JP5847586B2 - 置換された1,2−フェニレン芳香族ジエステルの内部供与体を有するプロ触媒組成物及び方法 - Google Patents
置換された1,2−フェニレン芳香族ジエステルの内部供与体を有するプロ触媒組成物及び方法 Download PDFInfo
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- JP5847586B2 JP5847586B2 JP2011544622A JP2011544622A JP5847586B2 JP 5847586 B2 JP5847586 B2 JP 5847586B2 JP 2011544622 A JP2011544622 A JP 2011544622A JP 2011544622 A JP2011544622 A JP 2011544622A JP 5847586 B2 JP5847586 B2 JP 5847586B2
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- 239000000203 mixture Substances 0.000 title claims description 181
- -1 1,2-phenylene aromatic diesters Chemical class 0.000 title claims description 134
- 238000000034 method Methods 0.000 title description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 80
- 229920000642 polymer Polymers 0.000 claims description 71
- 239000003054 catalyst Substances 0.000 claims description 69
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims description 61
- 239000001257 hydrogen Substances 0.000 claims description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- 239000011777 magnesium Substances 0.000 claims description 41
- 229910052749 magnesium Inorganic materials 0.000 claims description 39
- 239000010936 titanium Substances 0.000 claims description 37
- 229910052719 titanium Inorganic materials 0.000 claims description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 32
- 230000000694 effects Effects 0.000 claims description 30
- 125000005842 heteroatom Chemical group 0.000 claims description 30
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 29
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 239000012035 limiting reagent Substances 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 7
- LVTPRIAGCBEGPW-UHFFFAOYSA-N (2-benzoyloxyphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1OC(=O)C1=CC=CC=C1 LVTPRIAGCBEGPW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- DNSKBNRRRCLCAQ-UHFFFAOYSA-N 2-[2-(2-carboxyphenyl)-3,5-di(propan-2-yl)phenyl]benzoic acid Chemical compound C=1C=CC=C(C(O)=O)C=1C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1C(O)=O DNSKBNRRRCLCAQ-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- FSPCNXFZPIRBTB-UHFFFAOYSA-N (2-benzoyloxy-3,6-dimethylphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC=1C(C)=CC=C(C)C=1OC(=O)C1=CC=CC=C1 FSPCNXFZPIRBTB-UHFFFAOYSA-N 0.000 claims 1
- KARYFJLZXGWDIM-UHFFFAOYSA-N (2-benzoyloxy-4-methylphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC(C)=CC=C1OC(=O)C1=CC=CC=C1 KARYFJLZXGWDIM-UHFFFAOYSA-N 0.000 claims 1
- GBMGZWZFFDWLGC-UHFFFAOYSA-N (2-benzoyloxy-4-tert-butylphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1 GBMGZWZFFDWLGC-UHFFFAOYSA-N 0.000 claims 1
- GXNXZJMAFGKLQI-UHFFFAOYSA-N (2-benzoyloxy-5-tert-butyl-3-methylphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC=1C(C)=CC(C(C)(C)C)=CC=1OC(=O)C1=CC=CC=C1 GXNXZJMAFGKLQI-UHFFFAOYSA-N 0.000 claims 1
- XVSGXAPGEXHIEN-UHFFFAOYSA-N 2-[1-(2-carboxyphenyl)naphthalen-2-yl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1C1=CC=CC=C1C(O)=O XVSGXAPGEXHIEN-UHFFFAOYSA-N 0.000 claims 1
