CN103772540A - Loaded chromium base catalyst, preparation method and application thereof - Google Patents
Loaded chromium base catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN103772540A CN103772540A CN201210401426.9A CN201210401426A CN103772540A CN 103772540 A CN103772540 A CN 103772540A CN 201210401426 A CN201210401426 A CN 201210401426A CN 103772540 A CN103772540 A CN 103772540A
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- China
- Prior art keywords
- chromium
- catalyst component
- aluminum
- carrier
- compound
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 59
- 239000011651 chromium Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- 239000011777 magnesium Substances 0.000 claims abstract description 42
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 39
- -1 aluminum compound Chemical class 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 229920002554 vinyl polymer Polymers 0.000 claims description 29
- 229960001866 silicon dioxide Drugs 0.000 claims description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 27
- 239000004411 aluminium Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000012041 precatalyst Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- CYHOFESITORDDD-UHFFFAOYSA-M C(CCC)O[Cr](=O)(=O)O Chemical group C(CCC)O[Cr](=O)(=O)O CYHOFESITORDDD-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- NPEFICOHWIZPMC-UHFFFAOYSA-L dichloroalumanylium;ethanolate Chemical compound [Cl-].[Cl-].CCO[Al+2] NPEFICOHWIZPMC-UHFFFAOYSA-L 0.000 claims description 2
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 8
- 150000002681 magnesium compounds Chemical class 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004711 α-olefin Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000001845 chromium compounds Chemical class 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 description 24
- 239000000741 silica gel Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000001994 activation Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 235000011147 magnesium chloride Nutrition 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- OAFMYIADTCIEFV-UHFFFAOYSA-N hexane;triethylalumane Chemical compound CCCCCC.CC[Al](CC)CC OAFMYIADTCIEFV-UHFFFAOYSA-N 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HJLHTTJLVALHOP-UHFFFAOYSA-N hexane;hydron;chloride Chemical compound Cl.CCCCCC HJLHTTJLVALHOP-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a preparation method and an application of a loaded catalyst component for ethylene homopolymerization or copolymerization of ethylene and alpha-olefin. The preparation method comprises that: an oxide contacts a magnesium compound to obtain a carrier, a chromium compound and an aluminum compound are loaded on the carrier, and high temperature activation is performed to obtain the loaded catalyst, wherein the chromium content in the catalyst is 0.05-5 wt%, the magnesium content in the catalyst is 0.1-10 wt%, and the aluminum content in the catalyst is 0.5-10 wt%. With the loaded catalyst, the ethylene polymerization catalysis activity is improved, and the fusion index of the polymer is increased.
Description
Technical field
The present invention relates to a kind of loaded catalyst component for ethylene homo or ethene and alpha-olefin copolymer, more particularly, relate to loaded catalyst component on the complex carrier that a kind of chromium cpd and aluminum compound be carried on inorganic oxide and magnesium halide and its preparation method and application.
Technical background
Ethene polymers has been widely used in various membrane product resin materials, and has different characteristics according to the film method processed ethene polymerss that require different from object.For example, the polymkeric substance that has lower molecular weight and a narrow molecular weight distributions is applicable to by the goods of injection moulding film system.On the other hand, the polymkeric substance that has higher molecular weight and a wide molecular weight distribution is applicable to by the goods of blowing or aerated film method for making film system.For example, in (pipe applications) needs polyethylene to high molecular in many application, this quasi-polyethylene has enough intensity, has good processing characteristics simultaneously.
The ethene polymers with wide molecular weight distribution can be by preparing with chromium-based catalysts, this class catalyst component composition generally comprises carrier, active ingredient, is with or without promotor, wherein carrier is inorganic oxide, active ingredient is the organic or inorganic compound of chromium, and promotor is organometallics.In the art, above-mentioned catalyzer is commonly referred to Phillips catalyzer.Typical example comprises that employing chromic salt is immersed on the carriers such as silicon-dioxide (silica gel), after the catalyzer obtaining is removed moisture, then with dry air fluidisation activation at 400～1000 ℃ of temperature, the chromium atom of partial load is converted into sexavalent chrome atom.This catalyzer can be deposited in dry air or in rare gas element.Because each concrete component concentration and the preparation method of catalyzer are different, thereby gained catalyst performance price differs greatly.
