CN114426599A - Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof - Google Patents
Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof Download PDFInfo
- Publication number
- CN114426599A CN114426599A CN202011105038.7A CN202011105038A CN114426599A CN 114426599 A CN114426599 A CN 114426599A CN 202011105038 A CN202011105038 A CN 202011105038A CN 114426599 A CN114426599 A CN 114426599A
- Authority
- CN
- China
- Prior art keywords
- substituents
- dibenzoate
- heptanediol
- methyl
- electron donor
- 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.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 41
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 12
- -1 glycol ester compound Chemical group 0.000 claims abstract description 137
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 46
- 150000002367 halogens Chemical class 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims description 92
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical group CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 17
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 10
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 0.000 claims description 10
- IIHAWQOFHTYWGM-UHFFFAOYSA-N 1,4-diethoxybutane Chemical compound CCOCCCCOCC IIHAWQOFHTYWGM-UHFFFAOYSA-N 0.000 claims description 9
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 235000011147 magnesium chloride Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- MISPJWXLQJXWHM-UHFFFAOYSA-N (5-benzoyloxy-4-ethylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)C(CC)C(CC)OC(=O)C1=CC=CC=C1 MISPJWXLQJXWHM-UHFFFAOYSA-N 0.000 claims description 6
- IIYIECVYGJTMQU-UHFFFAOYSA-N (5-benzoyloxy-6-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(C(C)C)OC(=O)C1=CC=CC=C1 IIYIECVYGJTMQU-UHFFFAOYSA-N 0.000 claims description 6
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 6
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000005916 2-methylpentyl group Chemical group 0.000 claims description 6
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000005917 3-methylpentyl group Chemical group 0.000 claims description 6
- OPASQUXNJYNOCO-UHFFFAOYSA-N 4-(1-benzoyloxypropyl)octan-3-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CCCC)C(CC)OC(=O)C1=CC=CC=C1 OPASQUXNJYNOCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 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 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000005842 heteroatom Chemical group 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 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 6
- 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 claims description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Chemical group 0.000 claims description 6
- 125000003367 polycyclic group Chemical group 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Chemical group 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- UGVIHDDRPUSMBC-UHFFFAOYSA-N (5-benzoyloxy-4,6-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)C(C)C(CC)OC(=O)C1=CC=CC=C1 UGVIHDDRPUSMBC-UHFFFAOYSA-N 0.000 claims description 5
- YVVDKVRIXQXQGL-UHFFFAOYSA-N (5-benzoyloxy-4-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)C(CC)OC(=O)C1=CC=CC=C1 YVVDKVRIXQXQGL-UHFFFAOYSA-N 0.000 claims description 5
- ZPWNCBGJRCGIKO-UHFFFAOYSA-N (6-benzoyloxy-6-ethyl-5-methylnonan-4-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)(CCC)C(C)C(CCC)OC(=O)C1=CC=CC=C1 ZPWNCBGJRCGIKO-UHFFFAOYSA-N 0.000 claims description 5
- RWRVHUGUGAVJTL-UHFFFAOYSA-N 1,4-dibutoxybutane Chemical compound CCCCOCCCCOCCCC RWRVHUGUGAVJTL-UHFFFAOYSA-N 0.000 claims description 5
- HMCUNLUHTBHKTB-UHFFFAOYSA-N 1,4-dimethoxybutane Chemical compound COCCCCOC HMCUNLUHTBHKTB-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 5
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 5
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 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 description 3
- 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 description 3
- 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 description 3
- AXUIEEPFBMGZLS-UHFFFAOYSA-N (4-benzoyloxy-3-methylpentan-2-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)C(C)C(C)OC(=O)C1=CC=CC=C1 AXUIEEPFBMGZLS-UHFFFAOYSA-N 0.000 claims description 3
- BUCBXHLZGJGGCA-UHFFFAOYSA-N (5-benzoyloxy-2,6-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)CC(C(C)C)OC(=O)C1=CC=CC=C1 BUCBXHLZGJGGCA-UHFFFAOYSA-N 0.000 claims description 3
- ORGLYAYBXMZVAV-UHFFFAOYSA-N (5-benzoyloxy-4-butyloctan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)C(CCCC)C(CC)OC(=O)C1=CC=CC=C1 ORGLYAYBXMZVAV-UHFFFAOYSA-N 0.000 claims description 3
- UCYYLAMYFFDGJB-UHFFFAOYSA-N (5-benzoyloxy-4-ethyl-4-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)(CC)C(CC)OC(=O)C1=CC=CC=C1 UCYYLAMYFFDGJB-UHFFFAOYSA-N 0.000 claims description 3
- PMWVFSWUEQEGCJ-UHFFFAOYSA-N (5-benzoyloxy-4-ethyl-4-methyloctan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)(CC)C(CCC)OC(=O)C1=CC=CC=C1 PMWVFSWUEQEGCJ-UHFFFAOYSA-N 0.000 claims description 3
- RAMDWQXDLFRDBH-UHFFFAOYSA-N (5-benzoyloxy-4-ethyl-6-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)C(CC)C(CC)OC(=O)C1=CC=CC=C1 RAMDWQXDLFRDBH-UHFFFAOYSA-N 0.000 claims description 3
- QMGMGHXBGNOJMD-UHFFFAOYSA-N (5-benzoyloxy-4-ethyloctan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CC)C(CCC)OC(=O)C1=CC=CC=C1 QMGMGHXBGNOJMD-UHFFFAOYSA-N 0.000 claims description 3
- QLDKOQJYGKBTEW-UHFFFAOYSA-N (5-benzoyloxy-4-methyl-4-propylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)(CCC)C(CC)OC(=O)C1=CC=CC=C1 QLDKOQJYGKBTEW-UHFFFAOYSA-N 0.000 claims description 3
- WLHWKRGOKDDQNU-UHFFFAOYSA-N (5-benzoyloxy-4-methyloctan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)C(CCC)OC(=O)C1=CC=CC=C1 WLHWKRGOKDDQNU-UHFFFAOYSA-N 0.000 claims description 3
- BRUAPAODBHIIME-UHFFFAOYSA-N (5-benzoyloxy-4-propylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CCC)C(CC)OC(=O)C1=CC=CC=C1 BRUAPAODBHIIME-UHFFFAOYSA-N 0.000 claims description 3
- CCDYRQJEEJXSGW-UHFFFAOYSA-N (5-benzoyloxy-4-propyloctan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CCC)C(CCC)OC(=O)C1=CC=CC=C1 CCDYRQJEEJXSGW-UHFFFAOYSA-N 0.000 claims description 3
- XTOLJLHPCKTDBE-UHFFFAOYSA-N (5-benzoyloxy-5-ethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(CC)(CC)OC(=O)C1=CC=CC=C1 XTOLJLHPCKTDBE-UHFFFAOYSA-N 0.000 claims description 3
- REFZFCGEQBVWRZ-UHFFFAOYSA-N (5-benzoyloxy-6-ethyl-2-methyloctan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(CC)CC)CC(C(C)C)OC(=O)C1=CC=CC=C1 REFZFCGEQBVWRZ-UHFFFAOYSA-N 0.000 claims description 3
- ILGNOFOLEBPBBK-UHFFFAOYSA-N (5-benzoyloxy-6-methyl-4-propylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)C(CCC)C(CC)OC(=O)C1=CC=CC=C1 ILGNOFOLEBPBBK-UHFFFAOYSA-N 0.000 claims description 3
- GWSKTIMWRDPCFN-UHFFFAOYSA-N (6-benzoyloxy-5-butylnonan-4-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)C(CCCC)C(CCC)OC(=O)C1=CC=CC=C1 GWSKTIMWRDPCFN-UHFFFAOYSA-N 0.000 claims description 3
- XBPADSFPRJOKNF-UHFFFAOYSA-N (6-benzoyloxy-5-ethylnonan-4-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)C(CC)C(CCC)OC(=O)C1=CC=CC=C1 XBPADSFPRJOKNF-UHFFFAOYSA-N 0.000 claims description 3
- DWNRZZOZTVXCFT-UHFFFAOYSA-N (6-benzoyloxy-5-methylnonan-4-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)C(C)C(CCC)OC(=O)C1=CC=CC=C1 DWNRZZOZTVXCFT-UHFFFAOYSA-N 0.000 claims description 3
- BZHRLSHCNNKLHX-UHFFFAOYSA-N (6-benzoyloxy-5-phenylnonan-4-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)C(C=1C=CC=CC=1)C(CCC)OC(=O)C1=CC=CC=C1 BZHRLSHCNNKLHX-UHFFFAOYSA-N 0.000 claims description 3
- RMGIRHJKNXLSAH-UHFFFAOYSA-N (6-benzoyloxy-5-propylnonan-4-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)C(CCC)C(CCC)OC(=O)C1=CC=CC=C1 RMGIRHJKNXLSAH-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- GJLQZOPUIIUVGL-UHFFFAOYSA-N 6-benzoyloxynonan-4-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)CC(CCC)OC(=O)C1=CC=CC=C1 GJLQZOPUIIUVGL-UHFFFAOYSA-N 0.000 claims description 3
