CN112552434A - Multi-center supported catalyst and preparation method and application thereof - Google Patents
Multi-center supported catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112552434A CN112552434A CN201910910248.4A CN201910910248A CN112552434A CN 112552434 A CN112552434 A CN 112552434A CN 201910910248 A CN201910910248 A CN 201910910248A CN 112552434 A CN112552434 A CN 112552434A
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- CN
- China
- Prior art keywords
- vanadium
- pyrrole
- supported catalyst
- nme
- net
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 111
- -1 pyrrole heterocyclic compound Chemical class 0.000 claims abstract description 73
- 239000011651 chromium Substances 0.000 claims abstract description 60
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims abstract description 52
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 52
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 14
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 14
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 13
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 13
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 51
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 51
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 36
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 28
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 27
- 125000000623 heterocyclic group Chemical group 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 19
- 238000007598 dipping method Methods 0.000 claims description 18
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012968 metallocene catalyst Substances 0.000 claims description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QMFQJBURIUFBHV-UHFFFAOYSA-N [Cr].C(C)(C)C1=CC=CC1.C(C)(C)C1=CC=CC1 Chemical compound [Cr].C(C)(C)C1=CC=CC1.C(C)(C)C1=CC=CC1 QMFQJBURIUFBHV-UHFFFAOYSA-N 0.000 claims description 4
- WGABQJATLAZQIM-UHFFFAOYSA-N [Cr].C(C)C1=CC=CC1.C(C)C1=CC=CC1 Chemical compound [Cr].C(C)C1=CC=CC1.C(C)C1=CC=CC1 WGABQJATLAZQIM-UHFFFAOYSA-N 0.000 claims description 4
- TYYBBNOTQFVVKN-UHFFFAOYSA-N chromium(2+);cyclopenta-1,3-diene Chemical compound [Cr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 TYYBBNOTQFVVKN-UHFFFAOYSA-N 0.000 claims description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- OUGBCEDZHZZVKV-UHFFFAOYSA-N [Cr].CC1=C(C(=C(C1)C)C)C.CC1=C(C(=C(C1)C)C)C Chemical compound [Cr].CC1=C(C(=C(C1)C)C)C.CC1=C(C(=C(C1)C)C)C OUGBCEDZHZZVKV-UHFFFAOYSA-N 0.000 claims description 3
- HAYOHZFDTZSDPS-UHFFFAOYSA-N [Cr].CC1C(=C(C(=C1C)C)C)C.CC1C(=C(C(=C1C)C)C)C Chemical compound [Cr].CC1C(=C(C(=C1C)C)C)C.CC1C(=C(C(=C1C)C)C)C HAYOHZFDTZSDPS-UHFFFAOYSA-N 0.000 claims description 3
- HPLXJFZCZSBAAH-UHFFFAOYSA-N [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HPLXJFZCZSBAAH-UHFFFAOYSA-N 0.000 claims description 3
- ZZRNJMAKTWOSPG-UHFFFAOYSA-N [V+3].CCC[O-].CCC[O-].CCC[O-] Chemical compound [V+3].CCC[O-].CCC[O-].CCC[O-] ZZRNJMAKTWOSPG-UHFFFAOYSA-N 0.000 claims description 3
- MGSCVPSSIVOYMY-UHFFFAOYSA-N [V+3].CC[O-].CC[O-].CC[O-] Chemical compound [V+3].CC[O-].CC[O-].CC[O-] MGSCVPSSIVOYMY-UHFFFAOYSA-N 0.000 claims description 3
- CPLPNZFTIJOEIN-UHFFFAOYSA-I [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O CPLPNZFTIJOEIN-UHFFFAOYSA-I 0.000 claims description 3
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
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- 238000010668 complexation reaction Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
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- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 2
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
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- 230000009471 action Effects 0.000 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
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- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
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- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- GJNQCYRXLGWGCO-UHFFFAOYSA-N C(C)(=O)CC(C)=O.[O-2].[V+5].[O-2].[O-2].[O-2].[O-2].[V+5] Chemical group C(C)(=O)CC(C)=O.[O-2].[V+5].[O-2].[O-2].[O-2].[O-2].[V+5] GJNQCYRXLGWGCO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000203354 Melanophylla Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- OGJYVTQMGLVHSE-UHFFFAOYSA-N [Cr+2].CC1=C(C(=C(C1)C)C)C.CC1=C(C(=C(C1)C)C)C Chemical compound [Cr+2].CC1=C(C(=C(C1)C)C)C.CC1=C(C(=C(C1)C)C)C OGJYVTQMGLVHSE-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- VKTGMGGBYBQLGR-UHFFFAOYSA-N [Si].[V].[V].[V] Chemical compound [Si].[V].[V].[V] VKTGMGGBYBQLGR-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- 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
- C08F110/02—Ethene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a multi-center supported catalyst and a preparation method and application thereof, wherein the multi-center supported catalyst comprises a carrier and active components, wherein the active components are vanadium oxide, chromium-containing organic compound and pyrrole heterocyclic compound; the chromium-containing organic compound comprises the following structure: Cr-R, wherein R is substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2‑C10One of the hydrocarbon groups; r4Is straight-chain or branched C1‑C5An alkyl group; m is Ti or Zr. The catalyst has excellent copolymerization performance and can be used for producing ethylene homopolymer and ethylene/alpha-olefin copolymer.
Description
Technical Field
The invention relates to an inorganic carrier loaded organic metal multi-center composite polyethylene catalyst and a preparation method and application thereof.
Background
Polyethylene is a variety with the largest yield in general synthetic resin, and has the characteristics of chemical resistance, good mechanical strength, electrical insulation property and the like; polypropylene is a thermoplastic synthetic resin with excellent performance, has the advantages of no toxicity, stable chemical properties, easy processing and the like, and is the product with the best heat resistance in general resins. Polyethylene and polypropylene are widely applied to various aspects of human daily life, medical treatment and health, industry and agriculture and the like, and polyolefin products with excellent performance are closely related to used catalysts.