The feature of chrome catalysts is to have different active centre ratios for chainpropagation in vinyl polymerization and chain transfer.This catalyzer tends to produce short polymer chain and comonomer is combined with short polymer chain with high frequency, has comonomer and the side chain of uneven distribution between each macromole of the polymkeric substance obtaining thus.Therefore, the polymkeric substance of making can be wide molecular weight distribution, and this polymkeric substance has good processing characteristics.But this catalyzer also often has the shortcomings such as induction time is long, polymerization activity is low, product melting index is low, hydrogen regulation performance is insensitive.In order to overcome these shortcomings of chrome catalysts, there is successively the chromium-based catalysts of many modifications.By the chemical modification to active centre chromium or carrier, improve the catalytic performance of chromium-based catalysts.
For normally used silica-based inorganic oxide carrier in chrome catalysts system, in the time that catalyzer is heated or is dry, be easy to cause silicon oxide melting or sintering, thereby the surface-area of catalyzer is reduced.If selective oxidation aluminium is as solid support material, heated oxide aluminium can cause aluminum oxide to break, and produces inhomogeneous and coarse granules of catalyst, can cause polymeric articles to be difficult to process.
For this reason, Chinese patent CN101081877A discloses a kind of preparation method of supported chrome series catalysts.It contacts with magnesium compound by the inorganic oxide that makes silicon oxide-containing, obtain a kind of magnesium and process complex carrier, prepare the cogelled of magnesium oxide and silicon-dioxide, utilize such as magnesium oxide of magnesium compound or finally can generate the carriers such as magnesian salt pair silica gel by methods such as roastings and carry out modification, finally changed surface-area and the pore property of carrier.The catalyzer of the unmodified carrier of ethene polymers prepared by the supported chrome series catalysts obtaining after load chromium cpd is again compared, and density increases, and molecular weight distribution broadens.
But in this patent, the complex treatment process of magnesium compound.For example, it adds ammoniacal liquor to form gel and aging in the aqueous solution of magnesium nitrate and tetraethoxy-silicane, then repeatedly washes with water and with alcohol washing, finally also need be in vacuum drying oven high temperature drying.Therefore, preparation process is very loaded down with trivial details.
In addition, Chinese patent CN101343336 discloses a kind of improved olefin polymerization catalysis and preparation method, it adopts silicon oxide and aluminum chloride as complex carrier, and bistriphenyl silane chromate activeconstituents and aluminum alkyls are loaded on described complex carrier, the catalyzer of gained can improve ethylene polymerization activity effectively, hydrogen response and the copolymerization performance of adjusting catalyzer, the polyvinyl resin of preparation can be used for producing high-performance polyethylene tubing, coating materials etc.But disclosed technology, take bistriphenyl silane chromate as chromium source, after bistriphenyl silane chromate is loaded on complex carrier, also needs the catalyzer containing chromium with aluminum alkyls reduction in this patent, complicated process of preparation, the production cycle is longer.
Summary of the invention
The present invention, in order to overcome above-mentioned technical defect, provides a kind of loaded catalyst component for vinyl polymerization and preparation method thereof.During for catalyzed ethylene polymerization, improved the polymerization activity of catalyzer, the ethene polymers of gained has higher melting index simultaneously.
The invention provides a kind of loaded catalyst component for vinyl polymerization, it is characterized in that:
Take the reaction product of inorganic oxide and magnesium halide as carrier, chromium cpd and aluminum compound are carried on this carrier, after activated, obtain described loaded catalyst component, wherein in the gross weight of loaded catalyst component, chromium content is 0.05-5wt%, Mg content is 0.1-10wt%, and aluminium content is 0.5-10wt%; Preferably, chromium content is 0.1～4.0wt%, and Mg content is 0.5～8.0wt%, and aluminium content is 0.6～6.0wt%.
