CN104926967A - Olefin polymerization catalyst with silica gel microsphere/magnesium chloride as carrier, and preparation method and application thereof - Google Patents
Olefin polymerization catalyst with silica gel microsphere/magnesium chloride as carrier, and preparation method and application thereof Download PDFInfo
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- CN104926967A CN104926967A CN201510121260.9A CN201510121260A CN104926967A CN 104926967 A CN104926967 A CN 104926967A CN 201510121260 A CN201510121260 A CN 201510121260A CN 104926967 A CN104926967 A CN 104926967A
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- Prior art keywords
- silica gel
- catalyst
- gel microball
- carrier
- magnesium chloride
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000000741 silica gel Substances 0.000 title claims abstract description 86
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 86
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 title claims description 35
- 239000002685 polymerization catalyst Substances 0.000 title abstract description 5
- 239000004005 microsphere Substances 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 24
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- -1 alkyl metal compound Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000713 high-energy ball milling Methods 0.000 claims abstract 2
- 239000011806 microball Substances 0.000 claims description 67
- 239000011805 ball Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000002203 pretreatment Methods 0.000 claims description 18
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 18
- 238000007725 thermal activation Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920001195 polyisoprene Polymers 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 3
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical class C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 58
- 229960002337 magnesium chloride Drugs 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229920001083 polybutene Polymers 0.000 description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 4
- 229940091250 magnesium supplement Drugs 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- QWJUMUXQFFWLIF-UHFFFAOYSA-N 9,9-dimethoxyfluorene Chemical class C1=CC=C2C(OC)(OC)C3=CC=CC=C3C2=C1 QWJUMUXQFFWLIF-UHFFFAOYSA-N 0.000 description 2
- ZFIVOWBNAYBZJR-UHFFFAOYSA-N CCCO[Mg] Chemical compound CCCO[Mg] ZFIVOWBNAYBZJR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 0.000 description 1
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 description 1
- NFOQRIXSEYVCJP-UHFFFAOYSA-N 2-propoxycarbonylbenzoic acid Chemical compound CCCOC(=O)C1=CC=CC=C1C(O)=O NFOQRIXSEYVCJP-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical compound CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 description 1
- OQICUELKMVKCFT-UHFFFAOYSA-N acetaldehyde;ethene Chemical compound C=C.CC=O OQICUELKMVKCFT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FWCTZJNNLCYVMA-UHFFFAOYSA-L butan-1-ol;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCCO.CCCCO FWCTZJNNLCYVMA-UHFFFAOYSA-L 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical class [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- NSYCXGBGJZBZKI-UHFFFAOYSA-L dichlorotitanium;ethanol Chemical compound CCO.CCO.Cl[Ti]Cl NSYCXGBGJZBZKI-UHFFFAOYSA-L 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- VVKJJEAEVBNODX-UHFFFAOYSA-N diethoxy-di(propan-2-yl)silane Chemical compound CCO[Si](C(C)C)(C(C)C)OCC VVKJJEAEVBNODX-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-UHFFFAOYSA-J 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses an olefin polymerization catalyst with silica gel microsphere/anhydrous magnesium chloride as a carrier, and a preparation method and an application thereof. The olefin polymerization catalyst comprises the silica gel microsphere/anhydrous magnesium chloride catalyst carrier and a catalytic active component. The catalytic active component is a Ziegler-Natta catalyst. The olefin polymerization catalyst is prepared with a high-energy ball milling in-situ reaction process. The silica gel microsphere/anhydrous magnesium chloride-loaded Ziegler-Natta catalyst provided by the invention has high catalytic efficiency, and the production method of the catalyst is suitable for industrialization. Under the existence of a co-catalyst of an alkyl metal compound, the olefin catalyst can initiate the polymerization of isoprene and butene. The apparent morphology of the polymer obtained under the initiation of the catalyst is spheroid. With the catalyst, problems of low catalytic activity and uncontrollable polymerization product structure of the type of catalysts are solved.
Description
Technical field
The present invention relates to carrier loaded polyolefin catalyst and preparation method thereof, particularly, the present invention relates to Ziegler-Natta catalyst, particularly a kind of with silica gel microball and magnesium chloride polyolefin catalyst that is carrier and preparation method thereof.