Currently, the widely used industrial polyethylene catalysts are mainly Ziegler-Natta (Z-N) type catalysts, metallocene catalysts and chromium-based catalysts. Among them, the chromium-based catalyst is favored by the market due to its outstanding contribution to HDPE production and its irreplaceability of the product, producing about 50% of HDPE worldwide.
J.P Hogan and R.L. Bank both reported in patent US2825721 a silica gel supported chromium oxide catalyst, the latter well known Phillips inorganic chromium catalyst. Leonard m. baker and Wayne l. carrick disclose an organochromium polyethylene catalyst, i.e., an S-2 organochromium catalyst from Union Carbide, in US3324101, US3324095 and CA 759121. George L.Karapinka discloses in U.S. Pat. Nos. 3709853 and FR1591425 an organochromium polyethylene catalyst, the S-9 organochromium catalyst by Union Carbide. Although the three catalysts are very similar in structure, there are large differences in the catalytic and polymerization behavior. The Phillips inorganic chromium catalyst has high polymerization activity and short induction period, and the produced polyethylene product has wider molecular weight distribution, higher comonomer insertion amount and higher catalyst efficiency; the S-2 organic chromium catalyst has lower polymerization activity and longer induction period, and the produced polyethylene product has wider molecular weight distribution and higher density; the S-9 organic chromium catalyst has relatively high polymerization activity, short induction period and poor copolymerization, and the produced polyethylene product has narrow molecular weight distribution, high density and good hydrogen regulation sensitivity, can produce various melt index products and can meet different market requirements. For many years, the literature mainly reports more about the modification of Phillips chromium-based catalysts, and the research on the modification of S-2 and S-9 catalysts reports less, particularly the research on the modification of the S-9 catalyst reports less.
Although a number of different polyethylene catalysts already exist, there is still a need in the market for catalysts with new properties and polyethylene products thereof.
Disclosure of Invention
The invention mainly aims to provide a multi-center supported catalyst, a preparation method and application thereof, wherein the catalyst has higher activity and can develop a polyethylene product with higher performance.
In order to achieve the above object, the present invention provides a multi-center supported catalyst comprising a support and active components, wherein the active components are vanadium oxide, a chromium-containing organic compound and a pyrrole metallocene heterocyclic compound, and the vanadium oxide, the chromium-containing organic compound and the pyrrole metallocene heterocyclic compound are supported on the support;
the chromium-containing organic compound comprises the following structure:
Cr-R
wherein R is substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl;
the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5An alkyl group; m is Ti or Zr.
The multicenter supported catalyst of the invention is characterized in that the content of vanadium oxide is 0.01-10 wt% calculated by vanadium, the content of chromium-containing organic compound is 0.01-10 wt% calculated by chromium, and the content of pyrrole heterocyclic compound is 0.01-5 wt% calculated by M based on the total mass of the multicenter supported catalyst.
The multi-center supported catalyst provided by the invention is characterized in that the carrier is one or more of the group consisting of silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, magnesium oxide, calcium oxide and inorganic clay; and/or the carrier is obtained by dehydration, deoxidation and modification.
The multi-center supported catalyst provided by the invention has the advantages that the modifier for modifying the carrier is one or more of the group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum.
The multi-center supported catalyst of the invention, wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C5One of the hydrocarbon groups; the R is4Is CH3-or CH3CH2-。
The multi-center supported catalyst provided by the invention is characterized in that the pyrrole metallocene heterocyclic compound is:
[(η5-C9H6)CH2(2-C4H3N)]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-C4H3N)]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-C4H3N)]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-C4H3N)]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Ti(NEt2)2and
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NEt2)2one or more of the group.
The multi-center supported catalyst provided by the invention is characterized in that the substituted or unsubstituted cyclopentadienyl has the following structure:
wherein, R is3、R4、R5、R6And R7Each independently hydrogen, aliphatic hydrocarbyl of 1-20 carbon atoms;
the substituted or unsubstituted indenyl group has the following structure:
wherein, R is8、R9、R10And R11Each independently is hydrogen, aliphatic hydrocarbyl of 1-10 carbon atoms; the R is12、R13And R14Each independently is hydrogen, aliphatic hydrocarbyl of 1-10 carbon atoms;
the substituted or unsubstituted fluorenyl group has the following structure:
wherein, R is15、R16、R17、R18、R19、R20、R21、R22And R23Each independently hydrogen, an aliphatic hydrocarbon group of 1 to 10 carbon atoms.
The multi-center supported catalyst of the invention, wherein R is3、R4、R5、R6And R7Each independently is one of hydrogen, methyl, ethyl, propyl, butyl, amyl and allyl; the R is8、R9、R10、R11、R12、R13And R14Each independently is one of hydrogen, methyl, ethyl, propyl, butyl, amyl and allyl; the R is15、R16、R17、R18、R19、R20、R21、R22And R23Each independently is one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and allyl.
In order to achieve the above object, the present invention also provides a preparation method of a multi-site supported catalyst, comprising the steps of:
step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting;
step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and
step 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain a multi-center supported catalyst;
the organic chromium source comprises the following structure:
R'-Cr-R
wherein R and R' are each independently substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl;
the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5An alkyl group; m is Ti or Zr.
The preparation method of the multi-center supported catalyst comprises the following steps of (1) preparing a vanadium source from water-soluble vanadium-containing salt or water-insoluble vanadium-containing salt; the water-soluble vanadium-containing salt is nitrate, phosphate, sulfate, acetate or metavanadate of vanadium, and the water-insoluble vanadium-containing salt is vanadium bisacetylacetonate oxide, vanadium triisopropoxide, vanadium tripropanolate oxide, vanadium acetylacetonate, vanadium triethoxide, vanadyl chloride or vanadium trisilicide.
