CN111072814A - Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method - Google Patents
Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method Download PDFInfo
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- CN111072814A CN111072814A CN201811224578.XA CN201811224578A CN111072814A CN 111072814 A CN111072814 A CN 111072814A CN 201811224578 A CN201811224578 A CN 201811224578A CN 111072814 A CN111072814 A CN 111072814A
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- Prior art keywords
- catalyst component
- substituted
- catalyst
- magnesium
- olefin polymerization
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- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 102
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 94
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 monocarboxylic acid ester compound Chemical class 0.000 claims abstract description 110
- 239000011777 magnesium Substances 0.000 claims abstract description 46
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 46
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000012662 bulk polymerization Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229920001384 propylene homopolymer Polymers 0.000 description 11
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical group C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical compound COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl 2-methoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- NOAIBMQZUGBONL-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)benzene Chemical compound COCC(C)(COC)C1=CC=CC=C1 NOAIBMQZUGBONL-UHFFFAOYSA-N 0.000 description 1
- HPOWOWTVWZELDK-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)cyclohexane Chemical compound COCC(C)(COC)C1CCCCC1 HPOWOWTVWZELDK-UHFFFAOYSA-N 0.000 description 1
- MEPSBRTXOHFWCF-UHFFFAOYSA-N (2-cyclohexyl-1,3-dimethoxypropan-2-yl)cyclohexane Chemical compound C1CCCCC1C(COC)(COC)C1CCCCC1 MEPSBRTXOHFWCF-UHFFFAOYSA-N 0.000 description 1
- VFIOZKTXVHLWRA-UHFFFAOYSA-N (2-ethylpiperidin-1-yl)-dimethoxy-(1,1,1-trifluoropropan-2-yl)silane Chemical compound CCC1CCCCN1[Si](OC)(OC)C(C)C(F)(F)F VFIOZKTXVHLWRA-UHFFFAOYSA-N 0.000 description 1
- CELOJHLXFPSJPH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylbenzene Chemical compound COCC(COC)C1=CC=CC=C1 CELOJHLXFPSJPH-UHFFFAOYSA-N 0.000 description 1
- NOWCPSTWMDNKTI-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylcyclohexane Chemical compound COCC(COC)C1CCCCC1 NOWCPSTWMDNKTI-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- HPFWUWXYBFOJAD-UHFFFAOYSA-N 1-chloro-4-(1,3-dimethoxypropan-2-yl)benzene Chemical compound COCC(COC)C1=CC=C(Cl)C=C1 HPFWUWXYBFOJAD-UHFFFAOYSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- ROSQVPGTZCDBOC-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C)(COC)CC(C)C ROSQVPGTZCDBOC-UHFFFAOYSA-N 0.000 description 1
- XAGXJWYEHBCLPN-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylbutane Chemical compound COCC(C)(CC)COC XAGXJWYEHBCLPN-UHFFFAOYSA-N 0.000 description 1
- SVJCEDKUVMVBKM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylpentane Chemical compound CCCC(C)(COC)COC SVJCEDKUVMVBKM-UHFFFAOYSA-N 0.000 description 1
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 1
- FDLMLTYTOFIPCK-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylpentane Chemical compound CCC(C)C(COC)COC FDLMLTYTOFIPCK-UHFFFAOYSA-N 0.000 description 1
- PPHMKLXXVBJEHR-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)hexane Chemical compound CCCCC(COC)COC PPHMKLXXVBJEHR-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006076 2-ethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 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 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FXPIHWVISVNIIK-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylheptane Chemical compound CCCC(C)C(COC)(COC)C(C)C FXPIHWVISVNIIK-UHFFFAOYSA-N 0.000 description 1
- HYNSSLXYPGIRFR-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylhexane Chemical compound CCC(C)C(COC)(COC)C(C)C HYNSSLXYPGIRFR-UHFFFAOYSA-N 0.000 description 1
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 description 1
- WAHDOBRAAIQNTA-UHFFFAOYSA-N 3,5-dimethoxypentylcyclohexane Chemical compound COCCC(OC)CCC1CCCCC1 WAHDOBRAAIQNTA-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 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 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 description 1
- CWVKCYDPJZCDMC-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)-2-methyloctane Chemical compound CCCCC(CC)CC(C)(COC)COC CWVKCYDPJZCDMC-UHFFFAOYSA-N 0.000 description 1