- KZDAPBVMMVECPH-UHFFFAOYSA-N 2-[3-(2-carboxyphenyl)naphthalen-2-yl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC2=CC=CC=C2C=C1C1=CC=CC=C1C(O)=O KZDAPBVMMVECPH-UHFFFAOYSA-N 0.000 claims 1
- WRJTTYZJLYEKDH-UHFFFAOYSA-N 2-[5-tert-butyl-2-(2-carboxy-5-fluorophenyl)-3-methylphenyl]-4-fluorobenzoic acid Chemical compound CC(C)(C)C(C=C1C)=CC(C(C=C(C=C2)F)=C2C(O)=O)=C1C(C=C(C=C1)F)=C1C(O)=O WRJTTYZJLYEKDH-UHFFFAOYSA-N 0.000 claims 1
- DCHLZPDJUCICIV-UHFFFAOYSA-N CC(C)(C)C(C=C1C)=CC(C(C=C(C=C2)Cl)=C2C(O)=O)=C1C(C=C(C=C1)Cl)=C1C(O)=O Chemical compound CC(C)(C)C(C=C1C)=CC(C(C=C(C=C2)Cl)=C2C(O)=O)=C1C(C=C(C=C1)Cl)=C1C(O)=O DCHLZPDJUCICIV-UHFFFAOYSA-N 0.000 claims 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-M p-toluate Chemical compound CC1=CC=C(C([O-])=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-M 0.000 claims 1
- 239000002243 precursor Substances 0.000 description 46
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 32
- 125000003118 aryl group Chemical group 0.000 description 25
- 230000008569 process Effects 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 24
- 239000000178 monomer Substances 0.000 description 19
- 230000026030 halogenation Effects 0.000 description 18
- 238000005658 halogenation reaction Methods 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 230000002140 halogenating effect Effects 0.000 description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 15
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 15
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical class CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 15
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical group O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229920005629 polypropylene homopolymer Polymers 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 5
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 4
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- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
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- 125000003342 alkenyl group Chemical group 0.000 description 2
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- 230000001174 ascending effect Effects 0.000 description 2
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- 229910052794 bromium Inorganic materials 0.000 description 2
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- 239000012159 carrier gas Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
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- 238000005649 metathesis reaction Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229940105132 myristate Drugs 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000004184 polymer manufacturing process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QMKUYPGVVVLYSR-UHFFFAOYSA-N propyl 2,2-dimethylpropanoate Chemical compound CCCOC(=O)C(C)(C)C QMKUYPGVVVLYSR-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- XBEXIHMRFRFRAM-UHFFFAOYSA-N tridodecylalumane Chemical compound CCCCCCCCCCCC[Al](CCCCCCCCCCCC)CCCCCCCCCCCC XBEXIHMRFRFRAM-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- 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