The preparation method of the multi-center supported catalyst comprises the following step of preparing a water-soluble vanadium-containing salt from ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate oxide (IV) hydrate, vanadium sulfate (III), vanadyl trichloride oxide, sodium orthovanadate, sodium metavanadate or vanadium acetate existing in an acid solution.
The preparation method of the multi-center supported catalyst comprises the step of preparing an organic chromium source, wherein the organic chromium source is one or more of the group consisting of bis (cyclopentadiene) chromium (II), bis (ethylcyclopentadiene) chromium (II), bis (pentamethylcyclopentadiene) chromium (II), bis (tetramethylcyclopentadiene) chromium (II) and bis (isopropylcyclopentadiene) chromium (II).
The preparation method of the multi-center supported catalyst comprises the following steps:
step a, reacting 2-pyrrole-carbaldehyde shown in formula II or a derivative thereof with indene to prepare nitrogen-containing fulvene shown in formula III R1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups;
b, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step c, ligand of formula IV containing pyrrole N heterocyclic ring and M [ N (R)4)2]4A complexation reaction occurs to produce a metallocene catalyst, R4Is straight-chain or branched C1-C5Alkyl, M is Ti or Zr;
the invention relates to a preparation method of a multi-center supported catalyst, wherein the step a is as follows: dissolving 2-pyrrole formaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent, cooling to-10-5 ℃, dropwise adding pyrrolidine, heating to room temperature, and stirring for reaction for 0.5-20 hours to obtain nitrogen-containing fulvene shown in the formula III;
wherein, the mass ratio of 2-pyrrole formaldehyde or its derivative, indene and tetrahydropyrrole in formula II is 1: 1-5: 1 to 5.
The preparation method of the multi-center supported catalyst comprises the following steps: dissolving the nitrogen-containing fulvene in the formula III obtained in the step a in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, heating to 40-70 ℃, and stirring for reaction for 5-50h to obtain a pyrrole N heterocyclic ring-containing ligand in the formula IV;
wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5.
The preparation method of the multi-center supported catalyst comprises the following steps: subjecting the product obtained in step bDissolving a pyrrole N heterocyclic ring-containing ligand in a formula IV in an organic solvent, cooling to-10-5 ℃, and then dropwise adding M [ N (R) dissolved in the organic solvent4)2]4Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;
wherein, formula IV contains pyrrole N heterocyclic ligand and M [ N (R)4)2]4In a molar ratio of 1: 0.5 to 5.
In order to achieve the above object, the present invention further provides an olefin polymerization process, which is carried out under the action of the above-mentioned multi-site supported catalyst.
The olefin polymerization reaction method is characterized in that the olefin is one or more of a group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
The olefin polymerization reaction method of the invention is characterized in that the multi-center supported catalyst is a main catalyst, the alkylaluminium or aluminoxane compound is a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.
The invention has the beneficial effects that:
according to the multi-center supported catalyst provided by the invention, organic chromium and a metallocene active component are loaded on an inorganic carrier supported inorganic vanadium catalyst to form the multi-active center catalyst, so that the copolymerization performance of the catalyst can be improved, the content and distribution of a comonomer are optimized, the amount of the comonomer inserted into a low molecular weight end is reduced, the amount of the comonomer inserted into a high molecular weight end is increased, more tie molecules are easily formed, a polyethylene product with higher performance is developed, and the catalyst also has higher activity.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The invention discloses a multi-center supported catalyst which comprises a carrier and active components, wherein the active components are vanadium oxide, chromium-containing organic compound and pyrrole heterocyclic compound;
the chromium-containing organic compound comprises the following structure:
Cr-R
wherein R is substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl;
the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5An alkyl group; m is Ti or Zr.
In the technical scheme of the invention, the carrier is generally an inorganic carrier, for example, selected from silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, magnesium oxide, calcium oxide, inorganic clay and the combination thereof; preferably, the support is an amorphous porous silica gel modified with Ti, Al, F, or the like. In another embodiment, the pore volume is 0.5-5.0 cm3A surface area of 50 to 800m2/g。
The active component vanadium of the invention is loaded on the carrier in the form of inorganic oxide, such as vanadium trioxide, vanadium dioxide, vanadium pentoxide and the like.
The chromium-containing organic compounds of the present invention generally comprise the following structure:
Cr-R
wherein R is substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl.
In detail, the substituted or unsubstituted cyclopentadienyl group has the following structure:
wherein, R is3、R4、R5、R6And R7Each independently hydrogen, aliphatic hydrocarbyl of 1-20 carbon atoms; preferably one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and allyl.
The substituted or unsubstituted indenyl group has the following structure:
wherein, R is8、R9、R10And R11Each independently is hydrogen, aliphatic hydrocarbyl of 1-10 carbon atoms; the R is12、R13And R14Each independently is hydrogen, aliphatic hydrocarbyl of 1-10 carbon atoms; r8、R9、R10、R11、R12、R13And R14Each independently is preferably one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and allyl.
The substituted or unsubstituted fluorenyl group has the following structure:
wherein, R is15、R16、R17、R18、R19、R20、R21、R22And R23Each independently hydrogen, an aliphatic hydrocarbon group of 1 to 10 carbon atoms, preferably one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and allyl.
The pyrrole cyclopentadiene heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups, preferably H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C5One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5Alkyl, preferably CH3-or CH3CH2-; m is Ti or Zr.
The azole metallocene heterocyclic compound of the present invention may further preferably be:
[(η5-C9H6)CH2(2-C4H3N)]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-C4H3N)]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-C4H3N)]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-C4H3N)]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Ti(NEt2)2and
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NEt2)2one or more of the group.
In the multi-center supported catalyst, the loading amount of the Cr active center on the inorganic carrier is calculated by Cr, and is preferably 0.01-10 wt% of the total weight of the catalyst. The V active center loading amount is calculated by V, and is preferably 0.01-10 wt% of the total weight of the catalyst. The M active center loading amount is calculated by M, and preferably 0.01-5 wt% of the total weight of the catalyst.