- VIJVFTUOJNTXCA-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)octane Chemical compound CCCCC(CC)CC(COC)COC VIJVFTUOJNTXCA-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CGGZLXFDAAGSKP-UHFFFAOYSA-N C(C)(C)C1=C(C=CC=C1)C(CCOC)OC Chemical compound C(C)(C)C1=C(C=CC=C1)C(CCOC)OC CGGZLXFDAAGSKP-UHFFFAOYSA-N 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- GTPNVKCFOPZHGG-UHFFFAOYSA-N COC(C1C2=CC=CC=C2C=2C=CC=CC1=2)OC Chemical compound COC(C1C2=CC=CC=C2C=2C=CC=CC1=2)OC GTPNVKCFOPZHGG-UHFFFAOYSA-N 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- VDZDYDLIDXQASZ-UHFFFAOYSA-N [1-cyclohexyl-3-methoxy-2-(methoxymethyl)propan-2-yl]cyclohexane Chemical compound C1CCCCC1C(COC)(COC)CC1CCCCC1 VDZDYDLIDXQASZ-UHFFFAOYSA-N 0.000 description 1
- AMDVEEKNUQSFMN-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]benzene Chemical compound COCC(COC)(C(C)C)C1=CC=CC=C1 AMDVEEKNUQSFMN-UHFFFAOYSA-N 0.000 description 1
- PQIDFVXMOZQINS-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclohexane Chemical compound COCC(COC)(C(C)C)C1CCCCC1 PQIDFVXMOZQINS-UHFFFAOYSA-N 0.000 description 1
- XMYDKOZNENQEHO-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclopentane Chemical compound COCC(COC)(C(C)C)C1CCCC1 XMYDKOZNENQEHO-UHFFFAOYSA-N 0.000 description 1
- FQRCETUIJFMCNV-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]benzene Chemical compound CCC(C)C(COC)(COC)C1=CC=CC=C1 FQRCETUIJFMCNV-UHFFFAOYSA-N 0.000 description 1
- IHLHFXVNTFWZRQ-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]cyclohexane Chemical compound CCC(C)C(COC)(COC)C1CCCCC1 IHLHFXVNTFWZRQ-UHFFFAOYSA-N 0.000 description 1
- NELZYGXHSKMGPM-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]cyclopentane Chemical compound CCC(C)C(COC)(COC)C1CCCC1 NELZYGXHSKMGPM-UHFFFAOYSA-N 0.000 description 1
- XHGYQNSJWDRDBT-UHFFFAOYSA-N [2,2-bis(methoxymethyl)-3-methylbutyl]benzene Chemical compound COCC(COC)(C(C)C)CC1=CC=CC=C1 XHGYQNSJWDRDBT-UHFFFAOYSA-N 0.000 description 1
- ZVGIBQMBZHWERX-UHFFFAOYSA-N [2-(cyclohexylmethyl)-3-methoxy-2-(methoxymethyl)propyl]cyclohexane Chemical compound C1CCCCC1CC(COC)(COC)CC1CCCCC1 ZVGIBQMBZHWERX-UHFFFAOYSA-N 0.000 description 1
- WVEZHRZEAFZJOI-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)-1-phenylpropyl]benzene Chemical compound C=1C=CC=CC=1C(C(COC)COC)C1=CC=CC=C1 WVEZHRZEAFZJOI-UHFFFAOYSA-N 0.000 description 1
- UKEUPAFEWAEVGQ-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)-2-methylpropyl]benzene Chemical compound COCC(C)(COC)CC1=CC=CC=C1 UKEUPAFEWAEVGQ-UHFFFAOYSA-N 0.000 description 1
- JXQCBJLNEGKSCN-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]benzene Chemical compound COCC(COC)CCC1=CC=CC=C1 JXQCBJLNEGKSCN-UHFFFAOYSA-N 0.000 description 1
- AWLBWJXVYGYRNY-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]cyclohexane Chemical compound COCC(COC)CCC1CCCCC1 AWLBWJXVYGYRNY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- FWCTZJNNLCYVMA-UHFFFAOYSA-L butan-1-ol;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCCO.CCCCO FWCTZJNNLCYVMA-UHFFFAOYSA-L 0.000 description 1
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- NSYCXGBGJZBZKI-UHFFFAOYSA-L dichlorotitanium;ethanol Chemical compound CCO.CCO.Cl[Ti]Cl NSYCXGBGJZBZKI-UHFFFAOYSA-L 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 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
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- REBFJHPJLSHCAF-UHFFFAOYSA-N ethyl hypochlorite;magnesium Chemical compound [Mg].CCOCl REBFJHPJLSHCAF-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VMLUVDHAXSZZSR-UHFFFAOYSA-L hexylaluminum(2+);dichloride Chemical compound CCCCCC[Al](Cl)Cl VMLUVDHAXSZZSR-UHFFFAOYSA-L 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- FLKPEMZONWLCSK-UHFFFAOYSA-N phthalic acid di-n-ethyl ester Natural products CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the field of catalysts, and relates to a catalyst component and a catalyst for olefin polymerization, application thereof and an olefin polymerization method. The catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor, wherein the internal electron donor is monocarboxylic ester and a diether compound; the amount of the monocarboxylic acid ester compound is 0.07-0.7 mole per mole of the diether compound. The catalyst component for olefin polymerization is prepared by compounding diether compounds and monocarboxylic acid ester in a specific ratio as an internal electron donor, and has high stereospecificity and hydrogen regulation sensitivity when used for olefin polymerization.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, application of the catalyst component and the catalyst, and an olefin polymerization method.