- RHYNZEFEZLMHIL-UHFFFAOYSA-N [2-benzoyloxy-3,5-di(propan-2-yl)phenyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OC=1C(C(C)C)=CC(C(C)C)=CC=1OC(=O)C1=CC=CC=C1 RHYNZEFEZLMHIL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000005647 linker group Chemical group 0.000 claims description 3
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- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- RNWGIMBQHWREFU-UHFFFAOYSA-N (5-benzoyloxy-2,2,6,6-tetramethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)(C)C)CC(C(C)(C)C)OC(=O)C1=CC=CC=C1 RNWGIMBQHWREFU-UHFFFAOYSA-N 0.000 claims description 2
- HDCPAWWIFPIIQB-UHFFFAOYSA-N (5-benzoyloxy-4,4-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)(C)C(CC)OC(=O)C1=CC=CC=C1 HDCPAWWIFPIIQB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
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- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OLNLMGUGLRLIQL-UHFFFAOYSA-N 6-benzoyloxydecan-4-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCCC)CC(CCC)OC(=O)C1=CC=CC=C1 OLNLMGUGLRLIQL-UHFFFAOYSA-N 0.000 claims description 2
- YHXLPTVPBGSYBR-UHFFFAOYSA-N CC(C)(C)C(C(C)=C1)=CC(OC(C2=CC=CC=C2)=O)=C1OC(C1=CC=CC=C1)=O Chemical compound CC(C)(C)C(C(C)=C1)=CC(OC(C2=CC=CC=C2)=O)=C1OC(C1=CC=CC=C1)=O YHXLPTVPBGSYBR-UHFFFAOYSA-N 0.000 claims description 2
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
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- QMJUEAKSVSCCQL-UHFFFAOYSA-N benzyl phosphite Chemical compound [O-]P([O-])OCC1=CC=CC=C1 QMJUEAKSVSCCQL-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
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- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 claims description 2
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
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- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000007791 liquid phase Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
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- MVJSLTMEEOSFIE-UHFFFAOYSA-N CC[AlH]CC.Cl Chemical compound CC[AlH]CC.Cl MVJSLTMEEOSFIE-UHFFFAOYSA-N 0.000 description 1
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- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- BTJCEVZMRIJBSM-UHFFFAOYSA-N dimethoxy-methyl-(1,1,1-trifluoropropan-2-yl)silane Chemical compound CO[Si](C)(OC)C(C)C(F)(F)F BTJCEVZMRIJBSM-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
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- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
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- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
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- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
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- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a catalyst component for preparing polyolefin, a preparation method thereof, an olefin polymerization catalyst and application thereof. The catalyst component contains magnesium element, halogen, titanium element, an internal electron donor a and an internal electron donor b, wherein the internal electron donor a is a diether compound shown as a formula I, and the internal electron donor b is a glycol ester compound shown as a formula II. The catalyst component can greatly improve the activity and hydrogen regulation sensitivity of the catalyst, can still keep higher isotacticity under the condition of high hydrogen concentration, can be used for propylene homopolymerization and propylene copolymerization, and has wider application range.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a catalyst component for preparing polyolefin, a preparation method thereof, an olefin polymerization catalyst and application thereof.
Background
The solid titanium catalyst component with magnesium, titanium, halogen and electron donor compound as basic components is used in olefin polymerization reaction, and has high polymerization activity and stereo orientation especially in propylene polymerization. Among them, the electron donor compound is one of the essential components in the catalyst component, and plays a decisive role in important indexes such as polymerization activity, isotactic index of polymer, molecular weight and molecular weight distribution. With the development of internal electron donor compounds, polyolefin catalysts are continuously updated.
In the industrial production of polyolefin, the requirement on the performance of materials is higher and higher, and the requirements of polymers in various aspects such as melt index, molecular weight distribution, steel toughness balance and the like cannot be realized by a single internal electron donor. In order to obtain polymer materials with more comprehensive performance, researchers have made efforts on modifying resins on one hand and on the other hand, have made continuous attempts on compounding internal electron donors of catalysts.
Ziegler-Natta type polyolefin catalysts have been developed to date, and several characteristic internal electron donors have been discovered, which are dicarboxylic acid ester compounds with high stereospecific capacity, moderate activity and moderate molecular weight distribution; 1, 3-diether compounds with higher activity, narrower molecular weight distribution and higher hydrogen regulation sensitivity; succinate compounds with wider molecular weight distribution and lower hydrogen regulation sensitivity; glycol ester compounds with good comprehensive performance and relatively weak hydrogen regulation sensitivity, and the like. Due to the superior performance of diether compounds, in recent years, reports of compounding different electron donors with 1, 3-diether electron donors are endless, and the hydrogen regulation sensitivity of the catalyst can be effectively improved. For example, in the catalyst component and the catalyst disclosed in CN101724102A, a glycol ester compound and a diether compound are compounded to be used as an internal electron donor, and the catalyst containing the combined internal electron donor has ultrahigh polymerization activity and higher stereospecificity when used for olefin polymerization. Compared with the similar catalyst, the activity and the stereospecificity of the catalyst are both at a higher level. However, the diether compound has a complex preparation method and high preparation cost, and the production cost is high in industrial large-scale application.
The CN103044586B patent and the CN101589068A patent respectively use long-chain and short-chain alpha, omega-diethers with more than 5 carbons, which are applied to polyethylene catalysts for reducing the molecular weight distribution of ethylene polymers, but the catalyst components are applied to polypropylene catalysts, and the isotacticity is lower and the catalyst effect is poorer.
Disclosure of Invention
The invention provides a novel catalyst component for preparing polyolefin, aiming at the problems that the existing catalyst component for preparing polyolefin has complex preparation method, higher preparation cost and low activity, can only be applied to ethylene polymerization reaction, can not be applied to propylene homopolymerization and propylene copolymerization, and has certain limitation in application aspect, the catalyst component adopts an internal electron donor a which has simple structure, is convenient and easy to obtain and has low price, and is compounded with an internal electron donor b for use, the hydrogen regulation sensitivity of the catalyst can be greatly improved, the obtained polymer has higher isotacticity, can be applied to propylene homopolymerization and propylene copolymerization, and has wider application range.