The invention also provides a preparation method of the supported multi-center composite catalyst, which comprises the following steps:
step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting;
step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and
step 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain a multi-center supported catalyst;
the organic chromium source comprises the following structure:
R'-Cr-R
wherein R and R' are each independently substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl;
the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-、Saturated or containing double bonds, straight or branched C2-C10One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5An alkyl group; m is Ti or Zr.
In a preferred embodiment, in step 1, the inorganic carrier is immersed in an aqueous solution of an inorganic vanadium source, kept at room temperature to 60 ℃ for 1 to 12 hours, and then dried at 100 to 200 ℃ for 1 to 18 hours, in which case the drying speed may be increased by forced air drying, and then calcined at 150 to 1000 ℃ in oxygen or air for 1 to 10 hours, and then cooled, wherein the air is replaced with an inert gas such as nitrogen or argon when cooled to 300 to 400 ℃.
Wherein the inorganic vanadium source is selected from water-soluble vanadium-containing salts and water-insoluble vanadium-containing salts; the water-soluble vanadium-containing salt is selected from the group consisting of nitrate, phosphate, sulfate, acetate of vanadium, and various salts of metavanadate, and the water-insoluble vanadium-containing salt is selected from the group consisting of vanadium bisacetylacetonate oxide, vanadium triisopropoxide, vanadium tripropanolate oxide, vanadium acetylacetonate, vanadium triethoxide, vanadyl chloride, trivanadium silicide, and the like.
The concentration and the amount of the vanadium source aqueous solution are not particularly limited in the present invention, as long as the loading amount of vanadium in the catalyst is 0.01 wt% to 10 wt% in terms of vanadium.
In a preferred embodiment, in the step 2, the catalyst precursor obtained in the step 1 is immersed in an organic metal promoter solution in an inert gas atmosphere, and is reacted at room temperature to 200 ℃ for 1 to 30 hours, and then dried at 60 to 200 ℃ for 1 to 12 hours to complete the modification of the catalyst precursor, and in this case, the drying speed can be increased by vacuum drying.
Wherein, the organic metal cocatalyst is used as a modifier to modify the carrier so as to remove the moisture and oxygen in the catalyst precursor. The organometallic cocatalyst can be one of methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum or a mixture of the methylaluminoxane, the trimethylaluminum, the triethylaluminum and the triisobutylaluminum. The amount of the organometallic cocatalyst may be generally 2 to 30 wt% based on the total weight of the catalyst, but the present invention is not particularly limited.
In a preferred embodiment, in the step 3, the catalyst precursor obtained in the step 2 is immersed in an organic solution of an organic chromium source and a heterocyclic pyrrole-metallocene compound in an inert gas atmosphere, the reaction is carried out for 1 to 10 hours at a temperature ranging from room temperature to 100 ℃, then a solvent is added, the reaction solution is stirred and washed for several times, the reaction solution is washed for 0.5 to 5 hours at a temperature ranging from room temperature to 100 ℃, and then the reaction solution is dried for 2 to 8 hours at a temperature ranging from 60 to 120 ℃, and at this time, the drying speed can also be accelerated by vacuum drying.
Wherein, the organic chromium source comprises the following structure:
R'-Cr-R
wherein R and R' are independently substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, and the substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl is described in detail above and will not be described herein again. As a preferred embodiment, the organic chromium source is selected from bis (cyclopentadiene) chromium (II), bis (ethylcyclopentadiene) chromium (II), bis (pentamethylcyclopentadiene) chromium (II), bis (tetramethylcyclopentadiene) chromium (II), bis (isopropylcyclopentadiene) chromium (II), and the like, and combinations thereof.
The structure of the heterocyclic azole compounds is also described in detail above and will not be described further. The concentration of the organic chromium source in the impregnation solution and the concentration of the heterocyclic pyrrole-metallocene compound in the impregnation solution are not particularly limited, as long as the loading of chromium on the catalyst is 0.01 to 10 wt% in terms of chromium and the loading of the heterocyclic pyrrole-metallocene compound on the catalyst is 0.01 to 5 wt% in terms of M.
The preparation method of the pyrrole metallocene heterocyclic compound provided by the invention comprises the following steps:
step a, reacting 2-pyrrole-carbaldehyde shown in formula II or a derivative thereof with indene to prepare nitrogen-containing fulvene shown in formula III R1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups;
b, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step c, ligand of formula IV containing pyrrole N heterocyclic ring and M [ N (R)4)2]4A complexation reaction occurs to produce a metallocene catalyst, R4Is straight-chain or branched C1-C5Alkyl, M is Ti or Zr;
in detail, the preparation method of the pyrrole metallocene heterocyclic compound comprises the following steps:
step a, dissolving 2-pyrrole-carbaldehyde or a derivative thereof and indene in a formula II in a Schlenk bottle in an organic solvent, cooling to-10-5 ℃, for example, placing in an ice water bath, and then slowly dropwise adding pyrrolidine, wherein the ratio of the amount of the 2-pyrrole-carbaldehyde or the derivative thereof to the amount of the indene to the amount of the pyrrolidine is 1: 1-5: 1-5; after the dropwise addition, the temperature is raised to the room temperature, and the mixture is stirred for 0.5 to 20 hours to react; and after the reaction is finished, carrying out liquid separation extraction and washing by using an organic solvent, taking an organic phase, drying the organic phase, and carrying out rotary evaporation to obtain the nitrogen-containing fulvene in the formula III. Wherein the organic solvent can be one or more of methanol, ethanol, formaldehyde, acetaldehyde, diethyl ether, toluene and ethylbenzene.
