CN116375911A - Catalyst for olefin polymerization, preparation method thereof and olefin polymerization method - Google Patents
Catalyst for olefin polymerization, preparation method thereof and olefin polymerization method Download PDFInfo
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- CN116375911A CN116375911A CN202310599016.8A CN202310599016A CN116375911A CN 116375911 A CN116375911 A CN 116375911A CN 202310599016 A CN202310599016 A CN 202310599016A CN 116375911 A CN116375911 A CN 116375911A
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- electron donor
- internal electron
- catalyst
- substituted
- unsubstituted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 44
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 23
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 7
- -1 succinic acid diester compound Chemical group 0.000 claims description 82
- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 54
- 229910052736 halogen Inorganic materials 0.000 claims description 36
- 150000002367 halogens Chemical group 0.000 claims description 36
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 34
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 34
- 125000005842 heteroatom Chemical group 0.000 claims description 33
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 27
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 18
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 235000011147 magnesium chloride Nutrition 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 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 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims 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 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000001384 succinic acid Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 6
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 5
- GFQUHXOKHFFPGI-UHFFFAOYSA-N CCC(CC)COC(=O)CCC(O)=O Chemical compound CCC(CC)COC(=O)CCC(O)=O GFQUHXOKHFFPGI-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- WGFNXLQURMLAGC-UHFFFAOYSA-N diethyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCC WGFNXLQURMLAGC-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 claims description 4
- YCYHZGIPKZHEEL-UHFFFAOYSA-N diethyl 2,3-bis(2,2-dimethylpropyl)butanedioate Chemical compound CCOC(=O)C(CC(C)(C)C)C(CC(C)(C)C)C(=O)OCC YCYHZGIPKZHEEL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 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 claims description 4
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 3
- HZXMLBSUEZTYHZ-UHFFFAOYSA-N 4-(cyclohexylmethoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCC1CCCCC1 HZXMLBSUEZTYHZ-UHFFFAOYSA-N 0.000 claims description 3
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- WNVMVIYFKFGESM-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-di(propan-2-yl)butanedioate Chemical compound CC(C)COC(=O)C(C(C)C)C(C(C)C)C(=O)OCC(C)C WNVMVIYFKFGESM-UHFFFAOYSA-N 0.000 claims description 3
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 claims description 3
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 claims description 3
- AVLHXEDOBYYTGV-UHFFFAOYSA-N diethyl 2,3-bis(2-methylpropyl)butanedioate Chemical compound CCOC(=O)C(CC(C)C)C(CC(C)C)C(=O)OCC AVLHXEDOBYYTGV-UHFFFAOYSA-N 0.000 claims description 3
- ISOWAXIPBFLPIC-UHFFFAOYSA-N diethyl 2,3-dicyclopentylbutanedioate Chemical compound C1CCCC1C(C(=O)OCC)C(C(=O)OCC)C1CCCC1 ISOWAXIPBFLPIC-UHFFFAOYSA-N 0.000 claims description 3
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 3
- ZGTWXDWFHBVRFP-UHFFFAOYSA-M magnesium propan-1-olate iodide Chemical compound CCCO[Mg]I ZGTWXDWFHBVRFP-UHFFFAOYSA-M 0.000 claims description 3
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 claims description 3
- MBTRTTIWMFMDQR-UHFFFAOYSA-M magnesium;butan-1-olate;bromide Chemical compound [Br-].CCCCO[Mg+] MBTRTTIWMFMDQR-UHFFFAOYSA-M 0.000 claims description 3
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 claims description 3
- FNZJIOZSENAPJJ-UHFFFAOYSA-M magnesium;butan-1-olate;iodide Chemical compound [Mg+2].[I-].CCCC[O-] FNZJIOZSENAPJJ-UHFFFAOYSA-M 0.000 claims description 3
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 3
- SWMSUKCRKOWDGN-UHFFFAOYSA-M magnesium;ethanolate;bromide Chemical compound [Br-].CCO[Mg+] SWMSUKCRKOWDGN-UHFFFAOYSA-M 0.000 claims description 3
- BVMVBWXWNFWCLX-UHFFFAOYSA-M magnesium;ethanolate;iodide Chemical compound [I-].CCO[Mg+] BVMVBWXWNFWCLX-UHFFFAOYSA-M 0.000 claims description 3
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 3
- WIMVJXDEZAGHEM-UHFFFAOYSA-M magnesium;methanolate;bromide Chemical compound [Br-].CO[Mg+] WIMVJXDEZAGHEM-UHFFFAOYSA-M 0.000 claims description 3
- ZHLDMBMNKCIBQN-UHFFFAOYSA-M magnesium;methanolate;chloride Chemical compound [Cl-].CO[Mg+] ZHLDMBMNKCIBQN-UHFFFAOYSA-M 0.000 claims description 3
- HTJCTGUUGHHFRJ-UHFFFAOYSA-M magnesium;methanolate;iodide Chemical compound [Mg+2].[I-].[O-]C HTJCTGUUGHHFRJ-UHFFFAOYSA-M 0.000 claims description 3
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 claims description 3
- CGCFXQQNVNZPKC-UHFFFAOYSA-M magnesium;propan-1-olate;bromide Chemical compound [Br-].CCCO[Mg+] CGCFXQQNVNZPKC-UHFFFAOYSA-M 0.000 claims description 3
- UYICAKKJLNIPRK-UHFFFAOYSA-M magnesium;propan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCC[O-] UYICAKKJLNIPRK-UHFFFAOYSA-M 0.000 claims description 3
- DQZLQYHGCKLKGU-UHFFFAOYSA-N magnesium;propane Chemical compound [Mg+2].C[CH-]C.C[CH-]C DQZLQYHGCKLKGU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 3
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- CXKANZAMPQTLBJ-UHFFFAOYSA-N diethyl 2,3-dicyclohexylbutanedioate Chemical compound C1CCCCC1C(C(=O)OCC)C(C(=O)OCC)C1CCCCC1 CXKANZAMPQTLBJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000037048 polymerization activity Effects 0.000 abstract description 18
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 206010070834 Sensitisation Diseases 0.000 abstract 1
- 230000008313 sensitization Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- 230000000694 effects Effects 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 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 6
- 238000012360 testing method Methods 0.000 description 6
- VTCHFSNTCCVHRC-UHFFFAOYSA-N dibutyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCCCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCCCC VTCHFSNTCCVHRC-UHFFFAOYSA-N 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VSRWWHOJVGFSFA-UHFFFAOYSA-N (3-benzoyloxy-2-ethylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CC)COC(=O)C1=CC=CC=C1 VSRWWHOJVGFSFA-UHFFFAOYSA-N 0.000 description 3
- VQKYNXVAUAQAPS-UHFFFAOYSA-N (3-benzoyloxy-2-methylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)C(CC)OC(=O)C1=CC=CC=C1 VQKYNXVAUAQAPS-UHFFFAOYSA-N 0.000 description 3
- YEGVZUITMUKKBN-UHFFFAOYSA-N 2-(1-benzoyloxypropyl)hexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CCCC)COC(=O)C1=CC=CC=C1 YEGVZUITMUKKBN-UHFFFAOYSA-N 0.000 description 3
- 239000002879 Lewis base Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- URYLLQVLNOEEBA-UHFFFAOYSA-N [2-benzyl-3-methoxy-2-(methoxymethyl)propyl]benzene Chemical compound C=1C=CC=CC=1CC(COC)(COC)CC1=CC=CC=C1 URYLLQVLNOEEBA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QFESMHZEKSRNQO-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-ditert-butylbutanedioate Chemical compound CC(C)COC(=O)C(C(C)(C)C)C(C(C)(C)C)C(=O)OCC(C)C QFESMHZEKSRNQO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- KRTCPMDBLDWJQY-UHFFFAOYSA-M magnesium;ethanolate;chloride Chemical compound [Mg+2].[Cl-].CC[O-] KRTCPMDBLDWJQY-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 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 2
- 239000002245 particle Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010792 warming Methods 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
- HJCICGUHPWKGOL-UHFFFAOYSA-N (3-benzoyloxy-2-propylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CCC)COC(=O)C1=CC=CC=C1 HJCICGUHPWKGOL-UHFFFAOYSA-N 0.000 description 1
- LESIHUNAOSLPSU-UHFFFAOYSA-N (4-benzoyloxy-3-ethylpentan-2-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(CC)C(C)OC(=O)C1=CC=CC=C1 LESIHUNAOSLPSU-UHFFFAOYSA-N 0.000 description 1
- AXUIEEPFBMGZLS-UHFFFAOYSA-N (4-benzoyloxy-3-methylpentan-2-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(C)C(C)OC(=O)C1=CC=CC=C1 AXUIEEPFBMGZLS-UHFFFAOYSA-N 0.000 description 1