Background
In plastic processing, melt flow rate is an important index for measuring the fluidity of plastic melt, and is an important reference for selecting plastic processing materials and grades. The melt flow rate is largely dependent on the molecular weight of the polymer, with low molecular weight polymers having high melt flow rates. In order to obtain an olefin polymer having a high melt flow rate, it is generally necessary to add a large amount of hydrogen during polymerization to reduce the molecular weight of the polymer. However, the upper limit of the amount of hydrogen that can be added is limited by the pressure resistance of the polymerization reactor. The partial pressure of the olefin gas to be polymerized has to be lowered in order to add more hydrogen, in which case the productivity is lowered. In addition, the high-volume use of hydrogen also causes the obtained polypropylene to have low isotacticity, thereby causing the problem of unqualified product quality. Therefore, it is highly desirable to develop a catalyst having high hydrogen response (a small amount of hydrogen can provide a polymer having a high melt flow rate) and high stereospecificity (the polymer can maintain a high isotacticity under polymerization conditions with a large amount of hydrogen).
US4298718 and US4495338 disclose Ziegler-Natta catalysts using magnesium halides as support. The catalyst formed by the action of the carrier and titanium tetrachloride shows higher catalytic activity in catalyzing propylene polymerization, but the isotacticity of the obtained polypropylene is lower, which indicates that the stereospecific capacity of the catalyst is poorer. Then, researchers add an electron donor compound (such as ethyl benzoate or phthalate) in the preparation process of the Ziegler-Natta catalyst to form a solid titanium catalyst, and add another electron donor (an alkoxysilane compound) during olefin polymerization to obtain polypropylene with higher isotacticity during propylene polymerization catalysis, which indicates that the addition of the electron donor compound improves the stereotactic ability of the catalyst. However, the hydrogen regulation sensitivity of the catalyst is insufficient, and the direct hydrogen regulation method is difficult to produce products with high melt index. Moreover, it is found that the phthalate compound (plasticizer) can cause serious damage to the growth and development of animals and reproductive systems, and simultaneously, the phthalate compound can also have similar influence on human beings.
CN1580034A, CN1580035A, CN1580033A, CN1436766A and CN1552740A disclose that glycol ester compounds are used as electron donors of Ziegler-Natta catalysts for propylene polymerization, which are characterized by wider molecular weight distribution and higher polymerization activity, but when a spherical catalyst containing carboxylic glycol ester internal electron donor is used for propylene polymerization, the stereotactic ability is poorer, and the isotacticity of the obtained polypropylene is lower.
Therefore, it is urgently required to develop a catalyst having high hydrogen response and high stereospecificity and containing no phthalate compound (plasticizer).
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component and use thereof, and a process for olefin polymerization. The catalyst component has high hydrogen regulation sensitivity and stereospecificity, and does not contain phthalate compounds (plasticizers).
During the research process, the inventor of the present invention unexpectedly found that when the internal electron donor only contains a monocarboxylic acid ester compound and a diether compound, and when the molar ratio of the monocarboxylic acid ester compound to the diether compound is 0.07-0.7: 1, preferably 0.15 to 0.35: 1, the two internal electron donors can be perfectly matched, so that the hydrogen response and the stereospecificity of the catalyst are more effectively improved.
Based on the above, the first aspect of the present invention provides a catalyst component for olefin polymerization, which contains a product obtained by reacting a magnesium source, a titanium source and an internal electron donor, wherein the internal electron donor is monocarboxylic ester and a diether compound represented by formula I; the dosage of the monocarboxylic ester compound is 0.07-0.7 mol per mol of the diether compound;
the monocarboxylic acid ester compound is a monocarboxylic aromatic carboxylic acid ester and/or a monocarboxylic aliphatic carboxylic acid ester;
in the formula I, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is one of substituted or unsubstituted alkaryl groups.
A second aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:
(i) the catalyst component is the catalyst component for olefin polymerization provided by the invention;
(ii) at least one alkyl aluminum compound; and
(iii) optionally an external electron donor.
In a third aspect the present invention provides the use of a catalyst as described above for the polymerisation of olefins in an olefin polymerisation reaction.
A fourth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions.