B, dissolving the nitrogen-containing fulvene of the formula III prepared in the step a in an organic solvent such as tetrahydrofuran in a Schlenk bottle, cooling to-10-5 ℃, for example, placing in an ice water bath, then dropwise adding lithium aluminum hydride dissolved in the solvent (such as tetrahydrofuran), withdrawing the ice water bath, slowly heating to 40-70 ℃, reacting for 5-50h, adding the organic solvent, separating, extracting, washing, drying the organic phase, and then performing rotary evaporation to obtain a ligand containing pyrrole N heterocycle of the formula IV; wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5. Wherein the organic solvent is one or more of ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.
Step c, mixing M (N (R) in Schlenk flask4)2)4Dissolving in an organic solvent, cooling to-10-5 ℃, for example, placing in an ice-water bath, dissolving the pyrrole N heterocycle-containing ligand of formula IV prepared in the step b in the organic solvent, slowly adding into a Schlenk bottle, removing the ice-water bath, heating to 50-100 ℃, and reacting for 1-30 h.
OrOr dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step b in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Zr [ N (R) dissolved in the organic solvent4)2]4After the dripping is finished, the temperature is raised to 50-100 ℃, and the stirring reaction is carried out for 1-30 h.
Wherein, formula IV contains pyrrole N heterocyclic ligand and M [ N (R)4)2]4In a molar ratio of 1: 0.5 to 5.
And after the reaction is finished, pumping the solvent, and finally recrystallizing in an organic solvent at a low temperature to obtain the product. Wherein the organic solvent is one or more of methane, ethane, ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.
The whole reaction process of the preparation method of the pyrrole metallocene heterocyclic compound is always carried out under the protection of inert gas, and the inert gas can be one of hydrogen, nitrogen, helium and argon.
In summary, the invention uses inorganic compound as carrier, firstly, the vanadium source is dipped on the carrier, and then the carrier is roasted at high temperature to prepare the catalyst parent body loaded with inorganic vanadium; and adding an organic metal cocatalyst into the solution containing the catalyst precursor to modify the carrier, and finally adding an organic solution of an organic chromium source and a pyrrole heterocyclic compound into the solution containing the catalyst precursor to carry out loading, thereby preparing the multi-center supported catalyst.
The multi-site supported catalyst of the present invention as described above can be used for producing ethylene homopolymers and ethylene/α -olefin copolymers.
The present invention is not particularly limited in the manner of olefin polymerization, and for example, the polymerization is carried out by a conventional slurry polymerization method, and the specific operations are as follows: firstly, heating a polymerization reaction kettle in vacuum (100 ℃), then replacing the polymerization reaction kettle with high-purity nitrogen, repeatedly operating for three times, then replacing the polymerization reaction kettle with a small amount of ethylene monomer once, and finally filling the reaction kettle with ethylene to a micro-positive pressure (0.12 MPa); adding a refined solvent subjected to dehydration and deoxidation treatment into a reaction kettle, taking a certain amount of alkyl aluminum as a cocatalyst, respectively adding a certain amount of hydrogen and a comonomer in a hydrogen blending copolymerization experiment, and finally adding the multi-center supported catalyst to start a polymerization reaction; the instantaneous consumption of monomer ethylene is collected on line in the reaction process (by connecting a high-precision ethylene mass flow meter with a computer) and recorded by the computer, and the reaction is stopped after the reaction is carried out for a certain time (for example, 1 hour) at a certain temperature (for example, 35 ℃ to 100 ℃); the polymer was washed, dried in vacuo, weighed and analyzed.
The catalyst of the present invention can produce ethylene homopolymers and ethylene/alpha-olefin copolymers (part of the product having a bimodal distribution) having a broad molecular weight distribution (MWD ═ 10 to 60) in a single reactor or a combination of reactors. By using the catalyst of the present invention, the molecular weight and distribution of ethylene homopolymer and ethylene and α -olefin copolymer and the comonomer content and distribution thereof can be conveniently and easily adjusted by changing the amount of co-catalyst used, polymerization temperature, molecular weight regulator and the like, so that a polymer product having desired properties can be conveniently and easily obtained.
The supported multi-center composite catalyst provided by the invention is characterized in that an organic chromium system and a metallocene active component are supported on an inorganic carrier supported inorganic vanadium catalyst to form a multi-active-center catalyst, the copolymerization performance of the catalyst can be improved, the content and the distribution of a comonomer are optimized, the amount of the comonomer inserted into a low molecular weight end is reduced, and the amount of the comonomer inserted into a high molecular weight end is increased, so that more tie molecules are easily formed, a polyethylene product with higher performance is developed, and the catalyst also has higher activity.
The present invention is explained in more detail with reference to the following examples, which do not limit the scope of the present invention.
The silica gel employed in the examples was commercially available as Davison 955.
Various polymer properties in the examples were measured according to the following methods:
example 1:
inorganic carrier supported multi-center composite catalyst, wherein the inorganic carrier is silicon dioxide (pore volume is 0.8 cm)3(ii)/g; the surface area of the inorganic carrier is 380m2(iv)/g); the inorganic vanadium source is vanadium nitrate, the organic chromium source is bis (cyclopentadiene) chromium (II), and the pyrrole heterocyclic compound is [ (. eta. ])5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NMe2)2。
The preparation method of the pyrrole heterocyclic compound comprises the following steps: reacting 3-CH3-4-CH3-5-CH3Cooling the-2-pyrrole-carbaldehyde and indene to-10 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 2: 1, heating to room temperature, stirring and reacting for 10 hours to obtain nitrogen-containing fulvene; then cooling to-4 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 2, heating to 70 ℃, and stirring for reaction for 10 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to-1 deg.C, and adding Zr (NMe) dissolved in organic solvent2)4And heating to 70 ℃, and stirring for reaction for 13h to obtain the pyrrole heterocyclic compound.