- ZHWDRENUJNGBCD-UHFFFAOYSA-N (6-benzoyloxy-3,5-dimethylheptan-2-yl) benzoate Chemical compound CC(CC(C)C(C)OC(=O)C1=CC=CC=C1)C(C)OC(=O)C2=CC=CC=C2 ZHWDRENUJNGBCD-UHFFFAOYSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- LNPGJLLHLZSLBC-UHFFFAOYSA-N 1,1-dimethoxy-2,4-dimethylpentane Chemical compound COC(OC)C(C)CC(C)C LNPGJLLHLZSLBC-UHFFFAOYSA-N 0.000 description 1
- RBQKFOAICHOKKU-UHFFFAOYSA-N 1,1-dimethoxy-2-methylpentane Chemical compound CCCC(C)C(OC)OC RBQKFOAICHOKKU-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-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
- 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 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
- 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
- FJZBADSJNSFVDO-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C(C)C)(C(C)C)COC FJZBADSJNSFVDO-UHFFFAOYSA-N 0.000 description 1
- SKWKIEFIPVHTHJ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)pentane Chemical compound COCC(CC)(CC)COC SKWKIEFIPVHTHJ-UHFFFAOYSA-N 0.000 description 1
- WAHDOBRAAIQNTA-UHFFFAOYSA-N 3,5-dimethoxypentylcyclohexane Chemical compound COCCC(OC)CCC1CCCCC1 WAHDOBRAAIQNTA-UHFFFAOYSA-N 0.000 description 1
- MHXGFZFAFFHXGF-UHFFFAOYSA-N 3-(1-benzoyloxyethyl)heptan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(CCCC)C(C)OC(=O)C1=CC=CC=C1 MHXGFZFAFFHXGF-UHFFFAOYSA-N 0.000 description 1
- RLPHPVUQNDTZEO-UHFFFAOYSA-N 3-(1-benzoyloxyethyl)hexan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(CCC)C(C)OC(=O)C1=CC=CC=C1 RLPHPVUQNDTZEO-UHFFFAOYSA-N 0.000 description 1
- PNCLVYKEOAAKCK-UHFFFAOYSA-N 3-(dimethoxymethyl)heptane Chemical compound CCCCC(CC)C(OC)OC PNCLVYKEOAAKCK-UHFFFAOYSA-N 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
- LZKBOCQYEOVUNZ-UHFFFAOYSA-N 4,4-dimethoxybutylbenzene Chemical compound COC(OC)CCCC1=CC=CC=C1 LZKBOCQYEOVUNZ-UHFFFAOYSA-N 0.000 description 1
- JHPBGTKLJMOWGK-UHFFFAOYSA-N C1(=CC=CC=C1)C(COC)(COC)C(C)CC.C1(=CC=CC=C1)C(COC)(COC)C(C)C Chemical compound C1(=CC=CC=C1)C(COC)(COC)C(C)CC.C1(=CC=CC=C1)C(COC)(COC)C(C)C JHPBGTKLJMOWGK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene 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
- 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
- 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
- WDINQFCMBGFZCN-UHFFFAOYSA-N [3-(1-benzoyloxyethyl)-3-methylheptan-2-yl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(C)(CCCC)C(C)OC(=O)C1=CC=CC=C1 WDINQFCMBGFZCN-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
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RWHFRGWHTJMEQP-UHFFFAOYSA-N bis(2-methylpropyl) 2-cyclohexyl-3-(3-methylbutyl)butanedioate Chemical compound CC(C)COC(=O)C(CCC(C)C)C(C(=O)OCC(C)C)C1CCCCC1 RWHFRGWHTJMEQP-UHFFFAOYSA-N 0.000 description 1
- WNEPUWJGDDGVJV-UHFFFAOYSA-N bis(2-methylpropyl) 2-cyclohexyl-3-propan-2-ylbutanedioate Chemical compound CC(C)COC(=O)C(C(C)C)C(C(=O)OCC(C)C)C1CCCCC1 WNEPUWJGDDGVJV-UHFFFAOYSA-N 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000003926 complexometric titration Methods 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
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency 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
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- UIZHEHICSUOPQL-UHFFFAOYSA-N diethyl 2,3-dibenzylbutanedioate Chemical compound C=1C=CC=CC=1CC(C(=O)OCC)C(C(=O)OCC)CC1=CC=CC=C1 UIZHEHICSUOPQL-UHFFFAOYSA-N 0.000 description 1
- DQNUPKXJISAAFG-UHFFFAOYSA-N diethyl 2,3-diethyl-2-propan-2-ylbutanedioate Chemical compound CCOC(=O)C(CC)C(CC)(C(C)C)C(=O)OCC DQNUPKXJISAAFG-UHFFFAOYSA-N 0.000 description 1
- ZUCVTIPWILNAMK-UHFFFAOYSA-N diethyl 2,3-ditert-butylbutanedioate Chemical compound CCOC(=O)C(C(C)(C)C)C(C(C)(C)C)C(=O)OCC ZUCVTIPWILNAMK-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-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
- 150000002148 esters Chemical class 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 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
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005375 photometry Methods 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
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 238000003786 synthesis reaction 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
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 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
- JAYPHJBLPAEMEX-UHFFFAOYSA-N trimethoxy(2-methylpentan-2-yl)silane Chemical compound CCCC(C)(C)[Si](OC)(OC)OC JAYPHJBLPAEMEX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 provides a catalyst for olefin polymerization, a preparation method thereof and a method for olefin polymerization. The preparation raw materials of the main catalyst comprise: (1) Titanium Compound Ti (OR) m‑y X y The method comprises the steps of carrying out a first treatment on the surface of the (2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O; (3) an internal electron donor; wherein the internal electron donor is an internal electron donor a, an internal electron donor b and an internal electron donor c, the three internal electron donors are compounds with certain structures, and the three are matched according to a certain proportion, so that the catalyst system has high polymerization activity and high hydrogen sensitization when the olefin polymerization is catalyzed to prepare polyolefinThe sensitivity, the molecular weight distribution are broad, and the olefin polymer having high isotacticity, a broad molecular weight distribution and low ash can be obtained with little or no external electron donor.
Description
Technical Field
The invention relates to the field of catalytic materials, in particular to a catalyst for olefin polymerization, a preparation method thereof and a method for olefin polymerization.
Background
Polypropylene is widely used in the fields of daily life and medical germany because of its good comprehensive properties, and is called a general plastic which develops rapidly. Among them, the catalyst is the core for improving the development of polypropylene industry. Currently, ziegler-Natta catalysts for the catalytic synthesis of polypropylene from olefins consist of titanium element, magnesium element, halogen element and one or several organic substances, i.e. MgCl 2 -TiCl 4 LB (Lewis base), wherein the Lewis base is an important component of the catalyst, is referred to as internal electron donor. The internal electron donor is a main factor for improving the performance of polypropylene, and has great influence on the characteristics of isotacticity, activity, hydrogen regulation sensitivity, molecular weight distribution and the like. Internal electron donors play an important role in the polymerization of propylene catalyzed by Ziegler-Natta catalysts.
An ideal catalyst system for olefin polymerization should have (or require) these good combinations of properties; 1. high activity, and can avoid post-treatment of polymerization products such as catalyst residue removal; 2. the active center is uniformly distributed, the polymerization rate is stable, the ideal polymerization kinetics behavior is realized, and the polymerization process is easy to control; 3. the catalyst and the polymerization product have good morphology, good particle shape (sphere or sphere-like) and narrow particle size distribution, and the polymer has higher bulk density and good fluidity; 4. the relative molecular mass and the relative molecular mass distribution of the polymerization product are adjustable; 5. slow activity attenuation of catalytic polymerization and long service life; 6. high stereotacticity, so that propylene is polymerized to obtain PP with high isotacticity, the procedure of removing random matters can be omitted, and the isotacticity is adjustable. Since the advent of Ziegler-Natta catalysts, continuous improvements and innovative research have been carried out, and existing workers have adopted catalysts containing two (or more) built-in electron donors to make up for the deficiency in performance of catalysts containing a single internal electron donor, thereby improving the performance of the catalysts. However, the effect of the compounding is not a simple superposition of several electron donor properties, and the components are mutually influenced and restricted.