The invention provides a catalyst component for preparing polyolefin, which contains magnesium element, halogen, titanium element, an internal electron donor a and an internal electron donor b, wherein the internal electron donor a is a diether compound shown in a formula I, the internal electron donor b is a dihydric alcohol ester compound shown in a formula II,
in the formula I, R'1And R'2Are the same or different and are each independently selected from C1-C30Alkyl of (C)6-C30With or without substituents aryl, C7-C30With or without substituents aralkyl and C7-C30With or without substituents of alkylaryl;
in the formula I, R'3、R’4、R’5And R'6The same or different, each independently selected from hydrogen, halogen, C1-C30Alkyl of (C)6-C30With or without substituents aryl, C7-C30With or without substituents aralkyl and C7-C30With or without substituents of alkylaryl;
in the formula I, n' is an integer of 1-10;
in the formula II, R1And R2Are the same or different and are each independently selected from C1-C20With or without substituents, C2-C20With or without substitution ofAlkenyl of radicals, C6-C20With or without substituents aryl, C7-C20With or without substituents, C7-C20With or without substituents aralkyl and C10-C20With or without substituents; m is a divalent linking group.
In the present invention, the term "alkyl" includes straight chain alkyl, branched chain alkyl and cycloalkyl. E.g. C1-C30Alkyl of (2) includes C1-C30Straight chain alkyl group of (1), C3-C30Branched alkyl and C3-C30A cycloalkyl group of (a).
According to some embodiments of the catalyst component of the present invention, the halogen is selected from one or more of bromine, chlorine and iodine.
According to some embodiments of the catalyst component of the present invention, R 'of formula I'1And R'2Wherein the substituents are each independently selected from halogen, C1-C10Alkyl and C1-C10One or more of alkoxy groups of (a). Preferably, R 'in formula I'1And R'2Wherein the substituents are each independently selected from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
In the context of the present invention, halogen means one or more selected from the group consisting of bromine, chlorine and iodine.
According to some embodiments of the catalyst component of the present invention, R 'of formula I'3、R’4、R’5And R'6Wherein each of said substituents is independently selected from hydrogen, halogen, C1-C10Alkyl and C1-C10One or more of alkoxy groups of (a). Preferably, R 'in formula I'3、R’4、R’5And R'6Wherein the substituents are each independently selected from one or more of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
According to a preferred embodiment of the catalyst component according to the present invention, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether, 1, 4-diethoxybutane and butylene glycol dibutyl ether. More preferably, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether and butylene glycol dibutyl ether. In the present invention, the internal electron donor a may be obtained by synthesis or commercially.
According to some embodiments of the catalyst component of the present invention, in formula II, R1And R2Each independently selected from C1-C10With or without substituents, C2-C10With or without substituents alkenyl, C6-C10With or without substituents aryl, C7-C10With or without substituents, C7-C10With or without substituents aralkyl and C10-C15With or without substituents.
According to some embodiments of the catalyst component of the present invention, R in formula II1And R2In (1), the substitutionThe radicals are selected from hydroxy, halogen, cyano, nitro, amino, mono- (C)1-C6Alkyl) amino, bis- (C)1-C6Alkyl) amino, aldehyde, carboxyl and heteroatom.
According to some embodiments of the catalyst component of the present invention, in formula II, M is selected from C1-C20With or without substituents alkylene, C3-C20With or without substituents cycloalkylene and C6-C20With or without substituents.
According to some embodiments of the catalyst component of the present invention, in M of formula II, the substituent is C1-C20One or more of alkyl groups, and substituents are optionally bonded to one or more rings.
According to some embodiments of the catalyst component of the present invention, the carbon atoms or/and the hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.
According to a preferred embodiment of the catalyst component of the present invention, the internal electron donor b is a diol ester compound represented by formula III,
in the formula III, R1And R2Are the same or different and are each independently selected from C1-C10With or without substituents, C2-C10With or without substituents alkenyl, C2-C10With or without substituents alkynyl, C6-C20With or without substituents aryl, C7-C20With or without substituents aralkyl and C7-C20With or without substituents. Preferably, in formula III, R1And R2Each independently selected from C1-C6With or without a substituent,C2-C6With or without substituents alkenyl, C2-C6With or without substituents alkynyl, C6-C10With or without substituents aryl, C7-C10With or without substituents aralkyl and C7-C10With or without substituents.
In the general formula III
Means that n carbon atoms are bonded in sequence and that each carbon atom is further bonded to 2 substituents, i.e. there are n carbon atoms and R in total in parentheses1、R2、R3…R2nAnd 2n substituents. In particular, the amount of the solvent to be used,
when n is 0, the bracketed moiety is absent, i.e., when formula III is of the formula
When n is equal to 1, the reaction is carried out,
is composed of
When n is 2, the compound is added,
is composed of
When n is 3, the compound is added,
is composed of
When n is equal to 4, the reaction solution is,
is composed of
When n is 5, the compound is added,
is composed of
When n is equal to 6, the reaction solution is,
is composed of
By the way of analogy, the method can be used,
when n is 10, the reaction time is 10,
is composed of
According to some embodiments of the catalyst component of the present invention, R of formula III1And R2Wherein the substituents are selected from halogen and C1-C6Alkyl and C1-C6One or more of alkoxy groups of (a).
According to some embodiments of the catalyst component of the present invention, in formula III, R3、R4、R5、R6And R1-R2nThe same or different, each independently selected from hydrogen, halogen, C1-C20With or without substituents, C2-C10With or without substituents alkenyl, C2-C10With or without substituentsAlkynyl of (A), C6-C20With or without substituents aryl, C7-C20With or without substituents, C7-C20With or without substituents aralkyl and C10-C20With or without substituents. Preferably, in formula III, R3、R4、R5、R6And R1-R2nEach independently selected from hydrogen, halogen, C1-C10With or without substituents, C2-C6With or without substituents alkenyl, C2-C6With or without substituents alkynyl, C6-C10With or without substituents aryl, C7-C10With or without substituents, C7-C10With or without substituents aralkyl and C10-C15With or without substituents.
According to some embodiments of the catalyst component of the present invention, R of formula III3、R4、R5、R6And R1-R2nWherein the substituents are selected from halogen and C1-C6Alkyl and C1-C6One or more of alkoxy groups of (a).
According to some embodiments of the catalyst component of the present invention, in formula III, R3、R4、R5、R6And R1-R2nOptionally containing heteroatoms selected from one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or, in formula III, R3、R4、R5、R6And R1-R2nTwo or more of them form a monocyclic ring and/or polycyclic ring; preferably, the monocyclic and/or polycyclic ring is each independently saturated or unsaturated.
According to some embodiments of the catalyst component of the present invention, in formula III, n is an integer from 0 to 10, preferably an integer from 1 to 8, more preferably an integer from 2 to 6.
According to some embodiments of the catalyst component of the present invention, in formula III, when n is 0, the substituent is R3And R4The carbon atom and substituent of (A) is R5And R6Is bonded to the carbon atom(s) of (a).