The preparation method of the catalyst comprises the following steps: step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting; step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain the multi-center supported catalyst. The catalyst prepared by the preparation method has the advantages that the Cr active center loading capacity is 3.2 wt% of the total weight of the catalyst, the V active center loading capacity is 3.9 wt% of the total weight of the catalyst, the Zr active center loading capacity is 0.8 wt% of the total weight of the catalyst, the organic metal cocatalyst is methylaluminoxane, and the dosage of the organic metal cocatalyst accounts for 8 wt% of the total weight of the catalyst. The copolymerisation of ethylene and 1-hexene was carried out using a conventional slurry polymerisation process with a 1-hexene/ethylene ratio of 0.2. The catalyst activity was found to be 8230g PE/g Cat and the product density was found to be 0.940g/cm3。
Example 2:
inorganic carrier supported multi-center composite catalyst, wherein the inorganic carrier is silicon dioxide (pore volume is 1.3 cm)3(ii)/g; the surface area of the inorganic carrier is 590m2(iv)/g); the inorganic vanadium source is vanadium sulfate, the organic chromium source is bis (ethylcyclopentadiene) chromium (II), and the pyrrole heterocyclic compound is [ (. eta. ])5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NMe2)2。
The preparation method of the pyrrole heterocyclic compound comprises the following steps: reacting 3-CH3-4-CH3Cooling the-2-pyrrole-carbaldehyde and indene to-5 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 2: 2, heating to room temperature, stirring and reacting for 5 hours to obtain nitrogen-containing fulvene; then cooling to-6 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 0.5, heating to 60 ℃, stirring and reacting for 15h to obtain a ligand containing pyrrole N heterocycle; cooling to-3 deg.C, and adding Zr (NMe) dissolved in organic solvent2)4And heating to 60 ℃, and stirring for reaction for 7 hours to obtain the pyrrole cyclopentadiene heterocyclic compound.
The preparation method of the catalyst comprises the following steps: step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting; step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain the multi-center supported catalyst. According to the catalyst prepared by the preparation method, the loading of a Cr active center is 1.2 wt% of the total weight of the catalyst, the loading of a V active center is 0.06 wt% of the total weight of the catalyst, the loading of a Zr active center is 0.15 wt% of the total weight of the catalyst, an organic metal cocatalyst is trimethylaluminum, and the dosage of the organic metal cocatalyst accounts for 22 wt% of the total weight of the catalyst. The copolymerisation of ethylene and 1-hexene was carried out using a conventional slurry polymerisation process with a 1-hexene/ethylene ratio of 0.2. The catalyst activity was found to be 5300g PE/g Cat, and the product density was found to be 0.948g/cm3。
Example 3:
inorganic carrier supported multi-center composite catalyst, wherein the inorganic carrier is silicon dioxide (pore volume is 2.8 cm)3(ii)/g; the surface area of the inorganic carrier was 720m2(iv)/g); the inorganic vanadium source is vanadium acetate, the organic chromium source is bis (pentamethylcyclopentadienyl) chromium (II), and the pyrrole heterocyclic compound is [ (. eta. ])5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NMe2)2。
The preparation method of the pyrrole heterocyclic compound comprises the following steps:reacting 3-CH3-4-CH3Cooling the-2-pyrrole-carbaldehyde and indene to 0 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 2: 3, heating to room temperature, stirring and reacting for 1 hour to obtain nitrogen-containing fulvene; then cooling to-10 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1:1, heating to 65 ℃, and stirring for reaction for 5 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to-7 deg.C, and adding Ti (NMe) dissolved in organic solvent2)4And heating to 80 ℃, and stirring for reacting for 19h to obtain the pyrrole heterocyclic compound.
The preparation method of the catalyst comprises the following steps: step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting; step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain the multi-center supported catalyst. The catalyst prepared by the preparation method has the advantages that the Cr active center loading amount is 1.8 wt% of the total weight of the catalyst, the V active center loading amount is 1.2 wt% of the total weight of the catalyst, the Ti active center loading amount is 0.25 wt% of the total weight of the catalyst, the organometallic cocatalyst is triethyl aluminum, and the dosage of the organometallic cocatalyst accounts for 28 wt% of the total weight of the catalyst. The copolymerisation of ethylene and 1-hexene was carried out using a conventional slurry polymerisation process with a 1-hexene/ethylene ratio of 0.2. The catalyst activity was found to be 8850g PE/g Cat, the product density was found to be 0.946g/cm3。
Example 4:
inorganic carrier supported multi-center composite catalyst, wherein the inorganic carrier is silicon dioxide (pore volume is 3.9 cm)3(ii)/g; the surface area of the inorganic carrier is 638m2(iv)/g); the inorganic vanadium source is triisopropoxytrianisum, the organic chromium source is bis (pentamethylcyclopentadienyl) chromium (II), and the pyrrole heterocyclic compound is [ (. eta. ])5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NEt2)2。
The preparation method of the pyrrole heterocyclic compound comprises the following steps: reacting 5-CH3Cooling the-2-pyrrole-carbaldehyde and indene to 5 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 3: 3, thenThen heating to room temperature, stirring and reacting for 0.5 hour to obtain nitrogen-containing fulvene; then cooling to-2 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 4, heating to 55 ℃, and stirring for reaction for 20 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to 5 deg.C, and adding Ti (NEt) dissolved in organic solvent2)4Heating to 100 ℃, and stirring for reaction for 30 hours to obtain the pyrrole heterocyclic compound.