The catalyst component for olefin polymerization is prepared by compounding diether compounds and monocarboxylic acid esters in a specific ratio as internal electron donors, and has high stereospecificity and hydrogen regulation sensitivity when used for olefin polymerization, and the obtained polyolefin product has high isotactic index and melt flow index.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Based on the above, the first aspect of the present invention provides a catalyst component for olefin polymerization, which contains a product obtained by reacting a magnesium source, a titanium source and an internal electron donor, wherein the internal electron donor is monocarboxylic ester and a diether compound represented by formula I; the dosage of the monocarboxylic ester compound is 0.07-0.7 mol per mol of the diether compound;
the monocarboxylic acid ester compound is a monocarboxylic aromatic carboxylic acid ester and/or a monocarboxylic aliphatic carboxylic acid ester;
in the formula I, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is one of substituted or unsubstituted alkaryl groups.
In the present invention, C1-C20Examples of the linear or branched alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecylAlkyl, n-octadecyl, n-nonadecyl and n-eicosyl.
In the present invention, C2-C20Examples of the linear or branched alkenyl groups of (a) may include, but are not limited to: vinyl, allyl, isopropenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, phenylvinyl, phenyl-n-butenyl, geranyl, 1-decenyl, 1-tetradecenyl, 1-octadecenyl, 9-octadecenyl, 1-eicosenyl, 1-octadecenyl, 3,7,11, 15-tetramethyl-1-hexadecenyl.
In the present invention, C3-C20Examples of the substituted or unsubstituted cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, cyclododecyl.
In the present invention, C6-C20The substituted or unsubstituted aryl group of (1) includes C6-C20Substituted or unsubstituted phenyl of, also including C10-C20Examples of the substituted or unsubstituted fused ring aryl group of (a) may include, but are not limited to: phenyl, halogen substituted phenyl, alkoxy substituted phenyl, naphthyl, methyl naphthyl, ethyl naphthyl, anthryl, methyl anthryl, ethyl anthryl, phenanthryl, methyl phenanthryl and ethyl phenanthryl, pyrenyl, indenyl.
In the present invention, C7-C20The substituted or unsubstituted aralkyl group of (2) means an alkyl group having an aryl substituent and having 7 to 20 carbon atoms. C7-C20Examples of the substituted or unsubstituted aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl-isopropyl, phenyl-n-pentyl.
In the present invention, C7-C20Is a substituted or unsubstituted alkylaryl groupRefers to an aryl group having an alkyl substituent having 7 to 20 carbon atoms. C7-C20Examples of substituted or unsubstituted alkaryl groups of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl, isopropylphenyl and n-pentylphenyl.
In the present invention, the above-mentioned groups in other carbon number ranges can be selected correspondingly within the carbon number range defined, and are not described in detail herein.
In the present invention, the aliphatic monocarboxylic acid ester is preferably a monoester comprising an aliphatic monocarboxylic acid having 2 to 10 carbon atoms and a monohydric or polyhydric aliphatic alcohol having 1 to 15 carbon atoms or an aromatic alcohol having 6 to 15 carbon atoms; the monobasic aromatic carboxylic ester is formed by monobasic aromatic carboxylic acid with 7-10 carbon atoms and monobasic or polybasic aliphatic alcohol with 1-15 carbon atoms or aromatic alcohol with 6-15 carbon atoms. The aliphatic monocarboxylic acid and the aromatic monocarboxylic acid may optionally have a substituent, and the substituent may be a hydroxyl group and/or an alkoxy group.
More preferably, the monocarboxylic acid ester compound is a monovalent aromatic carboxylic acid ester, and the monovalent aromatic carboxylic acid ester is particularly preferably at least one of benzoate, orthohydroxybenzoate, orthomethoxybenzoate, and orthoethoxybenzoate.
According to the invention, the diether compound is preferably a 1, 3-diether compound shown in formula II,
in the formula II, R9' and R10' same or different, each independently hydrogen, halogen, C1-C18Straight or branched alkyl of (2), C3-C18Substituted or unsubstituted cycloalkyl of (A), C6-C18Substituted or unsubstituted aryl of (1), C7-C18Substituted or unsubstituted aralkyl and C7-C18Substituted or not substitutedOne of the substituted alkaryl radicals, or, R9' and R10' bonding to each other to form a ring; r11' and R12' same or different, each independently C1-C10Linear or branched alkyl.
According to the present invention, examples of the diether-based compound may include, but are not limited to: 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-isopropylphenyl-1, 3-dimethoxypropane, 2-isopropyl, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-methyl, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene.
Most preferably, the internal electron donor compound b is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
In the present invention, the 1, 3-diether compound can be synthesized by the methods disclosed in CN1020448C, CN100348624C and CN 1141285A. The disclosure of which is incorporated herein by reference in its entirety. This is not described in detail herein.