According to a preferred embodiment of the catalyst component according to the present invention, the internal electron donor b is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-o-methylbenzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-o-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2,6, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, mixtures thereof, and mixtures thereof, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 8-naphthyl ester, 1, 8-naphthyl di-4-n-butylbenzoate, 1, 8-naphthyl di-4-isobutylbenzoate, 1, 8-naphthyl di-4-tert-butylbenzoate, 1, 8-naphthyl di-4-phenylbenzoate, 1, 8-naphthyl di-4-fluorobenzoate, 1, 8-naphthyl di-3-fluorobenzoate, 1, 8-naphthyl di-2-fluorobenzoate. In the present invention, the internal electron donor b can be prepared by referring to the method disclosed in CN 1213080C.
According to some embodiments of the catalyst component of the present invention, the amount of magnesium element is from 5 to 30%, preferably from 8 to 25%, more preferably from 10 to 22%, based on the total weight of the catalyst component; the content of halogen is 30-80%, preferably 40-70%; the content of titanium element is 0.5-10%, preferably 1-6%; the content of the internal electron donor a is 0.5-25 wt%, preferably 1-20 wt%; the content of the internal electron donor b is 0.5 to 25%, preferably 1 to 20% by weight. Within the preferred content range of the present invention, the olefin polymerization catalyst containing the catalyst component for preparing polyolefin of the present invention has higher activity, better hydrogen response, better isotacticity of the obtained polymer, and wider application reaction.
According to a preferred embodiment of the present invention, the weight ratio of the content of internal electron donor a to the content of internal electron donor b is 1: (0.1 to 10) has a better hydrogen response and isotacticity effect.
The internal electron donor a and the internal electron donor b are jointly used as the internal electron donor, and can play a synergistic role. The activity of the catalyst is greatly improved, and the hydrogen regulation sensitivity of the catalyst is greatly improved.
The second aspect of the present invention provides the above-mentioned method for preparing a catalyst component for polyolefin production, comprising the steps of:
step A: carrying out first contact on a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound and an optional internal electron donor a in a solvent to obtain a first mixture;
and B: and B: in the presence of a precipitation assistant, carrying out second contact on the first mixture, a titanium compound and an optional internal electron donor a to obtain a second mixture;
and C: carrying out third contact on the second mixture and an internal electron donor b and an optional internal electron donor a, washing and drying;
wherein at least one of the steps A, B and C uses an internal electron donor a,
wherein the internal electron donor a is a diether compound shown as a formula I; the internal electron donor b is a dihydric alcohol ester compound shown as a formula II,
in the formula I, R'1And R'2Are the same or different and are each independently selected from C1-C30Alkyl of (C)6-C30With or without substituents aryl, C7-C30With or without substituents aralkyl and C7-C30With or without substituents of alkylaryl;
in the formula I, R'3、R’4、R’5And R'6The same or different, each independently selected from hydrogen, halogen, C1-C30Alkyl of (C)6-C30With or without substituents aryl, C7-C30With or without substituents aralkyl and C7-C30With or without substituents of alkylaryl;
in the formula I, n' is an integer of 1-10;
in the formula II, R1And R2Are the same or different and are each independently selected from C1-C20With or without substituents, C2-C20With or without substituents alkenyl, C6-C20With or without substituents aryl, C7-C20With or without substituents, C7-C20With or without substituents aralkyl and C10-C20With or without substituents; m is a divalent linking group.
In the present invention, the term "alkyl" includes straight chain alkyl, branched chain alkyl and cycloalkyl. E.g. C1-C30Alkyl of (2) includes C1-C30Straight chain alkyl group of (1), C3-C30Branched alkyl and C3-C30A cycloalkyl group of (a).
According to some embodiments of the method of making of the present invention, the halogen is selected from one or more of bromine, chlorine, and iodine.
According to some embodiments of the preparation methods of the present invention, R 'of formula I'1And R'2Wherein the substituents are each independently selected from halogen, C1-C10Alkyl and C1-C10One or more of alkoxy groups of (a). Preferably, R 'in formula I'1And R'2Wherein said substituents are each independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-One or more of ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
In the context of the present invention, halogen means one or more selected from the group consisting of bromine, chlorine and iodine.
According to some embodiments of the preparation methods of the present invention, R 'of formula I'3、R’4、R’5And R'6Wherein each of said substituents is independently selected from hydrogen, halogen, C1-C10Alkyl and C1-C10One or more of alkoxy groups of (a). Preferably, R 'in formula I'3、R’4、R’5And R'6Wherein the substituents are each independently selected from one or more of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
According to a preferred embodiment of the preparation method of the present invention, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether, 1, 4-diethoxybutane and butylene glycol dibutyl ether. More preferably, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether and butylene glycol dibutyl ether. In the present invention, the internal electron donor a may be obtained by synthesis or commercially.
According to some embodiments of the preparation process of the present invention, R in formula II1And R2Each independently selected from C1-C10With or without substituents, C2-C10With or without substituents alkenyl, C6-C10With or without substituents aryl, C7-C10With or without substituents, C7-C10With or without substituents aralkyl and C10-C15With or without substituents.
According to some embodiments of the preparation process of the present invention, R in formula II1And R2Wherein the substituent is selected from the group consisting of hydroxy, halogen, cyano, nitro, amino, mono- (C)1-C6Alkyl) amino, bis- (C)1-C6Alkyl) amino, aldehyde, carboxyl and heteroatom.
According to some embodiments of the preparation method of the present invention, in formula II, M is selected from C1-C20With or without substituents alkylene, C3-C20With or without substituents cycloalkylene and C6-C20With or without substituents.
According to some embodiments of the preparation method of the present invention, in M of formula II, the substituent is C1-C20One or more of alkyl groups, and substituents are optionally bonded to one or more rings.
According to some embodiments of the preparation method of the present invention, the carbon atom or/and the hydrogen atom in M is optionally substituted by a nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atom.
According to the preferred embodiment of the preparation method of the invention, the internal electron donor b is a diol ester compound shown in formula III,
in the formula III, R1And R2Same or differentAnd each is independently selected from C1-C10With or without substituents, C2-C10With or without substituents alkenyl, C2-C10With or without substituents alkynyl, C6-C20With or without substituents aryl, C7-C20With or without substituents aralkyl and C7-C20With or without substituents. Preferably, in formula III, R1And R2Each independently selected from C1-C6With or without substituents, C2-C6With or without substituents alkenyl, C2-C6With or without substituents alkynyl, C6-C10With or without substituents aryl, C7-C10With or without substituents aralkyl and C7-C10With or without substituents.
According to some embodiments of the preparation method of the present invention, R of formula III1And R2Wherein the substituents are selected from halogen and C1-C6Alkyl and C1-C6One or more of alkoxy groups of (a).
According to some embodiments of the preparation process of the present invention, in formula III, R3、R4、R5、R6And R1-R2nThe same or different, each independently selected from hydrogen, halogen, C1-C20With or without substituents, C2-C10With or without substituents alkenyl, C2-C10With or without substituents alkynyl, C6-C20With or without substituents aryl, C7-C20With or without substituents, C7-C20With or without substituents aralkyl and C10-C20With or without substituents. Preferably, in formula III, R3、R4、R5、R6And R1-R2nEach independently selected from hydrogen, halogen, C1-C10With or without substituents, C2-C6With or without substituents alkenyl, C2-C6With or without substituents alkynyl, C6-C10With or without substituents aryl, C7-C10With or without substituents, C7-C10With or without substituents aralkyl and C10-C15With or without substituents.
According to some embodiments of the preparation method of the present invention, R of formula III3、R4、R5、R6And R1-R2nWherein the substituents are selected from halogen and C1-C6Alkyl and C1-C6One or more of alkoxy groups of (a).