The preparation method of the catalyst comprises the following steps: step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting; step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain the multi-center supported catalyst. The catalyst prepared by the preparation method has the advantages that the Cr active center loading amount is 0.9 wt% of the total weight of the catalyst, the V active center loading amount is 0.5 wt% of the total weight of the catalyst, the Ti active center loading amount is 1.6 wt% of the total weight of the catalyst, the organic metal cocatalyst is triisobutylaluminum, and the dosage of the organic metal cocatalyst accounts for 20 wt% of the total weight of the catalyst. The copolymerisation of ethylene and 1-hexene was carried out using a conventional slurry polymerisation process with a 1-hexene/ethylene ratio of 0.2. The catalyst activity was found to be 5950g PE/g Cat, the product density was found to be 0.938g/cm3。
Example 5:
inorganic carrier supported multi-center composite catalyst, wherein the inorganic carrier is silicon dioxide (pore volume is 5.0 cm)3(ii)/g; the surface area of the inorganic carrier was 650m2(iv)/g); the inorganic vanadium source is vanadium acetylacetonate, the organic chromium source is bis (isopropylcyclopentadiene) chromium (II), and the pyrrole heterocyclic compound is [ (. eta. ])5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NEt2)2。
The preparation method of the pyrrole heterocyclic compound comprises the following steps: reacting 3-CH3-4-CH3-5-CH3Cooling the-2-pyrrole-carbaldehyde and indene to-3 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 3: 2, heating to room temperature, stirring and reacting for 20 hours to obtain nitrogen-containing fulvene; cooling to 0 deg.C, and drippingAnd (3) adding aluminum lithium hydride, wherein the molar ratio of the nitrogen-containing fulvene to the aluminum lithium hydride is 1: 5, heating to 40 ℃, and stirring for reacting for 1h to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to-10 deg.C, and adding Ti (NEt) dissolved in organic solvent2)4And heating to 90 ℃, and stirring for reaction for 25 hours to obtain the pyrrole cyclopentadiene heterocyclic compound.
The preparation method of the catalyst comprises the following steps: step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting; step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain the multi-center supported catalyst. The catalyst prepared by the preparation method has the advantages that the Cr active center loading capacity is 0.6 wt% of the total weight of the catalyst, the V active center loading capacity is 1.4 wt% of the total weight of the catalyst, the Ti active center loading capacity is 2.2 wt% of the total weight of the catalyst, the organic metal cocatalyst is methylaluminoxane, and the dosage of the organic metal cocatalyst accounts for 18 wt% of the total weight of the catalyst. The copolymerisation of ethylene and 1-hexene was carried out using a conventional slurry polymerisation process with a 1-hexene/ethylene ratio of 0.2. The catalyst activity was found to be 9500g PE/g Cat, the product density was found to be 0.936g/cm3。
Example 6:
inorganic carrier supported multi-center composite catalyst, wherein the inorganic carrier is silicon dioxide (pore volume is 4.2 cm)3(ii)/g; the surface area of the inorganic carrier is 800m2(iv)/g); the inorganic vanadium source is acetylacetone vanadium oxide, the organic chromium source is bis (tetramethylcyclopentadiene) chromium (II), and the pyrrole heterocyclic compound is [ (. eta. ])5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NMe2)2。
The preparation method of the pyrrole heterocyclic compound comprises the following steps: 4-CH is added3Cooling the-2-pyrrole-carbaldehyde and indene to 3 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 1:1, then heating to room temperature, stirring and reacting for 8 hours to obtain nitrogen-containing fulvene; then cooling to 4 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 3, heating to 50 ℃, stirring and reacting for 30 hours to obtain the pyrrole N heterocyclic ring-containing ligand(ii) a Cooling to-7 deg.C, and adding Ti (NMe) dissolved in organic solvent2)4And heating to 50 ℃, and stirring for reaction for 1h to obtain the pyrrole heterocyclic compound.
The preparation method of the catalyst comprises the following steps: step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting; step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain the multi-center supported catalyst. The catalyst prepared by the preparation method has the advantages that the Cr active center loading capacity is 2.5 wt% of the total weight of the catalyst, the V active center loading capacity is 2.1 wt% of the total weight of the catalyst, the Ti active center loading capacity is 1.1 wt% of the total weight of the catalyst, the organic metal cocatalyst is methylaluminoxane, and the dosage of the organic metal cocatalyst accounts for 30 wt% of the total weight of the catalyst. The copolymerisation of ethylene and 1-hexene was carried out using a conventional slurry polymerisation process with a 1-hexene/ethylene ratio of 0.2. The catalyst activity was found to be 8500g PE/g Cat, and the product density was found to be 0.942g/cm3。
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (19)
1. A multi-center supported catalyst is characterized by comprising a carrier and active components, wherein the active components are vanadium oxide, a chromium-containing organic compound and a pyrrole metallocene heterocyclic compound, and the vanadium oxide, the chromium-containing organic compound and the pyrrole metallocene heterocyclic compound are supported on the carrier;
the chromium-containing organic compound comprises the following structure:
Cr-R
wherein R is substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl;
the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5An alkyl group; m is Ti or Zr.
2. The multi-center supported catalyst according to claim 1, wherein the content of the vanadium oxide is 0.01 to 10 wt% in terms of vanadium, the content of the chromium-containing organic compound is 0.01 to 10 wt% in terms of chromium, and the content of the azole heterocyclic compound is 0.01 to 5 wt% in terms of M, based on the total mass of the multi-center supported catalyst.
3. The multi-center supported catalyst according to claim 1, wherein the carrier is one or more selected from the group consisting of silica, alumina, titania, zirconia, magnesia, calcia and inorganic clay; and/or the carrier is obtained by dehydration, deoxidation and modification.
4. The multi-center supported catalyst according to claim 3, wherein the modifier for modifying the support is one or more selected from the group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum.
5. The multi-center supported catalyst of claim 1, wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C5One of the hydrocarbon groups; the R is4Is CH3-or CH3CH2-。
6. The multi-site supported catalyst according to claim 5, wherein the azole metallocene heterocyclic compound is:
[(η5-C9H6)CH2(2-C4H3N)]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NMe2)2、
[(η5-C9H6)CH2(2-C4H3N)]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Zr(NEt2)2、
[(η5-C9H6)CH2(2-C4H3N)]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NMe2)2、
[(η5-C9H6)CH2(2-C4H3N)]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(5-CH3-C4H2N))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-C4HN))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(3-CH3-5-CH3-C4HN))]Ti(NEt2)2、
[(η5-C9H6)CH2(2-(4-CH3-5-CH3-C4HN))]Ti(NEt2)2and
[(η5-C9H6)CH2(2-(3-CH3-4-CH3-5-CH3-C4N))]Ti(NEt2)2one or more of the group.