Described inorganic oxide is a kind of in aluminum oxide, silicon-dioxide (silica gel), titanium dioxide, zinc oxide, boron oxide and zirconium white or their mixture; Take spherical soild oxide carrier as good, preferably silica gel.Can select specific surface area is 245-375m
2the silica-gel carrier of/g, also can select specific surface area is 410-620m
2the silica-gel carrier of/g.Along with carrier specific surface area increases, the hydrogen tune ability of catalyzer reduces; Along with specific surface area reduces, the polymerization activity of catalyzer reduces; Selected carrier silica gel also should have suitable pore volume.Can select pore volume is 1.1-1.8cm
3the carrier silica gel of/g, also can select pore volume is 2.4-3.7cm
3the carrier silica gel of/g.Along with the pore volume of carrier silica gel reduces, the hydrogen tune ability of catalyzer declines, but high pore volume carrier silica gel must be prepared by solution extraction, and cost is higher.Can directly adopt the silica-gel carrier being purchased.Described inorganic oxide carrier, will carry out drying treatment conventionally to remove free-water.Drying treatment can be carried out in air, also can in rare gas element, carry out, and can also under vacuum state, complete.
Described magnesium halide is preferably magnesium chloride, magnesium bromide; Be preferably magnesium dichloride or dibrominated magnesium.
Wherein, the weight ratio of inorganic oxide and magnesium halide is 100:1～1:10.
Carrier take the reaction product of above-mentioned inorganic oxide and magnesium halide as catalyst component of the present invention, the content of carrier in catalyzer is 70-99wt%, preferably 80-98wt%.
Described chromium cpd can adopt those through high-temperature activations can be transformed into chromic oxide containing chromium cpd, organo-chromium compound or inorganic chromium compound all can, water-soluble or oil soluble also all can.Described water miscible chromium cpd is selected from a kind of in chromic oxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Described oil-soluble chromium cpd is selected from one or more in tertiary butyl chromate, two luxuriant chromium or Acetyl Acetone acid chromium.
Described aluminum compound is selected from general formula Al
y(OR
1)
m(R
2)
n(X)
zone or more in compound, wherein R
1and R
2identical or different, be selected from C
1-C
20the alkyl of straight or branched, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20one in aralkyl, X is halogen, wherein y be 1 or 2, m, n, z be 0,1,2 or 3, and will meet m+n+z=3y.Be preferably one or more of aluminum alkyls class, chlorination aluminum alkyls class, alkyl alkoxy aluminium class, aluminum halide class.Concrete as: triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, ethyl diethoxy aluminium, diethylaluminum ethoxide, sesquialter ethyl aluminum chloride, sesquialter methyl aluminum chloride, aluminium diethyl monochloride, a chlorine diethoxy aluminium, ethyl aluminum dichloride, dichloro aluminium isobutyl, dichloro aluminum ethoxide, aluminum chloride, alchlor, aluminium triiodide etc.Described aluminum compound can also be selected from alumina alkane, for example, be selected from one or more among methylaluminoxane, ethylaluminoxane, sec.-propyl aikyiaiurnirsoxan beta.
Can select to prepare as follows the loaded catalyst component for vinyl polymerization of the present invention, the method comprises the following steps:
(1) drying treatment inorganic oxide carrier 1～10 hour at 100～800 ℃;
(2) magnesium halide is contacted with electron donor compound and form solution, the oxide carrier contact reacts obtaining with step (1), oxide carrier is 100:1～1:10 with the weight ratio of the magnesium halide adding, obtain magnesium-containing carrier through 20～400 ℃ of vacuum-dryings, wherein the weight ratio of magnesium halide magnesium and electron donor compound is 10:1～1:1000;
(3) the magnesium-containing carrier contact reacts that aluminum compound and chromium cpd and step (2) is obtained, inorganic oxide carrier is 1:10～100:1 with the weight ratio of the aluminum compound adding, inorganic oxide carrier is 1:10～100:1 with the weight ratio of the chromium cpd adding, the temperature of reaction is-20 ℃～200 ℃, the time of reaction is 0.5～50hr, obtains the pre-catalyst component of load chromium and aluminium;
(4) the pre-catalyst component of load chromium step (3) being obtained in oxygen-containing atmosphere, calcine after 1-10 hour at 400～1000 ℃, obtains loaded catalyst component.
Wherein the electron donor compound described in step (2) is selected from a kind of in the fatty alcohol of alkyl ester, C2～C6 aliphatic ether, C3～C4 cyclic ethers, C3～C6 saturated fatty ketone, C1～C20 side chain or side chain of alkyl ester, C7～C8 aromatic carboxylic acid of C1～C4 aliphatic saturated monocarboxylic acid or their mixture.Particularly, be selected from a kind of in methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone, methyl iso-butyl ketone (MIBK), ethanol, butanols, isooctyl alcohol or their mixture.Preferably tetrahydrofuran (THF).