The inventor of the present invention has found that, when the molar ratio of the monocarboxylic acid ester compound to the diether compound is preferably 0.15 to 0.35: 1, the two can be better blended cooperatively, so that the catalyst with higher hydrogen regulation sensitivity and stereotactic ability is obtained.
The catalyst component of the invention can be prepared by the following method: the method comprises the steps of carrying out contact reaction on a magnesium source and a titanium source, and adding an internal electron donor in one or more time periods before, during and after the contact reaction of the magnesium source and the titanium source, wherein the internal electron donor is a monocarboxylic acid ester compound and a diether compound. Preferably, the catalyst component is prepared by the following method: contacting a low-temperature titanium source with a magnesium compound carrier, then heating to a reaction temperature for reaction, and adding the internal electron donor in one or more time periods before, during and after the contact reaction of the magnesium compound carrier and the titanium source. When the catalyst component obtained by the preparation method is used for olefin polymerization reaction, particularly propylene polymerization reaction, the obtained polymer with high melt index simultaneously has high isotactic index.
Specifically, the reaction of the magnesium source with the titanium source may be carried out in the same manner as in the prior art, for example, the titanium source may be cooled to 0 ℃ or less (preferably-5 ℃ to-25 ℃), then the magnesium source may be added and mixed with stirring at that temperature for 10 to 60 minutes, followed by warming to the reaction temperature (i.e., about 60 to 130 ℃) and maintaining at that reaction temperature for 0.5 to 10 hours. In the preparation method of the catalyst component for olefin polymerization, the internal electron donor is added in one or more time periods before, during and after the reaction of the magnesium source and the titanium source. The time period before the reaction of the magnesium source with the titanium source refers to a time period after the magnesium source is added to the reactor and before the temperature is raised to the reaction temperature.
In the present invention, the magnesium source may be various magnesium-containing compounds that can be used in catalysts for olefin polymerization, for example, the magnesium source may be magnesium halide, alcoholate of magnesium, or haloalcoholate and magnesium halide adduct support, and the like; the magnesium halide may be, for example, magnesium chloride and/or magnesium bromide; the alcoholate of magnesium may be, for example, diethoxymagnesium; the haloalcoholate of magnesium may be, for example, magnesium ethoxychloride; the types of the magnesium halide adduct carrier are well known to those skilled in the art, for example, the magnesium halide adduct carriers disclosed in CN1091748A, CN101050245A, CN101486722A, 201110142357.X, 201110142156.X and 201110142024.7, etc., and the relevant contents of the disclosures of these patents are incorporated into the present invention by reference in their entirety.
In the present invention, the magnesium source is preferably a magnesium halide adduct carrier. A specific method of preparing the magnesium halide adduct carrier may include the steps of: mixing the components for forming the magnesium halide adduct, heating to react to generate magnesium halide adduct melt, wherein the reaction temperature is 90-140 ℃, putting the magnesium halide adduct melt into a cooling medium after high shear action in a dispersion medium to form spherical magnesium halide adduct particles, washing and drying to obtain a spherical carrier, and optionally adding an internal electron donor during or after the process. The high shear may be achieved by conventional means such as high speed stirring (eg CN1330086), spraying (eg US6020279) and high gravity rotating beds (eg CN1580136A) and emulsifying machine (CN 1463990A). The dispersion medium may be, for example, a hydrocarbon-based inert solvent such as one or more of kerosene, white oil, silicone oil, paraffin oil, vaseline oil, and the like. The cooling medium may be selected from one or more of pentane, hexane, heptane, petroleum ether, raffinate oil, etc., for example.
According to the invention, the titanium source may be conventional in the artAlternatively, for example, the titanium source may be of the formula Ti (OR')3-aZaand/OR Ti (OR')4-bZbWherein R' is C1-C20Z is F, Cl, Br or I, a is an integer of 1 to 3, and b is an integer of 1 to 4. Preferably, the titanium source is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride, ethoxy titanium trichloride, and titanium trichloride.
The contents of magnesium, titanium and an internal electron donor in the catalyst component are not particularly limited, and may be any value in the catalyst component conventional in the art, and preferably, the content of the magnesium element is 2 to 15 parts by weight, preferably 3 to 12 parts by weight, and more preferably 4 to 10 parts by weight, per part by weight of the titanium element; the content of the internal electron donor is 2 to 10 parts by weight, preferably 3 to 8 parts by weight, and more preferably 4 to 7 parts by weight.
According to the present invention, in the preparation process of the catalyst component for olefin polymerization, preferably, the molar ratio of the magnesium source calculated as magnesium element, the titanium source calculated as titanium element and the internal electron donor is 1: 20-150: 0.1-0.9, more preferably 1: 30-120: 0.15-0.6.