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emergency Medicine (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
本出願は、2008年12月31日出願の米国仮特許出願第61/141,902号の優先権を主張し、その全内容が参照により本明細書中に組み込まれる。
本開示は、置換フェニレン芳香族ジエステルの内部電子供与体を含有するプロ触媒(procatalyst)組成物、並びに、触媒組成物における該プロ触媒組成物の組み込み、及び、前記触媒組成物を使用するオレフィン系ポリマーの作製プロセスに関する。
定義
本明細書中における元素周期表に対するすべての参照は、CRC Press,Inc.が2003年に発行し、版権を有する元素周期表を参照しなければならない。同様にまた、族(1つ又はそれ以上)に対する参照はどれも、族に番号を与えるためのIUPACシステムを使用してこの元素周期表に反映される当該族(1つ又はそれ以上)に対するものでなければならない。反することが述べられる場合、文脈から暗黙的である場合、又は、当分野において慣例的である場合を除き、すべての部及びパーセントが重量に基づく。米国特許実務の目的のために、本明細書中で参照される特許、特許出願又は公開物はどれもその内容が、とりわけ当分野における合成技術、定義(本明細書中に提供されるどの定義とも矛盾にしない程度に)及び一般的知識に関して、本明細書によりそれらの全体において参照によって組み込まれる(或いは、それらの相当する米国対応版が参照によってそのように組み込まれる)。
試験方法
曲げ弾性率が、ASTM D790−00に従って求められる。
(1)コーン&プレートサンプルホルダーをETC炉において180℃で2時間加熱する。その後、隙間を窒素ガスの雰囲気下でゼロに合わせる。
(2)コーンを2.5mmに上げ、サンプルを底部プレートの上部に載せる。
(3)2分間の時間調整を開始する。
(4)上部コーンを直ちに下げて、法線力を観測することによってサンプルの上部にかすかに載せる。
(5)2分後、サンプルを、上部コーンを下げることによって165ミクロンの隙間にまで押しつける。
(6)法線力を観測する。法線力が0.05ニュートン未満になったとき、過剰なサンプルをスパチュラによってコーン及びプレートサンプルホルダーの縁から除く。
(7)上部コーンを、149ミクロンである截頭隙間に再び下げる。
(8)振動周波数掃引試験をこれらの条件のもとで行う:
試験を180℃で5分間延ばす。
(9)試験が完了したとき、交差弾性率(crossover modulus)(Gc)が、TA Instrumentsによって提供されるRheology Advantage Data Analysisプログラムによって検出される。
(10)PDI=100,000÷Gc(Pa単位)。
(1)装置を、高純度インジウムを標準物として用いて校正する。
(2)装置のヘッド/セルを50ml/分の一定流速の窒素により絶えずパージする。
(3)サンプル調製:
1.5gの粉末サンプルを、30−G302H−18−CX Wabash Compression Molder(30トン)を使用して圧縮成形する:(a)混合物を接触させて230℃で2分間加熱する;(b)サンプルを、20トンの圧力により1分間、同じ温度で圧縮する;(c)サンプルを45°Fに冷却し、20トンの圧力とともに2分間保つ;(d)サンプルを均質にするために、試料板を4つのほぼ同じサイズに切断し、それらを積み重ねて一緒に、工程(a)〜工程(c)を繰り返す。
(4)サンプル試料板からの1つのサンプルを重量測定し(好ましくは5mg〜8mgの間)、そのサンプルを標準的なアルミニウム製サンプル皿において密封する。サンプルを含有する密封された皿を装置のヘッド/セルのサンプル側に置き、空の密封された皿を参照側に置く。自動サンプラーを使用する場合、数個の異なるサンプル試料を事前に重量測定し、装置を連続測定のために設定する。
(5)測定:
(i)データ保存:オフ
(ii)温度勾配、240.00℃まで80.00℃/分
(iii)1.00分間の等温
(iv)温度勾配、0.00℃まで80.00℃/分
(v)1.00分間の等温
(vi)温度勾配、150.00℃まで80.00℃/分
(vii)5.00分間の等温
(viii)温度勾配、180.00℃まで1.25℃/分
(x)方法の終了
(6)計算:Tm(f)を2つの線の交差によって求める。1つの線を高温のベースラインから引く。別の線を曲線の偏位部から高温側での曲線の終点の近くに引く。
I.置換フェニレン芳香族ジエステル
置換フェニレン芳香族ジエステルを、2008年12月31日出願の米国特許出願第61/141,959号(文書番号68188)に従って合成することができる(その全内容が参照によって本明細書中に組み込まれる)。好適な置換フェニレン芳香族ジエステルの限定されない例が下記の表1に提供される。
プロ触媒前駆体を、機械的撹拌及び底部ろ過を備えるフラスコに、表2に示される重量に従って装荷する。TiCl4及びクロロベンゼンの混合された溶媒(体積比で1/1)の60mlをフラスコに導入し、その後、2.52mmolの内部電子供与体を加える。混合物を115℃に加熱し、そして、液体をろ過して除く前に250rpmでの撹拌とともに60分間、同じ温度で引き続き維持する。60mlの混合された溶媒を再び加え、反応が、撹拌とともに60分間、同じ所望される温度で続けられ、その後、反応液をろ過する。このプロセスを1回繰り返す。70mlのiso−オクタンを使用して、生じた固体を周囲温度で洗浄する。溶媒をろ過によって除いた後、固体をN2流によって乾燥する。
重合が、別個の注入を使用して、1ガロンのオートクレーブにおいて液状のプロピレンで行われる。外部電子供与体がn−プロピルトリメトキシシラン(NPTMS)又はジシクロペンチルジメトキシシラン(DCPDMS)である。状態調節の後、リアクターに1375gのプロピレン及び所望量の水素を装荷し、リアクターを62℃にする。外部電子供与体、iso−オクタンにおける0.27Mトリエチルアルミニウムの溶液、及び、鉱油における5.0wt%触媒スラリーの適量(下記のデータ表に示される通り)を、室温で20分間、同じバイアルにおいて予備混合し、その後、重合を開始するために、高圧触媒注入ポンプを使用してリアクターに装荷し、続いて、イソオクタンによりフラッシングする。発熱の後、温度を67℃に制御する。運転時間が1時間である。
Claims (19)
- マグネシウム成分と、チタン成分と、下記の構造(I)を有する置換1,2−フェニレン芳香族ジエステルを含む内部電子供与体との組合せを含むチーグラー・ナッタ重合のプロ触媒(procatalyst)組成物。
(A)R1〜R14は同じであるか、又は異なり、R1〜R14のそれぞれが、水素、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択され、かつ、
(B)R1〜R4の少なくとも1つが、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択される。) - R5〜R14の少なくとも1つが、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択される、請求項1に記載のプロ触媒組成物。