The present invention also provides a kind of catalyzer for vinyl polymerization, comprises following component:
(1) the above-mentioned loaded catalyst component for vinyl polymerization of the present invention;
(2) promotor, for the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or the second transition group in the periodic table of elements, the mol ratio of organometallic compound and chromium is 0.1:1～100:1, preferably 0.5:1～50:1.
Described promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or the second transition group in the periodic table of elements.As aluminum alkyls or lithium alkylide or boron alkyl etc., particularly: n-Butyl Lithium, triethyl-boron, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride and zinc ethyl etc.And for example: the C of alkoxide
1-C
10aluminum alkyls, oxyethyl group diethyl aluminum, methoxyl group diethyl aluminum etc.In addition, also can use methylaluminoxane, ethylaluminoxane or butyl aikyiaiurnirsoxan beta etc.
Catalyzer of the present invention can be for ethylene homo, also can be for ethene and other olefin-copolymerization.Other described alkene can be to contain C
3-C
20alpha-olefin, aromatic vinyl compound, alicyclic ring vinyl compound, one or more in cycloolefin.As propylene, butylene, hexene, 3-methyl-1-butene, 3-ethyl-1-amylene, vinylbenzene, allyl benzene, vinyl cyclohexane, vinyl pentamethylene, tetrahydrobenzene, norbornylene, 5-methyl-2-norbornylene etc.
Catalyzer of the present invention can be used for intermittently or continuous mode is produced, and can be used for solution, gas phase and slurry phase polymerisation technique, is specially adapted to slurry polymerization processes.When using when slurry polymerization processes, generally select a kind of alkane of inertia as thinner, make the polymer beads can be discrete in thinner with slurry form, after reaction finishes by flash distillation or remove by filter thinner.Common thinner has propane, Trimethylmethane, pentane, hexane, heptane.Typical polymerizing condition be polymerization temperature at 20 ℃-250 ℃, be preferably in 50 ℃-160 ℃; The pressure of polymerization, at 1-100atm, is preferably in 5-60atm.
The present invention is incorporated into magnesium compound in oxide carrier under gentle condition, and then contacts with aluminum compound with chromium cpd.The preparation of catalyzer does not relate to cogelled technology, does not change carrier hole structure, and method is simple.Prepared catalyzer has improved polymerization activity while being used for vinyl polymerization, has increased the melting index of polymkeric substance.
Embodiment
Provide following examples to the present invention is described better, be not used for limiting the scope of the invention.
Testing method:
1, melt index (M.I): measure (190 ℃, 21.6kg) according to ASTM D1238-10
2, ethylene polymerization activity: represent by the weight of every gram of catalyzer gained resin
3, the ultimate analysis of Cr/Mg/Al/Si in solid: Xray fluorescence spectrometer is measured
4, measure the content of the THF in carrier: by gas-chromatography sign, tetrahydrofuran (THF) minimum detectable activity is 0.1wt%
Vinyl polymerization:
Polyreaction evaluation is carried out in the autoclave of 2 liters, and the speed of stirring is 450rmp, and reactor has stainless steel chuck, and the liquid medium in chuck can accurately be controlled temperature of reaction.After fully replacing with High Purity Nitrogen, add the purifying hexane of 1 liter under a little more than atmospheric condition, then add 0.4ml triethyl aluminium solution (concentration is 1M) and 200-400mg ingredient of solid catalyst, the temperature of system is raised to 80 ℃, finally pass into ethene and make the pressure in still reach 13.0atm, keep the constant reaction of stagnation pressure one hour, after polymerization finishes, stop passing into ethene, after the slow release of reactor, polyethylene is separated from hexane, after being finally dried, weighed.Polymerization activity represents by the polymkeric substance total amount (gPE/gCat.hr) of every gram of Catalyst Production per hour.
Embodiment 1
(W.R.Grace & Co.-Com, pore volume is about 1.1-1.8cm to the silica gel that is 955 by model
3/ g, surface-area is about 245-375m
2/ g) under nitrogen fluidisation, be warmed up to 200 ℃ to be dried 4 hours.