The present invention also provides a catalyst for olefin polymerization, the catalyst comprising:
(i) the catalyst component is the catalyst component for olefin polymerization provided by the invention;
(ii) at least one alkyl aluminum compound; and
(iii) optionally an external electron donor.
In the catalyst for olefin polymerization, the aluminum alkyl compound may be various aluminum alkyl compounds conventionally used in the art, for example, the aluminum alkyl may have a general formula of AlR16R16′R16", wherein R16、R16' and R16Each independently is C1-C8And one or two radicals thereofThe group can be halogen, and hydrogen on the alkyl can also be replaced by halogen; said C is1-C8Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl and the halogen may be fluorine, chlorine, bromine, iodine. In particular, the alkyl aluminium compound may be chosen, for example, from one or more of triethylaluminium, triisobutylaluminium, tri-n-butylaluminium, tri-n-hexylaluminium, diethylaluminium monochloride, diisobutylaluminium monochloride, di-n-butylaluminium monochloride, di-n-hexylaluminium monochloride, ethylaluminium dichloride, isobutylaluminium dichloride, n-butylaluminium dichloride and n-hexylaluminium dichloride.
In the catalyst for olefin polymerization, the external electron donor may be various external electron donors commonly used in the art, and for example, the external electron donor may be selected from carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organic phosphorus compounds, and organic silicon compounds. Preferably, the external electron donor contains at least one Si-OR bond and has the general formula (R)17)x(R18)ySi(OR19)zWherein R is17、R18And R19Is C1-C18X and y are each independently an integer from 0 to 2, z is an integer from 1 to 3, and the sum of x, y and z is 4. Preferably, R17、R18Is C3-C10Alkyl, cycloalkyl, optionally containing heteroatoms; r19Is C1-C10Optionally containing heteroatoms. Specifically, the external electron donor may be selected from, for example, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.
Further, in general, in the catalyst for olefin polymerization, the molar ratio of the catalyst component for olefin polymerization in terms of titanium element to the amount of aluminum alkyl in terms of aluminum element may be 1: 1-2000, preferably 1: 20-500; the molar ratio of the external electron donor to the amount of aluminum alkyl compound used, calculated as aluminum element, may be 1: 2-200, preferably 1: 2.5-100.
According to the present invention, in the preparation process of the catalyst for olefin polymerization, the alkylaluminum and the optional external electron donor may be mixed with the catalyst component for olefin polymerization and then reacted, or the alkylaluminum and the optional external electron donor may be mixed in advance and then mixed with the catalyst component for olefin polymerization and reacted.
According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor may be added into the polymerization reactor separately, or may be added into the polymerization reactor after mixing, or may be added into the polymerization reactor after olefin prepolymerization by a prepolymerization method known in the art.
The invention also provides the application of the catalyst for olefin polymerization in olefin polymerization reaction.
The invention specifically provides an olefin polymerization method, which comprises the following steps: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions.
The improvement of the present invention is that a new catalyst for olefin polymerization is used, and the specific kind of olefin, the polymerization reaction method and conditions of olefin can be the same as those in the prior art.
According to the invention, the above-mentioned catalysts are particularly suitable for use with catalysts of the formula CH2CHR (wherein R is hydrogen, C)1-C6Alkyl or C6-C12Aryl) of (a) a (b) an olefin.
According to the present invention, the polymerization of the olefin can be carried out according to the existing methods, specifically, under the protection of inert gas, in a liquid phase monomer or an inert solvent containing a polymeric monomer, or in a gas phase, or by a combined polymerization process in a gas-liquid phase. The polymerization temperature may be generally 0 to 150 ℃ and preferably 60 to 90 ℃. The pressure of the polymerization reaction may be normal pressure or higher; for example, it may be in the range of 0.01 to 10MPa, preferably 0.01 to 5MPa, and more preferably 0.1 to 4 MPa. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen may be added to the reaction system as a polymer molecular weight regulator to regulate the molecular weight and melt index of the polymer. In addition, the kinds and amounts of the inert gas and the solvent are well known to those skilled in the art during the polymerization of olefins, and will not be described herein.
The invention is further illustrated by the following examples.
In the following examples and comparative examples:
(1) polymer melt index: measured according to the method of GB 3682-2000.
(2) Polymer isotactic index: the determination is carried out by adopting a heptane extraction method (boiling extraction for 6 hours by heptane), namely, a 2g dried polymer sample is taken and placed in an extractor to be extracted for 6 hours by boiling heptane, then, the residue is dried to constant weight, and the ratio of the weight (g) of the obtained polymer to 2 is the isotactic index.