- R1〜R4の少なくとも1つ、R5〜R9の少なくとも1つ、及びR10〜R14の少なくとも1つが、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択される、請求項1又は2に記載のプロ触媒組成物。
- R1及びR3が同じであるか、又は異なり、かつ、それぞれが、C1〜C8アルキル基、C3〜C6シクロアルキル基及び置換されたC3〜C6シクロアルキル基からなる群より選択される、請求項1から3のいずれかに記載のプロ触媒組成物。
- R1及びR3が同じであるか、又は異なり、かつ、それぞれが、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、t−ブチル基、イソブチル基、sec−ブチル基、2,4,4−トリメチルペンタン−2−イル基、シクロペンチル基、シクロヘキシル基及びそれらの組合せからなる群より選択される、請求項1〜4のいずれかに記載のプロ触媒組成物。
- R2及びR4が水素である、請求項1から5のいずれかに記載のプロ触媒組成物。
- R1がメチル基であり、かつ、R3がt−ブチル基である、請求項1から5のいずれかに記載のプロ触媒組成物。
- R1及びR3のそれぞれがイソプロピル基である、請求項1から5のいずれかに記載のプロ触媒組成物。
- 重合条件下、オレフィンを、請求項1に記載のプロ触媒組成物及び助触媒を含む触媒組成物と接触させること、及び
オレフィン系ポリマーを形成すること
を含む、オレフィン系ポリマーを製造するためのチーグラー・ナッタ重合のプロセス。 - R5〜R14のそれぞれが水素である、請求項1及び4から8のいずれかに記載のプロ触媒組成物。
- R2、R3及びR4のそれぞれが水素であり、R1が、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択される、請求項1又は2に記載のプロ触媒組成物。
- R5〜R14の少なくとも1つが、水素、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ハロゲン及びそれらの組合せからなる群より選択される、請求項6に記載のプロ触媒組成物。
- R1〜R4の少なくとも2つが、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜10個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択される、請求項1に記載のプロ触媒組成物。
- R1及びR3のそれぞれが、C1〜C8アルキル基、C3〜C6シクロアルキル基、置換されたC3〜C6シクロアルキル基及びそれらの組合せからなる群より選択される、請求項13に記載のプロ触媒組成物。
- 置換1,2−フェニレン芳香族ジエステルが、3−メチル−5−t−ブチル−1,2−フェニレンジベンゾアート、3,6−ジメチル−1,2−フェニレンジベンゾアート、3,5−ジイソプロピル−1,2−フェニレンジベンゾアート、4−メチル−1,2−フェニレンジベンゾアート、4−t−ブチル−1,2−フェニレンジベンゾアート、2,3−ナフタレンジベンゾアート、1,2−ナフタレンジベンゾアート、3−メチル−5−t−ブチル−1,2−フェニレンジ(4−メチルベンゾアート)、3,5−ジイソプロピル−1,2−フェニレンジベンゾアート、3−メチル−5−t−ブチル−1,2−フェニレンジ(4−フルオロベンゾアート)、3−メチル−5−t−ブチル−1,2−フェニレンジ(2,4,6−トリメチルベンゾアート)、3−メチル−5−t−ブチル−1,2−フェニレンジ(4−クロロベンゾアート)、及び3,5−ジイソプロピル−1,2−フェニレンジベンゾアートからなる群より選択される、請求項1に記載のプロ触媒組成物。
- 請求項1に記載のプロ触媒組成物、助触媒、及び脂肪族モノカルボン酸エステルを含む活性制限剤を含む、重合触媒組成物。
- R5〜R12のそれぞれが水素である、請求項16に記載の触媒組成物。
- R1〜R3の少なくとも1つが、1個〜20個の炭素原子を有する置換されたヒドロカルビル基、1個〜20個の炭素原子を有する非置換のヒドロカルビル基、1個〜20個の炭素原子を有するアルコキシ基、ヘテロ原子及びそれらの組合せからなる群より選択される、請求項17に記載のプロ触媒組成物。
- アルコキシシランを含む外部電子供与体を含む、請求項16に記載の触媒組成物。
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ES2672069T3 (es) | 2018-06-12 |
MX2011007139A (es) | 2011-09-27 |
KR101600365B1 (ko) | 2016-03-07 |
MY153117A (en) | 2014-12-31 |
US9534063B2 (en) | 2017-01-03 |
CN102325808B (zh) | 2014-03-12 |
US9434799B2 (en) | 2016-09-06 |
US20150299346A1 (en) | 2015-10-22 |
RU2502746C2 (ru) | 2013-12-27 |
US8536372B2 (en) | 2013-09-17 |
US20140011670A1 (en) | 2014-01-09 |
KR20110110279A (ko) | 2011-10-06 |
JP2012514125A (ja) | 2012-06-21 |
US9045570B2 (en) | 2015-06-02 |
PL2373702T3 (pl) | 2018-07-31 |
BRPI0918698A8 (pt) | 2017-09-19 |
US20160280808A1 (en) | 2016-09-29 |
US8288585B2 (en) | 2012-10-16 |
WO2010078494A3 (en) | 2010-08-26 |
US20130035227A1 (en) | 2013-02-07 |
EP2373702B1 (en) | 2018-03-21 |
BRPI0918698A2 (pt) | 2015-12-01 |
CN102325808A (zh) | 2012-01-18 |
WO2010078494A2 (en) | 2010-07-08 |
RU2011132076A (ru) | 2013-02-10 |
WO2010078494A4 (en) | 2010-10-14 |
EP2373702A2 (en) | 2011-10-12 |
US20100222530A1 (en) | 2010-09-02 |
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MY166882A (en) | 2018-07-24 |
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