A dry reactor is replaced the magnesium chloride and the 200ml tetrahydrofuran (THF) that after three times, add 1g (10.5mmol) with High Purity Nitrogen, heating bath temperature to 65 ℃ stirring reaction five hours, forms magnesium chloride solution, cooling solution temperature to 35 ℃.Get the above-mentioned silica gel after treatment of 10g and join magnesium chloride solution and flood, 35 ℃ of stirring reactions, after 2 hours, are blown away solvent with nitrogen, obtain pressed powder.By pressed powder vacuum-drying 2 hours at 100 ℃, then vacuum-drying 10 hours at 300 ℃, fail to detect tetrahydrofuran (THF) through gas chromatographic analysis, obtain mobility well containing magnesium silica-gel carrier.Be 41.7wt% containing Si content in magnesium silica-gel carrier, Mg content is 2.1wt%.
Embodiment 2
The method preparation identical with embodiment 1 is containing the silica-gel carrier of magnesium, and just the add-on of magnesium chloride becomes 4g (42.0mmol) from 1g (10.5mmol), and other condition is constant.Be 30.4wt% containing Si content in magnesium silica-gel carrier, Mg content is 6.8wt%.
Embodiment 3
That gets prepared by 10g embodiment 1 adds 150ml hexane stirring at room temperature to form suspension containing magnesium silica-gel carrier, then in suspension, drip the triethyl aluminum hexane solution (concentration of Al is 2mmol/ml) of 4ml, after finishing, dropping at room temperature stirs 2 hours, leave standstill except after desolventizing the 200ml toluene solution that contains 1.2g chromium acetylacetonate is joined in reactant and flooded, stirring at room temperature reaction is after 4 hours, except desolventizing obtains the pre-catalyst containing chromium.Pre-catalyst is placed in to 1.75 inches of silica tubes and activates, sintered quartz dish is equipped with in the bottom of 1.75 inches of silica tubes.Pre-catalyst is loaded into dish upper, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open silica tube all electric furnaces around, make temperature rise to 800 ℃ of calcinings 6 hours with the speed of 300 ℃ per hour, obtain the chromium-based catalysts of activation.In catalyst component, the content of chromium, magnesium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1.
Embodiment 4
With the method Kaolinite Preparation of Catalyst identical with embodiment 3, just prepared by 10g embodiment 1 become prepared by 10g embodiment 2 containing magnesium silica-gel carrier containing magnesium silica-gel carrier, other condition is constant.In catalyst component, the content of chromium, magnesium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1.
Embodiment 5
With the method Kaolinite Preparation of Catalyst identical with embodiment 3, just the triethyl aluminum hexane solution of 4ml (concentration of Al is 2mmol/ml) is become to the triethyl aluminum hexane solution (concentration of Al is 2mmol/ml) of 8ml, other condition is constant.In catalyst component, the content of chromium, magnesium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1.
Embodiment 6
With the method Kaolinite Preparation of Catalyst identical with embodiment 3, just the triethyl aluminum hexane solution (concentration of Al is 2mmol/ml) of 4ml becomes the aluminium diethyl monochloride hexane solution (concentration of Al is 2mmol/ml) of 4ml, and other condition is constant.In catalyst component, the content of chromium, magnesium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1.
Embodiment 7
That gets prepared by 10g embodiment 1 adds 150ml toluene stirring at room temperature to form suspension containing magnesium silica-gel carrier, then in suspension, drip the methylaluminoxane toluene solution (concentration of Al is 2mmol/ml) of 4ml, after finishing, dropping at room temperature stirs 2 hours, leave standstill except after desolventizing the 200ml toluene solution that contains 1.2g chromium acetylacetonate is joined in reactant and flooded, stirring at room temperature reaction is after 4 hours, except desolventizing obtains the pre-catalyst containing chromium.Pre-catalyst is placed in to 1.75 inches of silica tubes and activates, sintered quartz dish is equipped with in the bottom of 1.75 inches of silica tubes.Pre-catalyst is loaded into dish upper, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open silica tube all electric furnaces around, make temperature rise to 800 ℃ of calcinings 6 hours with the speed of 300 ℃ per hour, obtain the chromium-based catalysts of activation.In catalyst component, the content of chromium, magnesium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1.