W003002617 discloses a catalyst component and a catalyst for olefin polymerization, which are obtained by compounding monocarboxylic acid esters and dicarboxylic acid esters, and have good hydrogen regulation sensitivity, but the stereospecificity and the polymerization activity are still not very high.
Disclosure of Invention
In view of this, the present invention provides a catalyst for olefin polymerization, a method for preparing the same, and a method for olefin polymerization. The catalyst provided by the invention can ensure high activity and wide molecular weight distribution of olefin polymerization, and can improve the stereospecificity and isotacticity of the polymer and reduce ash.
The invention provides a catalyst for olefin polymerization, which comprises a main catalyst; the main catalyst is prepared from the following raw materials:
(1) Titanium Compound Ti (OR) m-y X y The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is 1-4, m-y is 0-3, R is C1-C10 alkyl, X is halogen;
(2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O; wherein R is 13 And R is 14 Halogen and can be the same or different, f is 0.1-6, ro is C1-C18 alkyl, g is 0-2, E is electron donor compound, h is 0-0.7;
(3) An internal electron donor; the internal electron donor is an internal electron donor a, an internal electron donor b and an internal electron donor c;
wherein,,
3.1 The internal electron donor a is an asymmetric 1, 3-diether compound shown in the formula I:
In formula I:
R 3 ' and R 4 ' each independently selected from: hydrogen, halogen, C1-C18 straight or branched alkyl, C3-C18 substituted or unsubstituted cycloalkyl, C6-C18 substituted or unsubstituted aryl, C7-C18 substituted or unsubstituted aralkyl; alternatively, R 3 ' and R 4 ' bonding to each other to form a ring with the C atom to which it is attached;
R 1 ' and R 2 ' each independently selected from: a C1-C10 linear or branched alkyl group;
3.2 The internal electron donor b is a succinic acid diester compound shown in a formula II:
in formula II:
R 5 ' and R 6 ' each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups each containing or not containing heteroatoms;
R 7 '～R 10 ' each independently selected from: hydrogen, C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl, each of which contains heteroatoms or is free of heteroatoms;
3.3 The internal electron donor c is a glycol ester compound shown in a formula III:
in formula III:
R 7 and R is 8 Each independently selected from: a C1-C10 linear or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, a C7-C20 substituted or unsubstituted aralkyl group; wherein the aromatic ring in the aryl or aralkyl is an unsubstituted aromatic ring or a substituted aromatic ring, and the substituent groups in the substituted aromatic ring are independently selected from halogen, C1-C6 linear or branched alkyl and C1-C6 alkoxy;
R 1 ～R 6 Each independently selected from: hydrogen, halogen, C1-C20 linear or branched alkyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted aralkyl, C2-C10 linear or branched alkenyl, each of which contains heteroatoms or is free of heteroatoms; the heteroatom is one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; alternatively, R 1 ～R 6 Are bonded to each other.
Preferably, 3.2), the internal electron donor b is a succinic acid diester compound shown in a formula II':
in formula II':
R 1 and R is 2 Each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups each containing or not containing heteroatoms;
R 3 and R is 4 Each independently selected from: hydrogen, halogen, C1-C20 substituted or unsubstituted alkyl, C2-C10 substituted or unsubstituted alkenyl, C2-C10 substituted or unsubstituted alkynyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted alkylaryl, C7-C20 substituted or unsubstituted arylalkyl, C10-C20 substituted or unsubstituted fused ring aryl;
The two asymmetric carbon atoms defined in formula II' are stereoisomers of the (S, R) or (R, S) type;
3.3 The internal electron donor c is a glycol ester compound shown in a formula III':
in formula III':
R 7 ～R 12 each independently selected from: hydrogen, a C1-C20 linear or branched alkyl group.
Preferably, in formula ii':
R 1 and R is 2 Each independently selected from: C1-C8 straight or branched alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl;
R 3 and R is 4 Each independently selected from: a secondary alkyl group.
Preferably, in formula ii':
R 1 and R is 2 Each independently selected from: methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl;
R 3 and R is 4 Each independently selected from: isopropyl, sec-butyl, 2-pentyl, 3-pentyl, cycloalkyl.
Preferably, 3.1), the internal electron donor a is 2, 6-dimethyl-3, 3-dimethoxymethylheptane;
3.2 The internal electron donor b is at least one of diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-dibenzyl succinate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-dicyclopentylsuccinate and diethyl 2, 3-dicyclohexylsuccinate; and each of the above compounds is independently a stereoisomer of the (S, R) form and/or a stereoisomer of the (R, S) form; and each of the above compounds is independently a racemate or a meso form;
3.3 The internal electron donor c is 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate.
Preferably, the Ti content in the main catalyst is more than 2.0wt%;
the Mg content in the main catalyst is 10-70 wt%;
the total content of the internal electron donor in the main catalyst is 15-50 wt%; wherein the content of the internal electron donor a in the main catalyst is 5-25 wt%, the content of the internal electron donor b in the main catalyst is 5-25 wt%, and the content of the internal electron donor c in the main catalyst is 5-25 wt%.
Preferably, (1) titanium compound Ti (OR) m-y X y Selected from: at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxytrichloride, titanium triethoxide chloride, titanium diethoxide dichloride, titanium ethoxytrichloride and titanium trichloride;
(2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O is selected from: at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropylmagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymagnesium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dibromide, and an alcohol adduct of magnesium diiodide; wherein the alcohol adduct of magnesium dichloride is a spherical particle.
Preferably, the catalyst further comprises a cocatalyst or further comprises a cocatalyst and an external electron donor;
the cocatalyst is an alkyl aluminum compound;
the external electron donor is an organosilane compound;
the molar ratio of Al in the alkyl aluminum compound to Ti in the main catalyst is (1-500) to 1;
when the catalyst further comprises a cocatalyst and an external electron donor, the molar ratio of Al in the alkyl aluminum compound to the external electron donor is (2-500) to 1.
The invention also provides a preparation method of the olefin polymerization catalyst in the technical scheme, and the main catalyst is prepared by the following preparation method:
s1, titanizingCompound Ti (OR) m-y X y After cooling, the adduct MgR of magnesium compound is added 13 R 14 ·fRoOH·gE·hH 2 And stirring the O, heating and carrying out heat preservation reaction when the target temperature is reached, and adding an internal electron donor in the heating and/or heat preservation process to form the main catalyst.
The invention also provides a method for polymerizing olefins, comprising the following steps:
under the action of a catalyst, an olefin monomer is subjected to polymerization reaction to obtain polyolefin;
wherein the catalyst is the catalyst in the technical scheme.
The invention provides a catalyst for catalyzing olefin polymerization, wherein the preparation raw materials of a main catalyst comprise: (1) Titanium Compound Ti (OR) m-y X y The method comprises the steps of carrying out a first treatment on the surface of the (2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O; (3) an internal electron donor; the main catalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst comprises an inner electron donor a, an inner electron donor b and an inner electron donor c, the three inner electron donors a, b and c are compounds with certain structures, and the three inner electron donors are matched in a certain proportion, and finally the main catalyst comprises titanium element, magnesium element, halogen and the inner electron donor which are matched specifically. The catalyst system has high polymerization activity, high hydrogen regulating sensitivity, wide molecular weight distribution and capacity of obtaining olefin polymer with high isotacticity, wide molecular weight distribution and low ash content with less or no external electron donor.
The test result shows that the polymerization activity of the catalyst provided by the invention is 123kgPP/gCa t The obtained polymer has an isotactic index of 98.1% or more, a polymer ash content of 37ppm or less, a molecular weight distribution MWD of 9.7 or more, and shows high polymerization activity, high isotacticity, low ash content and broad molecular weight distribution.