According to some embodiments of the preparation process of the present invention, in formula III, R3、R4、R5、R6And R1-R2nOptionally containing heteroatoms selected from one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or, in formula III, R3、R4、R5、R6And R1-R2nTwo or more of them form a monocyclic ring and/or polycyclic ring; preferably, the monocyclic and/or polycyclic ring is each independently saturated or unsaturated.
According to some embodiments of the preparation method of the present invention, in formula III, n is an integer of 0 to 10, preferably an integer of 1 to 8, and more preferably an integer of 2 to 6.
According to some embodiments of the preparation method of the present invention, in formula III, when n is 0, the substituent is R3And R4The carbon atom and substituent of (A) is R5And R6Is bonded to the carbon atom(s) of (a).
According to a preferred embodiment of the preparation method of the present invention, the internal electron donor b is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-o-methylbenzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-o-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-4-heptanediol di (p-methylbenzoic acid) ester, 2, 5-heptanediol dibenzoate, 2-methyl-4-heptanediol di (p-methylbenzoic acid) ester, 4-methylbenzoic acid, 4-methyl ester, 4-heptanediol di (m-methylbenzoic acid) ester, 4-methylbenzoic acid, and mixtures thereof, 2,2,6, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-dibenzoate, 2-phenylene dibenzoate, and mixtures thereof, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 1, 8-naphthyl di-4-n-butylbenzoate, 8-naphthyl ester, 1, 8-naphthyl bis-4-isobutylbenzoate, 1, 8-naphthyl bis-4-tert-butylbenzoate, 1, 8-naphthyl bis-4-phenylbenzoate, 1, 8-naphthyl bis-4-fluorobenzoate, 1, 8-naphthyl bis-3-fluorobenzoate, 1, 8-naphthyl bis-2-fluorobenzoate. In the present invention, the internal electron donor b can be prepared by referring to the method disclosed in CN 1213080C.
According to some embodiments of the method of the present invention, the magnesium halide compound has a formula of MgX2Wherein, X is bromine, chlorine or iodine; preferably, the magnesium halide compound is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, more preferably magnesium dichloride, more preferably anhydrous magnesium dichloride.
According to some embodiments of the method of preparing of the present invention, the organophosphorus compound is selected from one or more of tripentyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite; more preferably tributyl phosphate or tripentyl phosphate.
According to some embodiments of the preparation method of the present invention, the organic epoxy compound is C2-C8One or more of the aliphatic olefin of (a), the oxidation product of a halogenated aliphatic olefin; more preferably ethylene oxide, propylene oxide, ethylene oxide chloride, epichlorohydrin, butylene oxide, butadiene double oxide, methyl glycidyl ether and diglycidyl etherOne or more of; more preferably epichlorohydrin.
According to some embodiments of the preparation method of the present invention, the solvent may be a mixture capable of dissolving a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an internal electron donor a and an internal electron donor b, and preferably, the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane; more preferably toluene.
According to some embodiments of the production method of the present invention, the precipitation aid is selected from one or more of organic acids, organic acid anhydrides, organic ethers, and organic ketones; more preferably one or more of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and amyl ether; more preferably phthalic anhydride.
According to some embodiments of the method of the present invention, the titanium compound has the general formula TiXm(ORn)4-mWherein X is halogen, preferably, X is bromine, chlorine or iodine, Rn is C1-C20M is an integer of 1 to 4; preferably, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium; more preferably titanium tetrachloride.
According to some embodiments of the preparation method of the present invention, the organic phosphorus compound is used in an amount of 0.1 to 5 moles, the organic epoxy compound is used in an amount of 0.2 to 10 moles, the total amount of the internal electron donors a is 0.0001 to 5 moles, the precipitation assistant is used in an amount of 0.025 to 1 mole, the titanium compound is used in an amount of 0.5 to 20 moles, and the internal electron donor b is used in an amount of 0.0001 to 5 moles, per mole of the magnesium halide compound; preferably, the organic phosphorus compound is used in an amount of 0.3 to 3 moles, the organic epoxy compound is used in an amount of 0.5 to 4 moles, the total amount of the internal electron donors a is 0.01 to 1 mole, the precipitation assistant is used in an amount of 0.05 to 0.5 mole, the titanium compound is used in an amount of 1 to 15 moles, and the internal electron donor b is used in an amount of 0.01 to 1 mole, per mole of the magnesium halide compound. Wherein, the total dosage of the internal electron donor a refers to the total dosage of the step A, the step B and the step C, and if the internal electron donor a is used only once, the total dosage is the dosage. For example, if only 0.05 mole of internal electron donor a is used in step C, the total amount of internal electron donor a used is 0.05 mole.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the first contacting comprise: the temperature is 10-100 deg.C, preferably 30-80 deg.C, and the time is 0.05-6 hr, preferably 0.1-2 hr.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the second contacting comprise: -30 to 60 ℃, preferably-30 to 20 ℃, for 0.1 to 5 hours, preferably 0.2 to 4 hours.
According to some embodiments of the preparation process of the present invention, the conditions of the third contacting comprise: the temperature is 30-200 deg.C, preferably 60-120 deg.C, and the time is 0.5-8 hr, preferably 1-6 hr.
According to some embodiments of the preparation method of the present invention, the drying condition may be conventional vacuum drying, and is not described herein again.
According to some embodiments of the preparation method of the present invention, the washing process may include: washed 2-5 times with toluene, 2-5 times with a mixture of titanium tetrachloride and toluene, and finally 4-6 times with hexane. Among them, the amount of titanium tetrachloride and toluene used in the mixture of titanium tetrachloride and toluene is in a wide range, and the purpose is to sufficiently perform washing. For example, 0.4 mol titanium tetrachloride and 60 ml toluene. For example, 2 washes with toluene, 2 washes with a mixture of 0.4 mol titanium tetrachloride and 60 ml toluene, and finally 5 washes with hexane.
In a third aspect, the present invention provides an olefin polymerization catalyst comprising the following catalyst components:
(1) the catalyst component for producing a polyolefin according to any one of claims 1 to 4 and/or the catalyst component for producing a polyolefin obtained by the production method according to any one of claims 5 to 8;
(2) an alkyl aluminum compound;
and (3) optionally an external electron donor compound.
According to some embodiments of the olefin polymerization catalyst of the present invention, the alkylaluminum compound has the formula AlRnX3-nThe compound shown in the specification, wherein R is hydrogen or C1-C20Preferably, R is alkyl, aralkyl or aryl, X is halogen, preferably, X is bromine, chlorine or iodine, n is an integer of 1 to 3; further preferably, the alkyl aluminum compound is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochlorchloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride, and still more preferably triethylaluminum and/or triisobutylaluminum.
According to some embodiments of the olefin polymerization catalyst of the present invention, the molar ratio of the alkyl aluminum compound, calculated as aluminum, to the catalyst component, calculated as titanium, is from 5 to 5000:1, more preferably from 20 to 1000: 1. E.g., 20:1, 50: 1. 100, and (2) a step of: 1. 200: 1. 300, and (2) 300: 1. 400: 1. 500: 1. 600: 1. 700: 1. 800: 1. 900: 1. 1000:1, and any value in between.
According to some embodiments of the olefin polymerization catalyst of the present invention, the external electron donor compound is an organosilicon compound, preferably having the formula R1nSi(ORy)4-nWherein n is an integer of 0 to 3, R1 is selected from one or more of alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, Ry is selected from one or more of alkyl, cycloalkyl, aryl and halogenated alkyl; preferably, the external electron donor compound is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and mixtures thereofOne or more of ethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, more preferably methylcyclohexyldimethoxysilane.