Comparative example 1
Get prepared by 10g embodiment 1 joining in the 200ml toluene solution that contains 1.2g chromium acetylacetonate and flood containing magnesium silica-gel carrier, stirring at room temperature reaction is after 4 hours, except desolventizing obtains the pre-catalyst containing chromium.Pre-catalyst is placed in to 1.75 inches of silica tubes and activates, sintered quartz dish is equipped with in the bottom of 1.75 inches of silica tubes.Pre-catalyst is loaded into dish upper, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open silica tube all electric furnaces around, make temperature rise to 800 ℃ of calcinings 6 hours with the speed of 300 ℃ per hour, obtain the chromium-based catalysts of activation.In catalyst component, the content of chromium and magnesium and catalyst vinyl polymerization evaluation result are listed in table 1.
Comparative example 2
The silica-gel carrier of getting after 10g embodiment 1 pyroprocessing directly adds 150ml hexane stirring at room temperature to form suspension, then in suspension, drip the triethyl aluminum hexane solution (concentration of Al is 2mmol/ml) of 4ml, after finishing, dropping at room temperature stirs 2 hours, leave standstill except after desolventizing the 200ml toluene solution that contains 1.2g chromium acetylacetonate is joined in reactant and flooded, stirring at room temperature reaction is after 4 hours, except desolventizing obtains the pre-catalyst containing chromium.Pre-catalyst is placed in to 1.75 inches of silica tubes and activates, sintered quartz dish is equipped with in the bottom of 1.75 inches of silica tubes.Pre-catalyst is loaded into dish upper, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open silica tube all electric furnaces around, make temperature rise to 800 ℃ of calcinings 6 hours with the speed of 300 ℃ per hour, obtain the chromium-based catalysts of activation.In catalyst component, the content of chromium and aluminium and catalyst vinyl polymerization evaluation result are listed in table 1.
Table 1. catalyst performance
As can be seen from Table 1, the present invention has adopted silicon/magnesium complex carrier, the loaded catalyst obtaining after the aluminium of load simultaneously, chromium has improved the activity of catalyzer and the melting index of polymkeric substance, polymkeric substance flowing better under stress, and this required character in many extruding shaping technique (as film forming and blowing) just, thereby be applicable to wider work range.
Claims (12)
1. for a loaded catalyst component for vinyl polymerization, it is characterized in that,
Take the reaction product of inorganic oxide and magnesium halide as carrier, chromium cpd and aluminum compound are carried on this carrier, after activated, obtain loaded catalyst component, in the gross weight of loaded catalyst component, chromium content is 0.05-5wt%, Mg content is 0.1-10wt%, and aluminium content is 0.5-10wt%;
Wherein said chromium cpd adopts those can be transformed into the chromium cpd that contains of chromic oxide through high-temperature activation;
Wherein said aluminum compound is selected from general formula Al
y(OR
1)
m(R
2)
n(X)
zone or more in compound, wherein R
1and R
2identical or different, be selected from C
1-C
20the alkyl of straight or branched, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20one in aralkyl, X is halogen, wherein y be 1 or 2, m, n, z be 0,1,2 or 3, and will meet m+n+z=3y, or described aluminum compound is selected from alkylaluminoxane class.
2. the catalyst component for vinyl polymerization according to claim 1, is characterized in that, described chromium content is 0.1～4.0wt%, and Mg content is 0.5～8.0wt%, and aluminium content is 0.6～6.0wt%.
3. the catalyst component for vinyl polymerization according to claim 1, is characterized in that, described inorganic oxide is a kind of in aluminum oxide, silicon-dioxide, titanium dioxide, zinc oxide, boron oxide and zirconium white or their mixture.
4. the catalyst component for vinyl polymerization according to claim 1, is characterized in that, described chromium cpd is water miscible or oil-soluble.
5. catalyst component according to claim 4, is characterized in that, described water miscible chromium cpd is selected from a kind of in chromic oxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Described oil-soluble chromium cpd is selected from one or more in tertiary butyl chromate, two luxuriant chromium or Acetyl Acetone acid chromium.