Detailed Description
The invention provides a catalyst for olefin polymerization, which comprises a main catalyst; the main catalyst is prepared from the following raw materials:
(1) Titanium Compound Ti (OR) m-y X y The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is 1-4, m-y is 0-3, R is C1-C10 alkyl, X is halogen;
(2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O; wherein R is 13 And R is 14 Halogen and can be the same or different, f is 0.1-6, ro is C1-C18 alkyl, g is 0-2, E is electron donor compound, h is 0-0.7;
(3) An internal electron donor; the internal electron donor is an internal electron donor a, an internal electron donor b and an internal electron donor c;
wherein,,
3.1 The internal electron donor a is an asymmetric 1, 3-diether compound shown in the formula I:
in formula I:
R 3 ' and R 4 ' each independently selected from: hydrogen, halogen, C1-C18 straight or branched alkyl, C3-C18 substituted or unsubstituted cycloalkyl, C6-C18 substituted or unsubstituted aryl, C7-C18 substituted or unsubstituted aralkyl; alternatively, R 3 ' and R 4 ' bonding to each other to form a ring with the C atom to which it is attached;
R 1 ' and R 2 ' each independently selected from: a C1-C10 linear or branched alkyl group;
3.2 The internal electron donor b is a succinic acid diester compound shown in a formula II:
In formula II:
R 5 ' and R 6 ' each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups each containing or not containing heteroatoms;
R 7 '～R 10 ' each independently selected from: hydrogen, C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl, each of which contains heteroatoms or is free of heteroatoms;
3.3 The internal electron donor c is a glycol ester compound shown in a formula III:
in formula III:
R 7 and R is 8 Each independently selected from: a C1-C10 linear or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, a C7-C20 substituted or unsubstituted aralkyl group; wherein the aromatic ring in the aryl or aralkyl is an unsubstituted aromatic ring or a substituted aromatic ring, and the substituent groups in the substituted aromatic ring are independently selected from halogen, C1-C6 linear or branched alkyl and C1-C6 alkoxy;
R 1 ～R 6 each independently selected from: hydrogen, halogen, C1-C20 linear or branched alkyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted aralkyl, C2-C10 linear or branched alkenyl, each of which contains heteroatoms or is free of heteroatoms; the heteroatom is one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; alternatively, R 1 ～R 6 Are bonded to each other.
[ concerning (1) titanium Compound Ti (OR) m-y X y ]：
In the present invention, y in the titanium compound is 1 to 4, and specifically may be 1, 2, 3 or 4.m-y is 0 to 3, and may be specifically 0, 1, 2 or 3.R is a C1-C10 alkyl group, more preferably ethyl, propyl or butyl. X is halogen, and can be Cl, br or I.
In the present invention, the above titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxytrichloride, titanium triethoxide chloride, titanium diethoxide dichloride, titanium ethoxytrichloride and titanium trichloride, more preferably titanium tetrachloride.
[ regarding (2) adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O]：
In the present invention, R in the adduct of the above magnesium compound 13 And R is 14 Are halogen and can be the same or different, and are independently selected from Cl, br or I. Ro is a C1-C18 hydrocarbon group, preferably a C1-C5 alkyl group, more preferably methyl, ethyl, n-propyl or isopropyl. E is an electron donor compound, the type of which is not particularly limited, and is a conventional electron donor compound in the field, and specifically may be phthalate esters, diethers, succinate esters or alcohol ester electron donor compounds, and the like.
f is 0.1 to 6, preferably 2 to 3.5, and may specifically be 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5.g is 0 to 2, and may be specifically 0, 0.5, 1.0, 1.5, 5.h is 0 to 0.7, and specifically may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7.
In the present invention, the adduct of the magnesium compound is preferably at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropylmagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymagnesium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dichloride, an alcohol adduct of magnesium dibromide and an alcohol adduct of magnesium diiodide, more preferably an alcohol adduct of magnesium dichloride, most preferably MgC1 2 ·f C 2 H 5 OH. In the present invention, the alcohol adducts of magnesium dichloride are preferably spherical particles.
The source of the adduct of the magnesium compound is not particularly limited in the present invention, and is commercially available or prepared as known in the art The method is simple. With MgC1 2 ·2.8C 2 H 5 OH is exemplified by synthesis with magnesium dichloride and ethanol according to the preparation method disclosed in CN 1330086A. Wherein, when the alcohol adduct of magnesium dichloride is spherical particles, the procatalyst obtained by reacting the alcohol adduct of magnesium dichloride with the titanium compound, the internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c is also spherical particles according to the mirror effect of the Ziegler-Natta catalyst.
[ concerning (3) internal electron donor ]:
according to the invention, the internal electron donor is an internal electron donor a, an internal electron donor b and an internal electron donor c.
The applicant finds that in the research process, an asymmetric 1, 3-diether, a dibutyl succinate compound and a symmetric glycol ester compound are adopted as internal electron donors to be compounded in a certain proportion, and the obtained olefin polymerization catalyst can further improve the high stereotacticity and isotacticity of the catalyst and has the characteristic of ultralow ash content on the premise of ensuring high activity, high hydrogen regulation sensitivity and wide molecular weight distribution.
With respect to 3.1) internal electron donor a：
In the invention, the internal electron donor a is an asymmetric 1, 3-diether compound shown in the formula I:
In formula I:
R 3 ' and R 4 ' each independently selected from: hydrogen, halogen, C1-C18 straight or branched alkyl, C3-C18 substituted or unsubstituted cycloalkyl, C6-C18 substituted or unsubstituted aryl, C7-C18 substituted or unsubstituted aralkyl; alternatively, R 3 ' and R 4 ' bonding to each other to form a ring with the C atom to which it is attached;
R 1 ' and R 2 ' each independently selected from: a C1-C10 linear or branched alkyl group;
in the present invention, preferably, the internal electron donor a includes at least one of the following compounds: 5, 7-diethyl-6, 6-dimethoxymethylundecane, 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, 1, 3-diphenyl-2, 2-dimethoxymethylpropane, 1, 3-dicyclohexyl-2, 2-dimethoxymethylpropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane 3, 3-dimethoxymethylpentane, 3-dimethoxymethylheptane, 2, 4-dimethyl-3, 3-dimethoxymethylpentane, 3-dimethoxymethylnonane, 2-dimethoxymethylpentane, 3-dimethoxymethyl-1-phenylpropane, 2-dimethoxymethylbutane 2, 2-Dimethoxymethyl-3-methylbutane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-dimethoxymethyl-4-methylpentane, 2, 2-Dimethoxymethyl-3-ethyloctane, 4-Dimethoxymethyl-2, 6-dimethylheptane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane 3, 3-Dimethoxymethyl-2, 5-dimethylhexane, 3-Dimethoxymethyl-2, 4-dimethylheptane, 2, 6-dimethyl-3, 3-Dimethoxymethyl-heptane, 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-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2, 4-dimethyl-3, 3-dimethoxymethylhexane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane.
In the present invention, most preferably, the internal electron donor a is 2, 6-dimethyl-3, 3-dimethoxymethylheptane.
With respect to 3.2) internal electron donor b：
In the invention, the internal electron donor b is a succinic acid diester compound shown in a formula II:
in formula II:
R 5 ' and R 6 ' each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups each containing or not containing heteroatoms;
R 7 '～R 10 ' each independently selected from: hydrogen, C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl, each of which contains heteroatoms or is free of heteroatoms.
In the present invention, preferably, the internal electron donor b is a succinic acid diester compound represented by formula ii':
in formula II':
R 1 and R is 2 Each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups, each containing or not containing heteroatoms. The heteroatom is selected from at least one of nitrogen, oxygen, sulfur, silicon, halogen, and phosphorus. Alternatively, R 1 And R is 2 Are connected together to form a ring; the rings are selected from the group consisting of saturated or unsaturated monocyclic rings, saturated or unsaturated polycyclic rings, and combinations of the foregoing monocyclic rings and polycyclic rings. Preferably, R 1 And R is 2 Each independently selected from: C1-C8 straight or branched chain alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl. More preferably, R 1 And R is 2 Each independently selected from primary alkyl groups, especially branched primary alkyl groups. Most preferably, R 1 And R is 2 Each independently selected from: methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl; ethyl is particularly preferred.