According to some embodiments of the olefin polymerization catalyst of the present invention, the molar ratio of the alkyl aluminum compound to the external electron donor compound, calculated as aluminum, is from 0.1 to 500:1, preferably from 1 to 300:1, more preferably from 3 to 100: 1. For example, 3:1, 5: 1. 10: 1. 20: 1. 30: 1. 40: 1. 50: 1. 60: 1. 70: 1. 80: 1. 90: 1. 100, and (2) a step of: 1, and any value in between.
In a fourth aspect, the present invention provides the use of an olefin polymerisation catalyst as described above in an olefin polymerisation reaction.
According to some embodiments of the use of the present invention, the reaction is a homopolymerization and/or a copolymerization.
According to some embodiments of the uses of the present invention, the alkene comprises a compound represented by formula CH2Olefins represented by CHR, wherein R is hydrogen, C1-C6Alkyl groups of (a); more preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene; further preferably, the olefin is selected from one or more of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene; even more preferably, the compound represented by the formula CH2The olefin represented by ═ CHR is propylene. Such as propylene homopolymerization, or copolymerization of propylene with other olefins, wherein the other olefins may be, but are not limited to: ethylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.
According to some embodiments of the applications described herein, the polymerization of the olefin may be carried out in the liquid phase of the monomer or of a solution of the monomer in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas-liquid phase. The polymerization temperature may be from 0 to 150 ℃ and preferably from 60 to 100 ℃. The polymerization pressure is from 0.01 to 10MPa, preferably from 0.5 to 5 MPa. The polymerization time is from 0.1 to 5 hours, preferably from 0.5 to 3 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention easier to understand, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the test methods involved are as follows:
1. determination of titanium content in catalyst: colorimetric measurements were performed using a UV-Vis Spectrophotometer type 722.
2. The magnesium content was determined by magnesium ion and EDTA complex titration.
3. The halogen content being AgNO3-NH4CNS back-drop method.
4. Measuring the content of the internal electron donor compound in the catalyst: the method comprises the steps of decomposing the catalyst dry powder by dilute acid by adopting a chromatography method, extracting an internal electron donor compound by using an extracting agent, and measuring by using a liquid chromatograph.
5. The melt flow index (MFR) of the polymer was determined using a melt flow index meter model 6932 from CEAST, Italy, with reference to GB/T3682.1-2018 standard.
6. The propylene polymer Isotacticity Index (II) was determined by heptane extraction: a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours and the residue was dried to constant weight, and the ratio of the weight (g) of the polymer to 2(g) was found to be the isotacticity.
7. The calculation method and formula of the AC are as follows: the polymerization gave the weight of the powder/(weight of catalyst. times.polymerization time).
In the following examples of the present invention,
ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 4-diethoxybutane, tributyl phosphate, tripentyl phosphate, phthalic anhydride, methylcyclohexyldimethoxysilane, triethylaluminum were purchased from carbofuran corporation.
Reference is made to CN1213080C for the preparation of 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate and 4-methyl-3, 5-heptanediol dibenzoate.
[ example 1 ]
(1) In a glove box protected by high-purity nitrogen, 0.04 mol of anhydrous magnesium dichloride, 80 mL of toluene, 0.0325 mol of epoxy chloropropane, 0.04 mol of tributyl phosphate and 0.0025 mol of ethylene glycol diethyl ether (internal electron donor a) are sequentially added into a 300mL reaction kettle, and the mixture reacts for 120 minutes at the temperature of 60 ℃ to obtain a uniform solution;
(2) adding 0.0075 mol of phthalic anhydride (precipitation assistant) into the uniform solution, continuing to react for one hour, then cooling to-28 ℃, and dropwise adding 0.4 mol of titanium tetrachloride;
(3) heating to 85 ℃ at a heating rate of 0.5 ℃/min, adding 0.004 mol of 2, 4-pentanediol dibenzoate (internal electron donor b) at the temperature of 80 ℃, keeping the temperature for one hour, filtering, washing the solid with toluene twice, adding a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene, keeping the temperature for 0.5 hour at 110 ℃, filtering and washing twice, washing the obtained solid with hexane for 5 times, and then drying in vacuum to obtain the catalyst component for preparing polyolefin. The data for the contents of the substances are shown in Table 1.
[ example 1A ]
This example serves to illustrate the use of the catalyst component for the preparation of polyolefins in example 1 in the polymerization of propylene.
Application 1:
a5-liter stainless steel autoclave was sufficiently purged with nitrogen, then, 5 ml of a 0.5 mol/l triethylaluminum hexane solution and 1 ml of a 1 mol/l methylcyclohexyldimethoxysilane (CMMS, external electron donor) hexane solution and 10 mg of the catalyst component prepared in example 1 were added, 10 ml of hexane was added to flush the feed line, 1 liter of hydrogen and 2 liters of purified propylene were added in a standard state, and polymerization was carried out at this temperature for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging reaction products to obtain olefin polymerization products, and weighing to calculate the catalyst Activity (AC)1) Testing the melt indexMFR1And isotacticity II1The specific results are detailed in table 2.
Application 2:
a5-liter stainless steel autoclave was sufficiently purged with nitrogen, then, 5 ml of a 0.5 mol/l triethylaluminum hexane solution and 1 ml of a 1 mol/l methylcyclohexyldimethoxysilane (CMMS, external electron donor) hexane solution and 10 mg of the catalyst component prepared in example 1 were added, 10 ml of hexane was added to flush the feed line, 4.5 l of hydrogen and 2 l of purified propylene were added in a standard state, and polymerization was carried out at this temperature for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging reaction products to obtain olefin polymerization products, and weighing to calculate the catalyst Activity (AC)2) Testing the melt index MFR2And isotacticity II2The specific results are detailed in table 2.
[ example 2 ]
The procedure of example 1 was followed except that ethylene glycol dibutyl ether was used in place of ethylene glycol diethyl ether in an amount of 0.0025 mol. The data for the contents of the substances are shown in Table 1.
[ example 2A ]
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in example 2 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
[ example 3 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium dichloride, 80 mL of toluene, 0.0325 mol of epoxy chloropropane and 0.04 mol of tributyl phosphate into a 300mL reaction kettle, and reacting at 60 ℃ for 120 minutes to obtain a uniform solution;
(2) adding 0.0075 mol of phthalic anhydride (precipitation assistant) into the uniform solution, continuing to react for one hour, then cooling to-28 ℃, and dropwise adding 0.4 mol of titanium tetrachloride;
(3) heating to 85 ℃ at a heating rate of 0.3 ℃/min, adding 0.0025 mol of ethylene glycol diethyl ether (internal electron donor a) at the temperature of 40 ℃, adding 0.004 mol of 2, 4-pentanediol dibenzoate (internal electron donor b) at the temperature of 80 ℃, keeping the temperature for one hour, filtering, washing the solid with toluene twice, adding a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene, keeping the temperature for 0.5 hour at 110 ℃, filtering and washing twice, washing the obtained solid with hexane for 5 times, and drying in vacuum to obtain the catalyst component for preparing polyolefin. The data for the contents of the substances are shown in Table 1.