7. The multi-site supported catalyst of claim 1, wherein the substituted or unsubstituted cyclopentadienyl group has the structure:
wherein, R is3、R4、R5、R6And R7Each independently hydrogen, aliphatic hydrocarbyl of 1-20 carbon atoms;
the substituted or unsubstituted indenyl group has the following structure:
wherein, R is8、R9、R10And R11Each independently is hydrogen, aliphatic hydrocarbyl of 1-10 carbon atoms; the R is12、R13And R14Each independently is hydrogen, aliphatic hydrocarbyl of 1-10 carbon atoms;
the substituted or unsubstituted fluorenyl group has the following structure:
wherein, R is15、R16、R17、R18、R19、R20、R21、R22And R23Each independently hydrogen, an aliphatic hydrocarbon group of 1 to 10 carbon atoms.
8. The multi-center supported catalyst of claim 7, wherein R is3、R4、R5、R6And R7Each independently is one of hydrogen, methyl, ethyl, propyl, butyl, amyl and allyl; the R is8、R9、R10、R11、R12、R13And R14Independently of one another are hydrogen, methyl, ethyl, propyl, butyl, pentyl and allylOne of (1); the R is15、R16、R17、R18、R19、R20、R21、R22And R23Each independently is one of hydrogen, methyl, ethyl, propyl, butyl, pentyl and allyl.
9. A preparation method of a multi-center supported catalyst is characterized by comprising the following steps:
step 1, dipping a carrier into a solution containing a vanadium source, drying and roasting;
step 2, carrying out dehydration, deoxidation and activation treatment on the carrier obtained in the step 1; and
step 3, dipping the activated carrier obtained in the step 2 into a solution containing an organic chromium source and a pyrrole metallocene heterocyclic compound to obtain a multi-center supported catalyst;
the organic chromium source comprises the following structure:
R'-Cr-R
wherein R and R' are each independently substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl;
the pyrrole heterocyclic compound has the following structure as shown in the formula I:
wherein R is1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups; r4Is straight-chain or branched C1-C5An alkyl group; m is Ti or Zr.
10. The method for preparing a multi-center supported catalyst according to claim 9, wherein the vanadium source is a water-soluble vanadium-containing salt or a water-insoluble vanadium-containing salt; the water-soluble vanadium-containing salt is nitrate, phosphate, sulfate, acetate or metavanadate of vanadium, and the water-insoluble vanadium-containing salt is vanadium bisacetylacetonate oxide, vanadium triisopropoxide, vanadium tripropanolate oxide, vanadium acetylacetonate, vanadium triethoxide, vanadyl chloride or vanadium trisilicide.
11. The method of claim 10, wherein the water-soluble vanadium-containing salt is ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (iv) oxide sulfate hydrate, vanadium (iii) sulfate, vanadium oxide trichloride, sodium orthovanadate, sodium metavanadate, or vanadium acetate present in an acid solution.
12. The method for preparing the multi-center supported catalyst according to claim 9, wherein the organic chromium source is one or more selected from the group consisting of bis (cyclopentadiene) chromium (II), bis (ethylcyclopentadiene) chromium (II), bis (pentamethylcyclopentadiene) chromium (II), bis (tetramethylcyclopentadiene) chromium (II), and bis (isopropylcyclopentadiene) chromium (II).
13. The method for preparing a multi-site supported catalyst according to claim 9, wherein the method for preparing the heterocyclic azole compound comprises the steps of:
step a, reacting 2-pyrrole-carbaldehyde shown in formula II or a derivative thereof with indene to prepare nitrogen-containing fulvene shown in formula III R1、R2And R3Each independently selected from H, CH3-, saturated or containing double bonds, straight-chain or branched C2-C10One of the hydrocarbon groups;
b, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step c, ligand of formula IV containing pyrrole N heterocyclic ring and M [ N (R)4)2]4A complexation reaction occurs to produce a metallocene catalyst, R4Is straight-chain or branched C1-C5Alkyl, M is Ti or Zr;
14. the method for preparing a multi-site supported catalyst according to claim 13, wherein the step a is: dissolving 2-pyrrole formaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent, cooling to-10-5 ℃, dropwise adding pyrrolidine, heating to room temperature, and stirring for reaction for 0.5-20 hours to obtain nitrogen-containing fulvene shown in the formula III;
wherein, the mass ratio of 2-pyrrole formaldehyde or its derivative, indene and tetrahydropyrrole in formula II is 1: 1-5: 1 to 5.
15. The method for preparing a multi-site supported catalyst according to claim 13, wherein the step b is: dissolving the nitrogen-containing fulvene in the formula III obtained in the step a in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, heating to 40-70 ℃, and stirring for reaction for 5-50h to obtain a pyrrole N heterocyclic ring-containing ligand in the formula IV;
wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5.
16. The method for preparing a multi-site supported catalyst according to claim 13, wherein the step c is: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step b in an organic solvent, cooling to-10-5 ℃, and then dropwise adding M [ N (R) dissolved in the organic solvent4)2]4Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;
wherein, formula IV contains pyrrole N heterocyclic ligand and M [ N (R)4)2]4In a molar ratio of 1: 0.5 to 5.
17. A process for the polymerization of olefins carried out under the action of a multi-site supported catalyst according to any of claims 1 to 8.
18. The method of claim 17, wherein the olefin is one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
19. The olefin polymerization reaction process of claim 17, wherein the multi-center supported catalyst of any one of claims 1 to 8 is a main catalyst, the aluminum alkyl or aluminoxane compound is a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.
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