6. the catalyst component for vinyl polymerization according to claim 1, it is characterized in that, described aluminum compound is one or more among triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, ethyl diethoxy aluminium, diethylaluminum ethoxide, sesquialter ethyl aluminum chloride, sesquialter methyl aluminum chloride, aluminium diethyl monochloride, a chlorine diethoxy aluminium, ethyl aluminum dichloride, dichloro aluminium isobutyl, dichloro aluminum ethoxide, aluminum chloride, alchlor, aluminium triiodide, methylaluminoxane, ethylaluminoxane, sec.-propyl aikyiaiurnirsoxan beta.
7. according to the preparation method of the loaded catalyst component for vinyl polymerization one of claim 1-6 Suo Shu, comprise the following steps:
(1) drying treatment oxide carrier 1～10 hour at 100～800 ℃;
(2) magnesium halide is contacted with electron donor compound and form solution, magnesium halide is 10:1～1:1000 with the ratio of the amount of substance of electron donor compound, the oxide carrier contact reacts obtaining with step (1), oxide carrier is 100:1～1:10 with the weight ratio of the magnesium halide adding, and obtains magnesium-containing oxide carrier through 20～400 ℃ of vacuum-dryings;
(3) the magnesium-containing carrier contact reacts that aluminum compound and chromium cpd and step (2) is obtained, carrier is 1:10～100:1 with the weight ratio of the aluminum compound adding, carrier is 1:10～100:1 with the weight ratio of the chromium cpd adding, the temperature of reaction is-20 ℃～200 ℃, the time of reaction is 0.5～50hr, obtains the pre-catalyst component of load chromium;
(4) the pre-catalyst component of load chromium step (3) being obtained in oxygen-containing atmosphere, calcine after 1-10 hour at 400～1000 ℃, obtains loaded catalyst component.
8. the preparation method of the loaded catalyst component for vinyl polymerization according to claim 7, wherein the electron donor compound described in step (2) is selected from a kind of in the fatty alcohol of alkyl ester, C2～C6 aliphatic ether, C3～C4 cyclic ethers, C3～C6 saturated fatty ketone, C1～C20 side chain or side chain of alkyl ester, C7～C8 aromatic carboxylic acid of C1～C4 aliphatic saturated monocarboxylic acid or their mixture.
9. the preparation method of the loaded catalyst component for vinyl polymerization according to claim 7, wherein the electron donor compound described in step (2) is selected from a kind of in methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone, methyl iso-butyl ketone (MIBK), ethanol, butanols, isooctyl alcohol or their mixture.
10. the preparation method of the loaded catalyst component for vinyl polymerization according to claim 7, wherein the electron donor compound described in step (2) is tetrahydrofuran (THF).
11. 1 kinds of catalyzer for vinyl polymerization, comprise following component:
(1) the described loaded catalyst component for vinyl polymerization of one of claim 1-6;
(2) promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or the second transition group in the periodic table of elements;
Ratio between component (1) and component (2), take organometallic compound in component (2) with the molar ratio computing of the middle chromium of component (1) as 0.1:1～100:1.
12. catalyzer for vinyl polymerization according to claim 11, in wherein said component (2), in organometallic compound and component (1), the mol ratio of chromium is 0.5:1～50:1.
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| CN109160963B (en) * | 2018-08-28 | 2021-05-04 | 吉化集团吉林市天龙催化剂有限公司 | Magnesium modified chromium catalyst for ethylene polymerization and preparation method thereof |
| CN111013610A (en) * | 2018-10-09 | 2020-04-17 | 中国石油天然气股份有限公司 | Immobilized Lewis acid catalyst, preparation method thereof and α -olefin oligomerization reaction using catalyst |
| CN114605579A (en) * | 2020-12-03 | 2022-06-10 | 万华化学集团股份有限公司 | Polypropylene catalyst, isotactic polypropylene and preparation method thereof |
| CN114605579B (en) * | 2020-12-03 | 2023-07-14 | 万华化学集团股份有限公司 | Polypropylene catalyst, isotactic polypropylene and preparation method thereof |
| CN116806169A (en) * | 2021-02-19 | 2023-09-26 | 切弗朗菲利浦化学公司 | Method for activating chromium catalysts using oxygen-enriched fluidizing gas |
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