R 3 And R is 4 Each independently selected from: hydrogen, halogen, C1-C20 substituted or unsubstituted alkyl, C2-C10 substituted or unsubstituted alkenyl, C2-C10 substituted or unsubstituted alkynyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted alkylaryl, C7-C20 substituted or unsubstituted arylalkyl, C10-C20 substituted or unsubstituted fused ring aryl. Preferably, R 3 And R is 4 Each independently selected from: C1-C20 substituted or unsubstituted alkyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted alkylaryl, C7-C20 substituted or unsubstituted arylalkyl, and R 3 And R is 4 At least one of which is a C1-C20 branched alkyl group. In the C1-C20 substituted or unsubstituted alkyl, the alkyl is a linear alkyl or a branched alkyl. In the above substituent-containing groups, the substituents are independently selected from the group consisting of halogen, C1-C6 alkyl and C1-C6 alkoxy. R is R 3 And R is 4 In the above-mentioned selective groups of (2), a hetero atom is contained or not contained; the heteroatom is at least one of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus. Most preferably, R 3 And R is 4 Each independently selected from secondary alkyl groups; specifically selected from isopropyl, sec-butyl, 2-pentyl, 3-pentyl, cycloalkyl (e.g. cyclohexyl, cyclopentyl, cyclohexylmethyl).
In the present invention, preferably, the two asymmetric carbon atoms defined in the formula II' are stereoisomers of the (S, R) or (R, S) type.
In the present invention, more preferably, the internal electron donor b is selected from at least one of the following compounds: diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropyl succinate, diethyl 2, 3-diisopropyl succinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-di-isobutyl succinate, diethyl 2,3- (bistrimethylsilyl) succinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisoamyl succinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2-isopropyl-3-isobutyl succinate, diethyl 2-tert-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexyl succinate, diethyl 2-isopentyl-3-cyclohexyl succinate, diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-di-diethyl-2-isopropyl succinate, diisobutyl 2, 3-di-tert-butyl-2, 3-di-isobutyl succinate, diisobutyl 2, 3-di-tert-butyl-2, 3-isobutyl succinate, diisobutyl-2-3-diisobutyl-2, 3-diisobutyl-2-isobutyl succinate, diisobutyl-3-di-isobutyl succinate, diisobutyl-2, 3-isobutyl-2-3-isobutyl succinate, diisobutyl-2, 3-diisobutyl-2-isobutyl succinate, 2-isopropyl-3-cyclohexylsuccinic acid diisobutyl ester, 2-isopentyl-3-cyclohexylsuccinic acid diisobutyl ester, and 2, 3-di-tert-butylsuccinic acid diisobutyl ester.
In the present invention, more preferably, the internal electron donor b is selected from at least one of the following compounds: diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-dibenzylsuccinate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-dicyclopentylsuccinate, diethyl 2, 3-dicyclohexyl succinate. And each of the above compounds is independently a stereoisomer of the (S, R) form and/or a stereoisomer of the (R, S) form; and each of the above compounds is independently a racemate or a meso form.
In the invention, most preferably, the internal electron donor b is diethyl 2, 3-diisopropyl succinate. The compounds are stereoisomers of the (S, R) type and/or stereoisomers of the (R, S) type; and the above compounds are independently racemates or meso.
With respect to 3.3) internal electron donor c：
In the invention, the internal electron donor c is a glycol ester compound shown in a formula III:
in formula III:
R 7 and R is 8 Each independently selected from: a C1-C10 linear or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, a C7-C20 substituted or unsubstituted aralkyl group; wherein the aromatic ring in the aryl or aralkyl is an unsubstituted aromatic ring or a substituted aromatic ring, and the substituent groups in the substituted aromatic ring are independently selected from halogen, C1-C6 straight-chain or branched-chain alkyl and C1-C6 alkoxy.
R 1 ～R 6 Each independently selected from: hydrogen, halogen, C1-C20 linear or branched alkyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted aralkyl, C2-C10 linear or branched alkenyl, each of which contains heteroatoms or is free of heteroatoms; the heteroatom is one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; alternatively, R 1 ～R 8 Are bonded to each other. Wherein the C1-C20 linear or branched alkyl groups 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-hexadecyl, n-octadecyl, n-nonadecyl, n-eicosyl.
In the present invention, preferably, the internal electron donor c is a glycol ester compound represented by formula iii':
In formula III':
R 7 ～R 12 each independently selected from: hydrogen, a C1-C20 linear or branched alkyl group. Wherein, the type selection range of the C1-C20 straight-chain or branched-chain alkyl is the same as that in the formula III, and the description is omitted here.
In the present invention, preferably, the internal electron donor c is selected from at least one of the following compounds: 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, and 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-dimethyl-1, 5-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate.
In the present invention, more preferably, the electron body c is 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate. In the present invention, it is further preferable that the electron body c is 2, 4-pentanediol dibenzoate. The above compound is at least one of (S, S) -type stereoisomers, (R, R) -type stereoisomers and (R, S) -type stereoisomers. The above compound is preferably a meso form.
The applicant researches show that the catalyst system formed by adopting 2, 6-dimethyl-3, 3-dimethoxymethane-level heptane as an internal electron donor compound a, adopting 2, 3-diisopropyl diethyl succinate as an internal electron donor compound b and adopting 2, 4-pentanediol dibenzoate as an internal electron donor compound c maintains a certain proportion, has high polymerization activity, high hydrogen regulation sensitivity, wider molecular weight distribution and can obtain olefin polymers with high isotacticity, wide molecular weight distribution and low ash content under the condition of using a small amount of external electron donor when catalyzing olefin polymerization to prepare polyolefin compared with other internal electron donors.
[ method for preparing a procatalyst ]:
the invention also provides a preparation method of the olefin polymerization catalyst in the technical scheme, wherein the main catalyst is prepared by the following preparation method:
S1, ti (OR) is a titanium compound m-y X y After cooling, the adduct MgR of magnesium compound is added 13 R 14 ·fRoOH·gE·hH 2 And stirring the O, heating and carrying out heat preservation reaction when the target temperature is reached, and adding an internal electron donor in the heating and/or heat preservation process to form the main catalyst.
Regarding step S1:
adducts MgR of the magnesium compounds 13 R 14 ·fRoOH·gE·hH 2 O, titanium compound Ti (OR) m-y X y The molar ratio of the organic compound to the internal electron donor is preferably 1:20-200:0.04-0.8, more preferably 1:50-180:0.05-0.5, and even more preferably 1:70-150:0.1-0.4. Wherein, the molar ratio of the internal electron donor a, the internal electron donor b and the internal electron donor c is preferably (0.5-10) to (2-18) to 1, more preferably (1-7) to (2.5-13) to 1.
The cooling is preferably to below 0 ℃, more preferably to-5 to-25 ℃, and in particular can be-5 ℃, -10 ℃, -15 ℃, -20 ℃, -25 ℃. Cooling to the above temperature and adding magnesium compound adduct MgR 13 R 14 ·f RoOH·gE·hH 2 O, and stirring and mixing under the temperature condition; the stirring time is preferably 30 to 90 minutes. Then, the temperature is raised. The temperature is preferably raised to a reaction temperature of 70 to 130 ℃, specifically 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃. After the temperature is raised to the target temperature, the heat-preserving reaction is carried out. The time of the heat preservation is preferably The time is 0.5-4 h, and can be specifically 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h and 4.0h.
And adding an internal electron donor in the heating and/or heat preserving process. In the present invention, the internal electron donor may be added during one or more of a period of time before, during and after the reaction of the adduct of the magnesium compound with the titanium compound. Wherein the period before the reaction refers to a period after the magnesium compound is added to the reactor and before the temperature is raised to the reaction temperature. The adding sequence of the internal electron donor a, the internal electron donor b and the internal electron donor c is not particularly limited, and the internal electron donor a, the internal electron donor b and the internal electron donor c can be added into the system sequentially or simultaneously; when the abc is added sequentially, the sequence is not particularly limited, and for example, the abc may be added sequentially in the order of a→b→c, a→c→b or c→a→b, or the abc may be added simultaneously, or the abc may be mixed in advance and then the mixture may be added. After the reaction, a main catalyst is obtained.
In the present invention, the whole step S1 is preferably performed under a protective atmosphere. In the present invention, the gas species providing the protective atmosphere is preferably nitrogen.