Example 1
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
(1) Preparation of the catalyst component
In a 300ml glass reaction flask, 90ml (820mmol) of titanium tetrachloride was charged and cooled to-20 ℃, 37mmol of magnesium halide support (prepared as disclosed in example 1 of CN 1330086A) as magnesium element was added thereto, then the temperature was raised to 110 ℃, and during the raising of the temperature, 0.6mmol of ethyl o-ethoxybenzoate and 8.5mmol of 9, 9-dimethoxymethylfluorene were added, the liquid was filtered after maintaining at 110 ℃ for 30min, washed 2 times with titanium tetrachloride, 5 times with hexane, and dried under vacuum to obtain catalyst component Cat-1 for olefin polymerization.
(2) Liquid phase bulk polymerization of propylene
The liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. To the reaction vessel were added 1ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 0.1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1mmol/ml) and 8mg of the above catalyst component Cat-1 for olefin polymerization in this order under a nitrogen blanket. The autoclave was closed and 6.5L of hydrogen (normal volume) and 2.3L of liquid propylene were added. Heating to 70 ℃, reacting for 1 hour, cooling, releasing pressure and discharging. The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Example 2
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that the amounts of ethyl benzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane charged during the temperature increase were 3.5mmol and 5mmol, respectively, to obtain a catalyst component Cat-2 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Example 3
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that the amounts of ethyl o-ethoxybenzoate (2 mmol) and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (7 mmol) added during the temperature increase were changed to obtain catalyst component Cat-3 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Example 4
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that 1.5mmol of ethyl o-ethoxybenzoate and 10mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase to obtain a catalyst component Cat-4 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Example 5
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in accordance with the procedure of example 1, except that 2.5mmol of ethyl o-ethoxybenzoate and 7.1mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase to obtain catalyst component Cat-5 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 1
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that 0.3mmol of ethyl o-ethoxybenzoate and 8.5mmol of 9, 9-dimethoxymethylfluorene were added during the preparation of the catalyst component to give a catalyst component DCat-1 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 2
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 2, except that, in the preparation of the catalyst component, the ethyl benzoate was replaced with the same parts by weight of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to give a catalyst component DCat-2 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 3
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in accordance with the procedure of example 3, except that, in the preparation of the catalyst component, the 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was replaced with the same parts by weight of ethyl o-methoxybenzoate to give a catalyst component DCat-3 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 4
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 3, except that ethyl o-ethoxybenzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added in amounts of 5mmol and 5mmol, respectively, during the preparation of the catalyst component, to give a catalyst component DCat-4 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 5
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
Liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that the catalyst component Cat-1 was replaced with the same parts by weight of a DQ catalyst component (hereinafter referred to as DCat-5, the internal electron donor being diisobutylphthalate) commercially available from Odada catalyst division, petrochemical, China.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 6
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A liquid bulk polymerization of propylene was carried out as in example 1, except that the internal electron donor contained 0.8mmol of 2, 4-pentanediol dibenzoate. To obtain the catalyst component DCat-6 for olefin polymerization.
The resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
TABLE 1
As can be seen from the results of the examples and comparative examples in Table 1, when the internal electron donor contains both the monocarboxylic acid ester compound and the diether compound, and the molar ratio of the monocarboxylic acid ester compound to the diether compound in the catalyst component is 0.07-0.7: 1, in particular between 0.15 and 0.35: 1, the prepared polypropylene has high isotactic index at high melt index, namely, the polypropylene can have high isotactic index and high melt index at the same time. The catalyst without the phthalate ester compound (plasticizer) has the characteristics of high stereospecificity and high hydrogen regulation sensitivity.
As can be seen from the results of example 1 and comparative example 6 in Table 1, the catalysts of the prior art containing glycol ester compounds, monocarboxylic acid ester compounds and diether compounds as internal electron donors have lower hydrogen response and lower melt index of the obtained polymer under the same polymerization conditions compared with the catalyst of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A catalyst component for olefin polymerization contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor, wherein the internal electron donor is monocarboxylic ester and a diether compound shown as a formula I; the dosage of the monocarboxylic ester compound is 0.07-0.7 mol per mol of the diether compound;
the monocarboxylic acid ester compound is a monocarboxylic aromatic carboxylic acid ester and/or a monocarboxylic aliphatic carboxylic acid ester;
in the formula I, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is one of substituted or unsubstituted alkaryl groups.
2. The catalyst component according to claim 1 in which the monoaliphatic carboxylic acid ester is a monoaliphatic ester formed from a monoaliphatic carboxylic acid having from 2 to 10 carbon atoms and a monohydric or polyhydric aliphatic alcohol having from 1 to 15 carbon atoms or an aromatic alcohol having from 6 to 15 carbon atoms;
the monobasic aromatic carboxylic ester is formed by monobasic aromatic carboxylic acid with 7-10 carbon atoms and monobasic or polybasic aliphatic alcohol with 1-15 carbon atoms or aromatic alcohol with 6-15 carbon atoms.
