりさらに乾燥させる。試料チューブを、窒素パージしながらVac Prep 061ユニットに接続する。Transealストッパーを開くことによって試料チューブを真空で処理し、真空にしたチューブをアルミニウムチューブプロテクター付きの加熱ブロック内に入れる。Vac Prep 061ユニットでの真空下で、試料を110℃で3時間乾燥させる。その後、窒素を試料チューブに導入する。乾燥させた試料を室温まで冷却し、その後試料チューブをVac Prep 061ユニットから外して、完全に乾燥させた試料を得る。不活性雰囲気下で、0.1500g~0.2000gの完全に乾燥させた試料をチューブフィラーロッド付きの清浄な試料チューブの中に移す。次いで、試料チューブをTransealストッパーで密封し、表面積測定のためにTristar 3020機器に接続する。データの取得には、QUICKSTART法を使用する。
流量(実効)=流量(公称)*(RV(FM較正済み)/RV(FM試料))(式7)
化合物(C1)。ExxonMobil Corporationから得られ、114℃~139℃の沸騰範囲を有する、>99.75重量%~99.9重量%のナフサ(石油)、軽質アルキレート、CAS 64741-66-8、および0.1重量%~0.25重量%未満のイソオクタン CAS 540-54-1(イソアルカン混合物)を含有するIsopar E流体。
30℃でかき混ぜながら、EADC/Mg比が0.3に達するまで、ヘプタン中の15重量%の二塩化エチルアルミニウム(EADC)溶液を上述のMgCl2微粒子状スラリー(D1)にゆっくりと添加する。添加中、反応混合物の温度を30℃±3℃に維持する。混合物を、30℃で4時間熟成させる。その後、30℃でかき混ぜながら、Ti/Mg比が0.075に達するまで、ヘプタン中の51重量%の(IV)イソプロポキシド溶液を混合物にゆっくりと添加する。添加中、反応混合物の温度を30℃±3℃に維持する。混合物を、30℃で少なくとも8時間熟成させる。触媒配合の正確さを確実にするために、濯ぎには、Isopar E溶媒(C1)を使用する。完成した触媒についての最終Ti濃度は、0.12mol/Lである。
実施例1:ビス(エチルシクロペンタジエニル)チタンクロリド(E1)。2オンスのボトル内に、1.000gのCp2TiCl2および撹拌棒を入れる。ヘプタン中の1.0mol/Lトリエチルアルミニウム(TEA)溶液20.1mLを、撹拌しながら約10分間かけてゆっくりと添加する。固体のCp2TiCl2は、可溶性になり、青色の溶液を形成する。
Claims (16)
- 触媒系であって、
チタン種、アルミニウム種、および塩化マグネシウム成分を含む不均一系プロ触媒と、
式Cp2TiX2TiCp2またはCp2TiXnを有する水素化プロ触媒と、を含み、
式中、
各Cpが、少なくとも1つの(C1-C10)アルキルで置換されたシクロペンタジエニルであり、
各Xが、独立して、モノアニオン性または中性であり、各Xが、独立して、(C1-C40)炭化水素、(C1-C40)ヘテロ炭化水素、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、またはハロゲン原子であり、
nが、1または2である、触媒系。 - 不均一系触媒が、担持されていないバルク触媒である、請求項1に記載の触媒系。
- 前記不均一系プロ触媒が、0.1ミクロン~10ミクロンの平均粒子径を有する不均一系プロ触媒粒子を含む、請求項1または2に記載の触媒系。
- 前記不均一系プロ触媒が、制御されていない形態を有する不均一系プロ触媒粒子を含む、請求項1~3のいずれか一項に記載の触媒系。
- 前記不均一系プロ触媒が、不均一系プロ触媒粒子を含み、前記不均一系プロ触媒粒子の10%以上が、1ミクロン以下の粒子径を有する、請求項1~4のいずれか一項に記載の触媒系。
- 前記水素化プロ触媒中のチタンのモル数の前記不均一系プロ触媒中のチタンのモル数との比が、1:2よりも大きい、請求項1~5のいずれか一項に記載の触媒系。
- アルキルアルミニウム助触媒Al(R2)3をさらに含み、式中、各R2が、独立して、(C1-C20)アルキルまたはハロゲン原子であり、ただし、少なくとも1つのR2が(C1-C20)アルキルであることを条件とする、請求項1~6のいずれか一項に記載の触媒系。
- トリアルキルアルミニウム化合物、塩化ジアルキルアルミニウム、二塩化アルキルアルミニウム、アルキルアルミニウムアルコキシド、およびアルキルアルミノキサン(alkylaluminoxane)からなる群から選択されるアルキルアルミニウム助触媒をさらに含む、請求項1~6のいずれか一項に記載の触媒系。
- 前記不均一系プロ触媒中のチタンのモル数の前記助触媒中のアルミニウムのモル数との比が、2:1よりも大きい、触媒系請求項7または8。
- 前記不均一系プロ触媒中のチタンのモル数の前記助触媒中のアルミニウムのモル数との比が、1000:1~2:1である、請求項7または8に記載の触媒系。
- 重合プロセスであって、
触媒系の存在下で、溶液中の(C2-C12)α-オレフィンを反応させることを含み、前記触媒系が、
チタン種、アルミニウム種、および塩化マグネシウム成分を含む不均一系プロ触媒と、
式Cp2TiXnTiCp2またはCp2TiXnを有する水素化プロ触媒と、を含み、
式中、
各Cpが、少なくとも1つの(C1-C10)アルキルで置換されたシクロペンタジエニルであり、
各Xが、独立して、モノアニオン性または中性であり、各Xが、独立して、(C1-C40)炭化水素、(C1-C40)ヘテロ炭化水素、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、またはハロゲン原子であり、
nが、1または2である、重合プロセス。 - 前記触媒系が、トリアルキルアルミニウム助触媒Al(R2)3をさらに含み、式中、各R2が、独立して、(C1-C20)アルキルである、請求項11に記載の重合プロセス。
- 前記不均一系触媒が、バルク触媒である、請求項11または12に記載の重合プロセス。
- 前記不均一系プロ触媒が、不均一系プロ触媒粒子を含み、前記粒子の10%以上が、1ミクロン以下の粒子径を有する、請求項11~13のいずれか一項に記載の重合プロセス。
- 前記不均一系触媒が、制御されていない粒子形態を有する不均一系プロ触媒粒子を含む、請求項11~14のいずれか一項に記載の重合プロセス。
- 溶液中の前記(C2-C12)α-オレフィンが、150℃~350℃の反応温度で、反応器内で反応する、請求項11~15のいずれか一項に記載の重合プロセス。
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