In the present invention, the above preparation method preferably specifically includes:
S1, ti (OR) is a titanium compound m-y X y After cooling, the adduct MgR of magnesium compound is added 13 R 14 ·fRoOH·gE·hH 2 Stirring O, heating and carrying out heat preservation reaction when the target temperature is reached, and adding an internal electron donor in the heating and/or heat preservation process to form a reaction solution;
s2, carrying out solid-liquid separation on the reaction liquid to remove liquid, and adding titanium compound Ti (OR) into the obtained solid m-y X y Then washing and drying are carried out to obtain the main catalyst.
Regarding step S2:
the solid-liquid separation mode is not particularly limited, and is a conventional solid-liquid separation operation in the art, and suction filtration is preferred. Thereafter, a titanium compound Ti (OR) is added to the obtained solid m-y X y Treating 1-2 times to perform secondary treatmentTitanium is supported with the aim of removing trivalent titanium ions free on the support and increasing the loading of tetravalent titanium ions. Wherein, in step S2, the titanium compound Ti (OR) m-y X y The amount of (C) is based on the titanium compound Ti (OR) m-y X y Total mass (i.e. Ti (OR) as titanium compound used in step S1 and step S2) m-y X y Total amount) 30% -50%. The washing is preferably with an inert solvent; the inert solvents include, but are not limited to: hexane, heptane, octane, decane or toluene, preferably n-hexane; the amount of inert solvent used in the washing is preferably the same as the amount of titanium compound used in the preparation of the catalyst. The drying is preferably vacuum drying. After the above treatment, a main catalyst is obtained.
After the reaction of step S1, raw material Ti (OR) m-y X y Adducts MgR of predominantly titanium halide and magnesium compounds as starting materials 13 R 14 ·f RoOH·gE·hH 2 O mainly forms magnesium halide, the internal electron donor remains unchanged, wherein magnesium halide is used as a carrier, and tetravalent titanium ions and the internal electron donor are supported on the magnesium halide carrier.
[ regarding the ratio of the components in the main catalyst product ]:
as described above, after the raw materials are reacted, the main catalyst mainly comprises: titanium element, magnesium element, halogen and internal electron donor.
In the present invention, the Ti content in the main catalyst is > 2.0wt%, preferably not less than 2.5wt%, more preferably 2.5wt% to 3.0wt%, and particularly may be 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3.0wt%.
In the present invention, the Mg content in the main catalyst is 10wt% to 70wt%, preferably 15wt% to 30wt%, and particularly 15wt%, 20wt%, 25wt%, 30wt%.
In the present invention, the halogen content in the main catalyst is 20wt% to 80wt%, preferably 30wt% to 70wt%, and specifically 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%.
In the invention, the total content of the internal electron donor in the main catalyst is 15-50 wt%, preferably 22-40 wt%, and particularly 22wt%, 25wt%, 30wt%, 35wt% and 40wt%. Wherein the content of the internal electron donor a in the main catalyst is 5-25 wt%, preferably 8-15 wt%; the content of the internal electron donor b in the main catalyst is 5-25 wt%, preferably 8-13 wt%; the content of the internal electron donor c in the main catalyst is 5 to 25wt%, preferably 6 to 12wt%.
[ regarding other components in the catalyst ]:
in the present invention, the catalyst system preferably further comprises a cocatalyst in addition to the procatalyst described above, or alternatively, a cocatalyst and an external electron donor. I.e. may or may not contain an external electron donor.
Regarding the cocatalyst:
in the invention, the cocatalyst is an alkyl aluminum compound. The general formula of the alkyl aluminum compound is AlR n X 3-n The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is C1-C8 alkyl or haloalkyl, X is halogen, preferably at least one of Cl, br and I, and n is an integer from 1 to 3. In the present invention, the alkyl aluminum compound is preferably triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, dichloroethylaluminum, al (n-C) 6 H 13 ) 3 And Al (n-C) 8 H 17 ) 3 More preferably triethylaluminum and/or triisobutylaluminum.
In the present invention, the amount of the cocatalyst for an alkylaluminum compound is not particularly limited, and may be a conventional amount in the art. Preferably, the molar ratio of Al in the alkyl aluminum compound to Ti in the main catalyst is preferably (1 to 500) to 1, more preferably (10 to 300) to 1, and most preferably (20 to 200) to 1.
Regarding the external electron donor:
in the present invention, the external electron donor is an organosilane compound. In the present invention, the organosilane compound has the general formula (R 1 ) a (R 2 ) b Si(OR 3 ) c . Wherein a and b are independently selected from integers from 0 to 2, c is selected from integers from 0 to 4, and a+b+c=4. R is R 1 、R 2 、R 3 Independently selected from C1-C18 groups, preferably independently selected from: a C3-C10 linear or branched alkyl group, a C3-C10 alkylene group, a C3-C10 substituted or unsubstituted cycloalkyl group, a C6-C10 substituted or unsubstituted aryl group; and each of the foregoing groups optionally contains heteroatoms (i.e., may or may not contain heteroatoms); the heteroatom is at least one of F, C1, br, N and I.
In the present invention, the external electron donor is preferably at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, t-hexyltrimethoxysilane and 2-ethylpiperidyl-2-t-butyldimethoxysilane, more preferably cyclohexylmethyldimethoxysilane and/or dicyclopentyldimethoxysilane.
In the present invention, when the catalyst contains an external electron donor, the molar ratio of Al in the alkyl aluminum compound to the external electron donor is preferably (2 to 500) to 1, more preferably (5 to 200) to 1.
[ method for olefin polymerization ]:
the invention also provides a method for polymerizing olefins, comprising the following steps:
under the action of a catalyst, an olefin monomer is subjected to polymerization reaction to obtain polyolefin;
wherein, the catalyst is the catalyst in the above technical scheme, and is not described herein.
In the present invention, the olefin monomer is selected from the group consisting of formula CH 2 =at least one of the olefin monomers shown by CHR. Wherein R is hydrogen or C1-C12 alkyl. Preferably, the olefin monomer is selected from ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexaneAt least one of ethylene, 1-n-octene and 4-methyl-1-pentene, more preferably at least one of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene, and most preferably propylene.
In the present invention, the reaction is preferably carried out in the presence of hydrogen. Wherein, the volume ratio of the hydrogen to the olefin monomer is preferably (8-10) nL:2.5L, and can be 9 nL:2.5L.
In the present invention, the ratio of the catalyst to the olefin monomer is preferably (15-20) mg/2.5L.
In the present invention, the polymerization conditions are preferably: the temperature is 0-140 ℃, the time is 0.5-3 h, and the pressure is 0.01-10 MPa. Wherein the temperature is more preferably 60 to 100 ℃, specifically 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃. The time is more preferably 1 to 3 hours, and may be specifically 1 hour, 2 hours, or 3 hours. The pressure is more preferably 0.5 to 5MPa, and may specifically be 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa, 5.0MPa. After the polymerization reaction, a polyolefin product is obtained.
In the present invention, the above-mentioned olefin polymerization method preferably specifically comprises: adding part of olefin monomers into a reaction vessel under inert atmosphere, then adding a cocatalyst or adding the cocatalyst and an external electron donor, and then adding a main catalyst; finally, hydrogenation and residual olefin monomers are carried out, and polymerization reaction is carried out by heating, so as to obtain polyolefin. The types, amounts, condition parameters, etc. of the substances are the same as those described above, and are not described here again. Wherein, the partial olefin monomer added first accounts for 20% -40% of the total mass of the olefin monomer, more preferably 40%, so that the catalyst is fully mixed with the olefin monomer first, and the catalyst added first is prevented from sinking into the bottom of the reactor and cannot fully react with the olefin monomer.
The invention provides a catalyst for catalyzing olefin polymerization, wherein the preparation raw materials of a main catalyst comprise: (1) Titanium Compound Ti (OR) m-y X y The method comprises the steps of carrying out a first treatment on the surface of the (2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O; (3) an internal electron donor; wherein the internal administrationThe electron body is an internal electron donor a, an internal electron donor b and an internal electron donor c, wherein three internal electron donors are compounds with a certain structure, and the three internal electron donors are matched according to a certain proportion, and finally the main catalyst comprises titanium element, magnesium element, halogen and the internal electron donor with specific matching. The catalyst system has high polymerization activity, high hydrogen regulating sensitivity, wide molecular weight distribution and capacity of obtaining olefin polymer with high isotacticity, wide molecular weight distribution and low ash content with less or no external electron donor.