[ example 3A ]
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in example 3 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
[ example 4 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium dichloride, 80 mL of toluene, 0.0325 mol of epoxy chloropropane and 0.04 mol of tributyl phosphate into a 300mL reaction kettle, and reacting at 60 ℃ for 120 minutes to obtain a uniform solution;
(2) adding 0.01 mol of phthalic anhydride (precipitation assistant) into the uniform solution, continuing to react for one hour, then cooling to-28 ℃, and dropwise adding 0.4 mol of titanium tetrachloride;
(3) heating to 85 ℃ at a heating rate of 0.3 ℃/min, adding 0.0025 mol of ethylene glycol dibutyl ether (internal electron donor a) at the temperature of 40 ℃, then adding 0.004 mol of 2, 4-pentanediol dibenzoate (internal electron donor b) at the temperature of 80 ℃, keeping the temperature for one hour, filtering, washing the solid with toluene twice, adding a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene, keeping the temperature for 0.5 hour at 110 ℃, filtering and washing twice, washing the obtained solid with hexane for 5 times, and then drying in vacuum to obtain the catalyst component for preparing polyolefin. The data for the contents of the substances are shown in Table 1.
[ example 4A ]
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in example 4 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
[ example 5 ]
The procedure of example 2 was followed except that ethylene glycol dibutyl ether was used in an amount of 0.004 mole. The data for the contents of the substances are shown in Table 1.
[ example 5A ]
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in example 5 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
[ example 6 ]
The procedure of example 2 was followed except that 0.0025 moles of 1, 4-diethoxybutane was used instead of ethylene glycol dibutyl ether. The data for the contents of the substances are shown in Table 1.
[ example 6A ]
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in example 6 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
[ example 7 ]
The procedure of example 2 was followed except that 0.004 mole of 3, 5-heptanediol dibenzoate was used instead of 2, 4-pentanediol dibenzoate. The data for the contents of the substances are shown in Table 1.
[ example 7A ]
An olefin polymerization product was prepared according to the method of example 1A, except that the catalyst component for preparing polyolefin prepared in example 7 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
[ example 8 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium chloride, 80 mL of toluene, 0.04 mol of epoxy chloropropane and 0.06 mol of tripentyl phosphate into a 300mL reaction kettle, and reacting at 60 ℃ for 120 minutes to obtain a uniform solution;
(2) 0.01 mol of phthalic anhydride (precipitation assistant) is added into the uniform solution, the reaction is continued for one hour, then the temperature is reduced to-20 ℃, 30mL of hexane and 0.01 mol of ethylene glycol dibutyl ether (internal electron donor a) are added, and 0.5 mol of titanium tetrachloride is added dropwise.
(3) Heating to 85 ℃ at a heating rate of 0.5 ℃/min, adding 0.002 mol of 4-methyl-3, 5-heptanediol dibenzoate (internal electron donor b) at the temperature of 80 ℃, keeping the temperature for one hour, filtering, washing the solid twice with toluene, adding a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene, keeping the temperature for 0.5 hour at 110 ℃, filtering and washing twice, washing the obtained solid with hexane for 5 times, and then drying in vacuum to obtain the catalyst component for preparing polyolefin. The data for the contents of the substances are shown in Table 1.
[ example 8A ]
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in example 8 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
Comparative example 1
The procedure of example 1 was followed, except that ethylene glycol diethyl ether (internal electron donor compound a) was not used. The data for the contents of the substances are shown in Table 1.
Comparative example 1B
An olefin polymerization product was prepared as in example 1A, except thatThe catalyst component for preparing polyolefin prepared in comparative example 1. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
Comparative example 2
The procedure is as in example 7, except that ethylene glycol dibutyl ether (internal electron donor compound a) is not used. The data for the contents of the substances are shown in Table 1.
Comparative example 2B
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in comparative example 2 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
Comparative example 3
The procedure of example 1 was followed except that 2, 4-pentanediol dibenzoate (internal electron donor compound b) was not used. The data for the contents of the substances are shown in Table 1.
Comparative example 3B
An olefin polymerization product was prepared by following the procedure of example 1A, except that the catalyst component for preparing polyolefin prepared in comparative example 3 was used. Catalyst activity AC1And AC2Melt index MFR1And MFR2Isotacticity II1And II2The specific results are detailed in table 2.
TABLE 1
TABLE 2
As can be seen from table 2, the catalyst components for preparing polyolefin of the present invention, i.e., the diether compound represented by formula I and the glycol ester compound represented by formula II, are used together as an internal electron donor, which can achieve a synergistic effect, greatly improve the catalyst activity, greatly improve the hydrogen response sensitivity of the catalyst, and particularly maintain a high isotacticity under a high hydrogen concentration condition.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. A catalyst component for preparing polyolefin contains magnesium element, halogen, titanium element, an internal electron donor a and an internal electron donor b, wherein the internal electron donor a is a diether compound shown as a formula I, the internal electron donor b is a dihydric alcohol ester compound shown as a formula II,
in the formula I, R'1And R'2Are the same or different and are each independently selected from C1-C30Alkyl of (C)6-C30With or without substituents aryl, C7-C30With or without substituents aralkyl and C7-C30With or without substituents of alkylaryl;
in the formula I, R'3、R’4、R’5And R'6The same or different, each independently selected from hydrogen, halogen, C1-C30Alkyl of (C)6-C30With or without substituents aryl, C7-C30Tool (A)Aralkyl with or without substituents and C7-C30With or without substituents of alkylaryl;
in the formula I, n' is an integer of 1-10;
in the formula II, R1And R2Are the same or different and are each independently selected from C1-C20With or without substituents, C2-C20With or without substituents alkenyl, C6-C20With or without substituents aryl, C7-C20With or without substituents, C7-C20With or without substituents aralkyl and C10-C20With or without substituents; m is a divalent linking group.
2. The catalyst component according to claim 1, characterized in that the halogen is selected from one or more of chlorine, bromine and iodine;
preferably, R 'in formula I'1And R'2Wherein the substituents are each independently selected from halogen, C1-C10Alkyl and C1-C10One or more of alkoxy groups of (a);
preferably, R 'in formula I'1And R'2Wherein the substituents are each independently selected from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl;
preferably, R 'in formula I'3、R’4、R’5And R'6Wherein each of said substituents is independently selected from hydrogen, halogen, C1-C10Alkyl of (2)Radical and C1-C10One or more of alkoxy groups of (a);
preferably, R 'in formula I'3、R’4、R’5And R'6Wherein the substituents are each independently selected from one or more of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl;
preferably, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether and butylene glycol dibutyl ether.