3. The catalyst component according to claim 1 in which the diether-based compound is a 1, 3-diether-based compound of formula II,
in the formula II, R9' and R10' same or different, each independently hydrogen, halogen, C1-C18Straight or branched alkyl of (2), C3-C18Substituted or unsubstituted cycloalkyl of (A), C6-C18Substituted or unsubstituted aryl of (1), C7-C18Substituted or unsubstituted aralkyl and C7-C18Or one of the substituted or unsubstituted alkylaryl groups of (A), or R9' and R10' bonding to each other to form a ring; r11' and R12' same or different, each independently C1-C10Linear or branched alkyl.
4. The catalyst component according to claim 1 in which the monocarboxylic acid ester compound is used in an amount of 0.15 to 0.35 mole per mole of the diether compound.
5. The catalyst component according to claim 1 in which the magnesium source is at least one of a magnesium halide, an alcoholate or haloalcoholate of magnesium and a magnesium halide adduct, preferably the magnesium source is a magnesium halide adduct support; the titanium source is Ti (OR')3-aZaand/OR Ti (OR')4-bZbWherein R' is C1-C20Z is F, Cl, Br or I, a is an integer of 1 to 3, and b is an integer of 1 to 4.
6. The catalyst component according to claim 1, wherein the weight ratio of titanium in terms of titanium element, magnesium in terms of magnesium element, halogen in terms of halogen element and internal electron donor in the catalyst component is 1: 2-15: 8-30: 2-10; preferably 1: 3-12: 10-25: 3-8.
7. The catalyst component according to any of claims 1 to 6, wherein the catalyst component is prepared by a process comprising: and carrying out contact reaction on a magnesium source and a titanium source, and adding the internal electron donor in one or more time periods before, during and after the contact reaction of the magnesium source and the titanium source.
8. The catalyst component according to claim 7, wherein the catalyst component is prepared by: contacting a low-temperature titanium source with a magnesium compound carrier, then heating to a reaction temperature for reaction, and adding the internal electron donor in one or more time periods before, during and after the contact reaction of the magnesium compound carrier and the titanium source.
9. A catalyst for the polymerization of olefins, the catalyst comprising:
(1) the catalyst component of any one of claims 1 to 8;
(2) at least one alkyl aluminum compound; and
(3) optionally an external electron donor compound.
10. Use of the catalyst of claim 9 in olefin polymerization reactions.
11. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of claim 9 under olefin polymerization conditions.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811224578.XA CN111072814A (en) | 2018-10-19 | 2018-10-19 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| EP19874270.2A EP3868796B1 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| FIEP19874270.2T FI3868796T3 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| PCT/CN2019/111252 WO2020078352A1 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| BR112021006289-0A BR112021006289B1 (en) | 2018-10-19 | 2019-10-15 | CATALYST COMPONENT AND CATALYST FOR OLEFIN POLYMERIZATION, ITS USE AND METHOD FOR OLEFIN POLYMERIZATION |
| SG11202103779QA SG11202103779QA (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| ES19874270T ES2986988T3 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| PT198742702T PT3868796T (en) | 2018-10-19 | 2019-10-15 | CATALYST COMPONENT AND CATALYST FOR OLEFIN POLYMERIZATION AND THEIR APPLICATION |
| MYPI2021001946A MY209414A (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| US17/286,776 US11970510B2 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| KR1020217015086A KR102868882B1 (en) | 2018-10-19 | 2019-10-15 | Catalyst components for olefin polymerization, catalysts and uses thereof |
| JP2021520594A JP7479361B2 (en) | 2018-10-19 | 2019-10-15 | Olefin polymerization catalyst components, catalysts and their applications |
| TW108137362A TWI851609B (en) | 2018-10-19 | 2019-10-17 | Catalyst components for olefin polymerization, catalysts and their applications |
| SA521421681A SA521421681B1 (en) | 2018-10-19 | 2021-04-07 | Catalyst component and catalyst for olefin polymerization, and application thereof |
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| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1268957A (en) * | 1998-05-06 | 2000-10-04 | 蒙特尔技术有限公司 | Catalyst components for the polymerization of olefins |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst components for olefin polymerization, catalysts and catalyst applications thereof |
| CN104250316A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method |
| CN104558284A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application |
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| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1268957A (en) * | 1998-05-06 | 2000-10-04 | 蒙特尔技术有限公司 | Catalyst components for the polymerization of olefins |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst components for olefin polymerization, catalysts and catalyst applications thereof |
| CN104250316A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method |
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