The test result shows that the polymerization activity of the catalyst provided by the invention is 123kgPP/gCa t The obtained polymer has an isotactic index of 98.1% or more, a polymer ash content of 37ppm or less, a molecular weight distribution MWD of 9.7 or more, and shows high polymerization activity, high isotacticity, low ash content and broad molecular weight distribution.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
1. Preparation of the procatalyst
Into a 300mL glass reaction flask with stirring, which had been sufficiently replaced with high-purity nitrogen gas, 100mL of titanium tetrachloride was added, cooled to-20℃and 5g of spherical magnesium chloride alkoxide (MgC 1) was added 2 ·2.8C 2 H 5 OH, synthesized with magnesium dichloride and ethanol according to the method disclosed in CN 1330086A), 2, 6-dimethyl-3, 3-dimethoxymethylheptane (internal electron donor compound a) 1.5mmol,2, 3-diisopropylbutanedioic acid dibutyl ester (internal electron donor compound b) 1.5mmol and 2, 4-pentanediol dibenzoate (internal electron donor compound c) 3.0mmol were added during the warming up with stirring and the temperature was kept constant for 2h after the warming up to 120 ℃. Then, the liquid was removed by suction filtration, and 100mL of titanium tetrachloride was added to the solid phase obtained by filtration for two times. Then washing with 60mL hexane for six times, and vacuum drying to obtain spherical main catalystAgent A1.
2. Propylene polymerization
In a 5L autoclave, purged with nitrogen gas flow, 1L of liquid propylene was first introduced, then 11.17mmol of triethylaluminum (co-catalyst), 1.8mmol of diphenyldimethoxysilane (DDS, external electron donor) were introduced into the nitrogen gas flow, and then 15mg of spherical procatalyst A1 was introduced into the nitrogen gas flow. The autoclave was closed and 9nL of hydrogen and 1.5L of liquid propylene were added. Heating to 70 ℃ for polymerization for 2 hours to obtain a polymer product.
Example 2
1. Preparation of the procatalyst
As in example 1, a spherical main catalyst A1 was obtained.
2. Propylene polymerization
The procedure is as in example 1, except that the external electron donor diphenyldimethoxysilane is not introduced.
Example 3
1. Preparation of the procatalyst
The procedure of example 1 was followed except that the amount of 2, 4-pentanediol dibenzoate (internal electron donor compound c) was adjusted to 1.5mmol, thereby obtaining a spherical procatalyst A2.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by a spherical procatalyst A2.
Example 4
1. Preparation of the procatalyst
As in example 3, a spherical main catalyst A2 was prepared.
2. Propylene polymerization
The procedure is as in example 3, except that the external electron donor diphenyldimethoxysilane is not introduced.
Example 5
1. Preparation of the procatalyst
The procedure was carried out as in example 1, except that the amount of 2, 6-dimethyl-3, 3-dimethoxymethylheptane (internal electron donor compound a) was adjusted to 3.0mmol, and the amount of dibutyl 2, 3-diisopropylsuccinate (internal electron donor compound b) was adjusted to 3.0mmol, to finally obtain spherical procatalyst A3.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by a spherical procatalyst A3.
Example 6
1. Preparation of the procatalyst
As in example 5, a spherical procatalyst A3 was prepared.
2. Propylene polymerization
The procedure is as in example 5, except that the external electron donor diphenyldimethoxysilane is not introduced.
Example 7
1. Preparation of the procatalyst
The procedure was carried out as in example 1, except that the amount of 2, 6-dimethyl-3, 3-dimethoxymethylheptane (internal electron donor compound a) was adjusted to 3.0mmol, and the amount of 2, 4-pentanediol dibenzoate (internal electron donor compound c) was adjusted to 1.5mmol, to finally obtain spherical procatalyst A4.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by a spherical procatalyst A4.
Example 8
1. Preparation of the procatalyst
As in example 7, a spherical procatalyst A4 was prepared.
2. Propylene polymerization
The procedure is as in example 7, except that the external electron donor diphenyldimethoxysilane is not introduced.
Comparative example 1
1. Preparation of the procatalyst
The procedure was carried out as in example 1, except that dibutyl 2, 3-diisopropylsuccinate (internal electron donor compound B) and 2, 4-pentanediol dibenzoate (internal electron donor compound c) were not added, to give a procatalyst B1.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by a procatalyst B1.
Comparative example 2
1. Preparation of the procatalyst
The procedure was carried out as in example 1, except that 2, 6-dimethyl-3, 3-dimethoxymethylheptane (internal electron donor compound a) and dibutyl 2, 3-diisopropylsuccinate (internal electron donor compound B) were not added, to give procatalyst B2.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by procatalyst B2.
Comparative example 3
1. Preparation of the procatalyst
The procedure was carried out as in example 1, except that 2, 6-dimethyl-3, 3-dimethoxymethylheptane (internal electron donor compound a) and 2, 4-pentanediol dibenzoate (internal electron donor compound c) were not added, to give a procatalyst B3.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by procatalyst B3.
Comparative example 4
1. Preparation of the procatalyst
The procedure is as in example 3, except that no dibutyl 2, 3-diisopropylsuccinate (internal electron donor compound B) is added, giving procatalyst B4.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by procatalyst B4.
Comparative example 5
1. Preparation of the procatalyst
The procedure is as in example 3, except that no 2, 4-pentanediol dibenzoate (internal electron donor compound c) is added, giving procatalyst B5.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by procatalyst B5.
Comparative example 6
1. Preparation of the procatalyst
The procedure was carried out as in example 1, except that 2, 6-dimethyl-3, 3-dimethoxymethylheptane (internal donor compound a), dibutyl 2, 3-diisopropylsuccinate (internal donor compound B) and 2, 4-pentanediol dibenzoate (internal donor compound c) were replaced by 1, 3-diphenyl-2, 2-dimethoxymethylpropane (internal donor compound a), diisobutyl 2, 3-di-tert-butylsuccinate (internal donor compound B) and 3, 5-dimethyl-2, 6-heptanediol dibenzoate (internal donor compound c), respectively, to give procatalyst B6.
2. Propylene polymerization
The procedure is as in example 1, except that only the spherical procatalyst A1 is replaced by procatalyst B6.
And (3) effect test:
the performance test involved is as follows:
(1) Determination of Ti content in the catalyst: and (3) performing photometric measurement calculation and determination by adopting an ultraviolet-visible spectrophotometer.
(2) Determination of Mg content in the catalyst: measured by using a complexometric titration method of magnesium ions and EDTA.
(3) Determination of the internal Electron donor Compound content in the catalyst: the method comprises the steps of adopting a chromatographic method, decomposing the catalyst dry powder by dilute acid, extracting an internal electron donor compound in the catalyst dry powder by using an extracting agent, and measuring by adopting a gas chromatograph.
(4) Determination of polymer ash: measured according to GB/T9345-1988.
(5) Determination of the isotactic index of the polymer: measurement was performed by heptane extraction (heptane boiling extraction 6 h): after 2g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, the ratio of the polymer weight (g) obtained by drying the residue to constant weight to the initial weight 2 (g) was the isotactic index.
(6) Determination of the melt flow index (MI) of the Polymer: the melt flow index is measured by a melt flow index meter, and the GB/T3682-2000 standard is referred to.
(7) Determination of the molecular weight distribution MWD (mwd=mw/Mn) of the polymer: the measurement was carried out by high temperature GPC using trichlorobenzene as a solvent at 150℃ (standard: polystyrene, flow rate: 1.0mL/min, column: 3xP1ge110um M1xED-B300X7.5 nm).
The test results are shown in Table 1.