3. The catalyst component according to claim 1 or 2 in which in formula II R1And R2Each independently selected from C1-C10With or without substituents, C2-C10With or without substituents alkenyl, C6-C10With or without substituents aryl, C7-C10With or without substituents, C7-C10With or without substituents aralkyl and C10-C15With or without substituents;
preferably, R in formula II1And R2Wherein the substituent is selected from the group consisting of hydroxy, halogen, cyano, nitro, amino, mono- (C)1-C6Alkyl) amino, bis- (C)1-C6Alkyl) one or more of amino, aldehyde, carboxyl and heteroatom;
preferably, in formula II, M is selected from C1-C20With or without substituentsAlkylene radical, C3-C20With or without substituents cycloalkylene and C6-C20One or more of arylene with or without substituents of (a);
preferably, in M of formula II, the substituent is C1-C20One or more of alkyl, and the substituents are optionally bonded to one or more rings;
preferably, the carbon atoms or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms;
preferably, the internal electron donor b is a diol ester compound shown in formula III,
in the formula III, R1And R2Are the same or different and are each independently selected from C1-C10With or without substituents, C2-C10With or without substituents alkenyl, C2-C10With or without substituents alkynyl, C6-C20With or without substituents aryl, C7-C20With or without substituents aralkyl and C7-C20With or without substituents of alkylaryl;
preferably, in formula III, R1And R2Each independently selected from C1-C6With or without substituents, C2-C6With or without substituents alkenyl, C2-C6With or without substituents alkynyl, C6-C10With or without substituents aryl, C7-C10With or without substituents aralkyl and C7-C10With or without substituents of alkylaryl;
preferably, R of formula III1And R2Wherein the substituents are selected from halogen and C1-C6Alkyl and C1-C6One or more of alkoxy groups of (a);
preferably, in formula III, R3、R4、R5、R6And R1-R2nThe same or different, each independently selected from hydrogen, halogen, C1-C20With or without substituents, C2-C10With or without substituents alkenyl, C2-C10With or without substituents alkynyl, C6-C20With or without substituents aryl, C7-C20With or without substituents, C7-C20With or without substituents aralkyl and C10-C20With or without substituents;
preferably, in formula III, R3、R4、R5、R6And R1-R2nEach independently selected from hydrogen, halogen, C1-C10With or without substituents, C2-C6With or without substituents alkenyl, C2-C6With or without substituents alkynyl, C6-C10With or without substituents aryl, C7-C10With or without substituents, C7-C10With or without substituents aralkyl and C10-C15With or without substituents;
preferably, R of formula III3、R4、R5、R6And R1-R2nWherein the substituents are selected from halogen and C1-C6Alkyl and C1-C6One or more of alkoxy groups of (a);
preferably, in formula III, R3、R4、R5、R6And R1-R2nOptionally containing heteroatoms selected from one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or, in formula III, R3、R4、R5、R6And R1-R2nTwo or more of them form a monocyclic ring and/or polycyclic ring; preferably, the monocyclic and/or polycyclic ring is each independently saturated or unsaturated;
preferably, in formula III, n is an integer from 0 to 10, preferably an integer from 1 to 8, more preferably an integer from 2 to 6;
preferably, in formula III, when n is 0, the substituent is R3And R4The carbon atom and substituent of (A) is R5And R6To the carbon atom of (a);
preferably, the internal electron donor b is selected from 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-o-methylbenzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-o-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2-heptanediol di (p-methylbenzoic acid) ester, and a mixture thereof, 2,2,6, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-dibenzoate, 2-phenylene dibenzoate, and mixtures thereof, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 1, 8-naphthyl di-4-n-butylbenzoate, 8-naphthyl ester, 1, 8-naphthyl bis-4-isobutylbenzoate, 1, 8-naphthyl bis-4-tert-butylbenzoate, 1, 8-naphthyl bis-4-phenylbenzoate, 1, 8-naphthyl bis-4-fluorobenzoate, 1, 8-naphthyl bis-3-fluorobenzoate, 1, 8-naphthyl bis-2-fluorobenzoate.
4. The catalyst component according to any of claims 1 to 3, characterized in that the content of magnesium element is 5-30%, preferably 8-25%, more preferably 10-22% by total weight of the catalyst component; the content of halogen is 30-80%, preferably 40-70%; the content of titanium element is 0.5-10%, preferably 1-6%; the content of the internal electron donor a is 0.5-25 wt%, preferably 1-20 wt%; the content of the internal electron donor b is 0.5 to 25%, preferably 1 to 20% by weight.
5. Process for the preparation of a catalyst component for the preparation of polyolefins according to any of claims 1 to 4, comprising the steps of:
step A: carrying out first contact on a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound and an optional internal electron donor a in a solvent to obtain a first mixture;
and B: in the presence of a precipitation assistant, carrying out second contact on the first mixture, a titanium compound and an optional internal electron donor a to obtain a second mixture;
and C: carrying out third contact on the second mixture and an internal electron donor b and an optional internal electron donor a, washing and drying;
wherein at least one of the steps A, B and C uses an internal electron donor a,
wherein the internal electron donor a is a diether compound shown as a formula I; the internal electron donor b is a dihydric alcohol ester compound shown as a formula II,
6. the method of claim 5, wherein the magnesium halide compound has the formula MgX2Wherein, X is bromine, chlorine or iodine; preferably, the magnesium halide compound is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, more preferably magnesium dichloride;
preferably, the organophosphorus compound is selected from one or more of tripentyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite; more preferably tributyl phosphate or tripentyl phosphate;
preferably, the organic epoxy compound is C2-C8One or more of the aliphatic olefin of (a), the oxidation product of a halogenated aliphatic olefin;more preferably one or more of ethylene oxide, propylene oxide, ethylene oxide chloride, epichlorohydrin, butylene oxide, butadiene dioxide, methyl glycidyl ether and diglycidyl ether; more preferably epichlorohydrin;
preferably, the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane; more preferably toluene;
preferably, the precipitation assistant is selected from one or more of organic acid, organic acid anhydride, organic ether and organic ketone; more preferably one or more of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and amyl ether; more preferably phthalic anhydride;
preferably, the titanium compound has the general formula TiXm(ORn)4-mWherein X is halogen, preferably, X is bromine, chlorine or iodine, Rn is C1-C20M is an integer of 1 to 4; preferably, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium; more preferably titanium tetrachloride.
7. The method according to claim 5 or 6, wherein the organic phosphorus compound is used in an amount of 0.1 to 5 moles, the organic epoxy compound is used in an amount of 0.2 to 10 moles, the total internal electron donor a is used in an amount of 0.0001 to 5 moles, the precipitation assistant is used in an amount of 0.025 to 1 mole, the titanium compound is used in an amount of 0.5 to 20 moles, and the internal electron donor b is used in an amount of 0.0001 to 5 moles, per mole of the magnesium halide compound;
preferably, the organic phosphorus compound is used in an amount of 0.3 to 3 moles, the organic epoxy compound is used in an amount of 0.5 to 4 moles, the total amount of the internal electron donors a is 0.01 to 1 mole, the precipitation assistant is used in an amount of 0.05 to 0.5 mole, the titanium compound is used in an amount of 1 to 15 moles, and the internal electron donor b is used in an amount of 0.01 to 1 mole, per mole of the magnesium halide compound.
8. The method of any one of claims 5-7, wherein the conditions of the first contacting comprise: the temperature is 10-100 ℃, preferably 30-80 ℃, and the time is 0.05-6 hours, preferably 0.1-2 hours;
preferably, the conditions of the second contacting include: -30 to 60 ℃, preferably-30 to 20 ℃, for 0.1 to 5 hours, preferably 0.2 to 4 hours;
preferably, the conditions of the third contacting include: the temperature is 30-200 ℃, preferably 60-120 ℃, and the time is 0.5-8 hours, preferably 1-6 hours;
preferably, in step C, after the third contacting and before the drying, the method further comprises: filtration and washing were carried out.
9. An olefin polymerization catalyst comprising the following components:
(1) the catalyst component for producing a polyolefin according to any one of claims 1 to 4 and/or the catalyst component for producing a polyolefin obtained by the production method according to any one of claims 5 to 8; (2) an alkyl aluminum compound; and (3) optionally an external electron donor compound.
10. Use of the olefin polymerization catalyst of claim 9 in olefin polymerization reactions;
preferably, the reaction is a homopolymerization and/or copolymerization;
preferably, the olefin comprises a compound represented by the formula CH2Olefins represented by CHR, wherein R is hydrogen, C1-C6Alkyl groups of (a); more preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene; further preferably, the olefin is selected from one or more of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene; even more preferably, the compound represented by the formula CH2The olefin represented by ═ CHR is propylene.
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| CN107129549A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN110938162A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof |
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| CN107129549A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
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