Table 1: test results for each example and comparative example
As can be seen from the test results of Table 1, the polymerization activities of examples 1 to 8 of the present invention were found to be 123kg PP/gCa t The polymer has an isotactic index of 98.1% or more, a polymer ash content of 37ppm or less, a molecular weight distribution MWD of 9.7 or more, and shows high polymerization activity, high isotacticity, low ash content and broad molecular weight distribution. While the polymerization activities of comparative examples 1 to 5 were 98kg PP/gCa t The polymer has an ash content of 35ppm or more, a molecular weight distribution MWD of 8.5 or less, and poor overall properties. It can be seen from the comparison of the effects of examples 1-8 and comparative examples 1-3 that the polymerization activity and stereospecificity of the catalyst system prepared by the method of the invention by adopting the compound catalyst system containing the internal electron donors a, b and c are obviously higher than those of the catalyst containing only one internal electron donor, the ash content of the polymer is far lower than that of the polymer obtained by the catalyst containing only one internal electron donor, and the molecular weight distribution width is obviously higher than that of the polymer obtained by the catalyst containing only one internal electron donor. As can be seen from the comparison of the effects of examples 1-8 and comparative examples 4-5, the polymerization activity of the catalyst system compounded by adopting the catalyst system containing the internal electron donors a, b and c is obviously improved, the ash content of the polymer is further reduced, and the molecular weight distribution is obviously widened compared with the catalyst system containing only two internal electron donors. As can be seen from the comparison of the effects of examples 1-8 and comparative example 6, the polymerization activity, the polymer isotactic index and the ash content effect of comparative example 6 are poor, and it is proved that the specific internal electron donors a, b and c are adopted for compounding, so that the effects of improving the polymerization activity, the polymer isotactic index, the polymer ash and the like are facilitated.
In each group, the latter (without external electron donor added) did not decrease the polymerization activity, even increased the polymerization activity, and also decreased the ash content of the polymer, and maintained high isotacticity and broad molecular weight distribution, compared to the former, and it was confirmed that the present invention, using the internal electron donor a+b+c for compounding, could achieve excellent and even better comprehensive effects, even without the external electron donor.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. A catalyst for olefin polymerization, comprising a main catalyst; the main catalyst is prepared from the following raw materials:
(1) Titanium Compound Ti (OR) m-y X y The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is 1-4, m-y is 0-3, R is C1-C10 alkyl, X is halogen;
(2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O; wherein R is 13 And R is 14 Halogen and can be the same or different, f is 0.1-6, ro is C1-C18 alkyl, g is 0-2, E is electron donor compound, h is 0-0.7;
(3) An internal electron donor; the internal electron donor is an internal electron donor a, an internal electron donor b and an internal electron donor c;
wherein,,
3.1 The internal electron donor a is an asymmetric 1, 3-diether compound shown in the formula I:
in formula I:
R 3 ' and R 4 ' each independently selected from: hydrogen, halogen, C1-C18 straight or branched alkyl, C3-C18 substituted or unsubstituted cycloalkyl, C6-C18 substituted or unsubstituted aryl, C7-C18 substituted or unsubstituted aralkyl; alternatively, R 3 ' and R 4 ' bonding to each other to form a ring with the C atom to which it is attached;
R 1 ' and R 2 ' each independently selected from: a C1-C10 linear or branched alkyl group;
3.2 The internal electron donor b is a succinic acid diester compound shown in a formula II:
In formula II:
R 5 ' and R 6 ' each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups each containing or not containing heteroatoms;
R 7 '～R 10 ' each independently selected from: hydrogen, C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl, each of which contains heteroatoms or is free of heteroatoms;
3.3 The internal electron donor c is a glycol ester compound shown in a formula III:
in formula III:
R 7 and R is 8 Each independently selected from: a C1-C10 linear or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, a C7-C20 substituted or unsubstituted aralkyl group; wherein the aromatic ring in the aryl or aralkyl is an unsubstituted aromatic ring or a substituted aromatic ring, and the substituent groups in the substituted aromatic ring are independently selected from halogen, C1-C6 linear or branched alkyl and C1-C6 alkoxy;
R 1 ～R 6 each independently selected from: hydrogen, halogen, C1-C20 linear or branched alkyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl, C7-C20 substituted or unsubstituted aralkyl, C2-C10 linear or branched alkenyl, each of which contains heteroatoms or is free of heteroatoms; the heteroatom is one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; alternatively, R 1 ～R 6 Are bonded to each other.
2. The catalyst of claim 1, wherein the catalyst is,
3.2 The internal electron donor b is a succinic acid diester compound shown in a formula II':
in formula II':
R 1 and R is 2 Each independently selected from: C1-C20 straight or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl groups each containing or not containing heteroatoms;
R 3 and R is 4 Each independently selected from: hydrogen, halogen, C1-C20 substituted or unsubstituted alkyl, C2-C10 substituted or unsubstituted alkenyl, C2-C10 substituted or unsubstituted alkynyl, C3-C20 substituted or unsubstituted cycloalkyl, C6-C20 substitutedOr unsubstituted aryl, C7-C20 substituted or unsubstituted alkylaryl, C7-C20 substituted or unsubstituted arylalkyl, C10-C20 substituted or unsubstituted fused ring aryl;
the two asymmetric carbon atoms defined in formula II' are stereoisomers of the (S, R) or (R, S) type;
3.3 The internal electron donor c is a glycol ester compound shown in a formula III':
in formula III':
R 7 ～R 12 each independently selected from: hydrogen, a C1-C20 linear or branched alkyl group.
3. The catalyst of claim 2, wherein in formula ii':
R 1 And R is 2 Each independently selected from: C1-C8 straight or branched alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl;
R 3 and R is 4 Each independently selected from: a secondary alkyl group.
4. A catalyst according to claim 3, characterized in that in formula ii':
R 1 and R is 2 Each independently selected from: methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl;
R 3 and R is 4 Each independently selected from: isopropyl, sec-butyl, 2-pentyl, 3-pentyl, cycloalkyl.
5. The catalyst according to any one of claims 1 to 4, characterized in that 3.1) the internal electron donor a is 2, 6-dimethyl-3, 3-dimethoxymethyl heptane;
3.2 The internal electron donor b is at least one of diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-dibenzyl succinate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-dicyclopentylsuccinate and diethyl 2, 3-dicyclohexylsuccinate; and each of the above compounds is independently a stereoisomer of the (S, R) form and/or a stereoisomer of the (R, S) form; and each of the above compounds is independently a racemate or a meso form;
3.3 The internal electron donor c is 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate.
6. The catalyst according to any one of claims 1 to 4, characterized in that the Ti content in the procatalyst is > 2.0wt%;
the Mg content in the main catalyst is 10-70 wt%;
the total content of the internal electron donor in the main catalyst is 15-50 wt%; wherein the content of the internal electron donor a in the main catalyst is 5-25 wt%, the content of the internal electron donor b in the main catalyst is 5-25 wt%, and the content of the internal electron donor c in the main catalyst is 5-25 wt%.
7. The catalyst of claim 1, wherein the catalyst is,
(1) Titanium Compound Ti (OR) m-y X y Selected from: at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxytrichloride, titanium triethoxide chloride, titanium diethoxide dichloride, titanium ethoxytrichloride and titanium trichloride;
(2) Adducts MgR of magnesium compounds 13 R 14 ·f RoOH·gE·hH 2 O is selected from: dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropylmagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxychloride At least one of magnesium, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymagnesium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dichloride, an alcohol adduct of magnesium dibromide, and an alcohol adduct of magnesium diiodide; wherein the alcohol adduct of magnesium dichloride is a spherical particle.
8. The catalyst of claim 1, further comprising a cocatalyst or, alternatively, a cocatalyst and an external electron donor;
the cocatalyst is an alkyl aluminum compound;
the external electron donor is an organosilane compound;
the molar ratio of Al in the alkyl aluminum compound to Ti in the main catalyst is (1-500) to 1;
when the catalyst further comprises a cocatalyst and an external electron donor, the molar ratio of Al in the alkyl aluminum compound to the external electron donor is (2-500) to 1.
9. A process for preparing a catalyst for the polymerization of olefins according to any of claims 1 to 8, characterized in that the procatalyst is prepared by the following preparation process:
S1, ti (OR) is a titanium compound m-y X y After cooling, the adduct MgR of magnesium compound is added 13 R 14 ·f RoOH·gE·hH 2 And stirring the O, heating and carrying out heat preservation reaction when the target temperature is reached, and adding an internal electron donor in the heating and/or heat preservation process to form the main catalyst.
10. A process for the polymerization of olefins comprising the steps of:
under the action of a catalyst, an olefin monomer is subjected to polymerization reaction to obtain polyolefin;
wherein the catalyst is the catalyst of any one of claims 1 to 8.
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| Country | Link |
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| CN (1) | CN116375911A (en) |
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2023
- 2023-05-25 CN CN202310599016.8A patent/CN116375911A/en active Pending
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