Background technology
Ziegler-Natta catalyst comes out 60 for many years, and the development from the first-generation to the 5th generation has promoted developing rapidly of polyolefin industry.During this period, people also develop the alkene catalyst of multiple other types in succession, such as metallocene catalyst and late transition metal catalyst, and demonstrate superiority in some respects, but it does not still obtain industrial applications widely.Traditional Ziegler-Natta catalyst occupies main status always in Catalysts for Olefin Polymerization, up to the present, it still in polyolefin industry in the highest flight.Ziegler-Natta catalyst, as the extensive industrialized catalyzer of one, is of great significance its linguistic term tool.
The supported of homogeneous catalyst is one of important directions of current olefinic polymerization catalysis, in maintenance or while improving homogeneous catalyst activity, reaches the object controlling catalyzer form and polymer performance.Common carrier for olefin polymerization catalyst comprises magnesium chloride, organic polymer, inorganic porous material (as SiO
2, Al
2o
3) and mesoporous material etc.Since U.S. Phillips the 1950's oil company is carrier loaded Cr series catalysts with silica gel, the research of porous material loading olefin polymerization catalysis receives increasing concern.Because silica gel has the fine quality being comparatively suitable as carrier, as acid resistance, high thermal resistance (can at 500-600 DEG C long reaction), good physical strength, controlled pore structure and specific surface area, excellent chemical stability and thermostability and lower surface acidity etc., so be more used as support of the catalyst, as reaction process such as oxidation, hydrogenation, dehydrogenation, hydration, polymerization such as ethylene gas phase oxidation preparing vinyl acetate, oxidation of ethylene acetaldehyde, oxidation of ethylene epoxy ethane, ethyl benzene dehydrogenation preparation of styrene, vinyl polymerization polyethylene.
Magnesium chloride becomes with the chemical structure of its uniqueness and character prepares the ideal carrier of effective catalyst, but the preparation process of spherical magnesium chloride supported catalyst very complicated and be difficult to control.Silica gel is also used as the carrier of polyolefin catalyst because of its porousness, high-specific surface area and good form and mobility, but is that the Ziegler-Natta catalyst of carrier often shows lower catalytic activity again with silica gel.Therefore attempt magnesium chloride and silica gel to combine, form titanium tetrachloride/silica gel/silica gel composite carried catalyst.This catalyzer is at complex carrier obtained on the silica gel of Second support using magnesium chloride load, then react obtained with titanium compound, it had both had the feature of magnesium chloride supported catalyst high catalytic activity, high stereospecificity, maintain again the good particle form of silica gel carrier catalyst, higher porosity and specific surface area, demonstrate unique catalytic performance for olefinic polymerization.Magnesium chloride-silica gel complex carrier type Ziegler-Natta catalyst not only has the highly active feature of Ti-Mg system supported catalyst, also there is higher physical strength, good dispersion flows and uniform particulate morphology, and the advantage such as stable polymerization reaction, morphology are good, bulk density is large and fine powder content is low.
Usually, silica gel can not directly as the carrier of catalyzer, the free water on its surface, even hydroxyl, two hydroxyl and free hydroxyl are all poisonous substances of catalyst ligand, belong to protonic acid, easily with strong donor residues part effect, thus make it to split away off from catalyzer, cause carrying active substance inactivation; In addition, catalyzer is also likely had an effect with other positions of silica gel and makes Si-O-Si bond rupture, generates active low active centre.Therefore before use certain process is carried out to it in order to heighten silica gel as the performance of carrier.First regulate the silica-gel carrier concentration of surface hydroxyl groups in anchor catalyst active centre by thermal activation process, thus obtain best active centre density; Then can chemical activation further, thermal activation is mainly used in reducing the already present hydroxyl value volume and range of product of Silica Surface, only rely on the more difficult regular alignment heightening Silica Surface group of the migration of surface hydroxyl, after thermal activation, Silica Surface group major part is free hydroxyl, and it is grappling center and the poisonous substance of catalyst ligand of catalyzer.Chemical activation reacts away or covers surface hydroxyl, forms a kind of barrier at Silica Surface, is blocked in catalyzer in follow-up catalyst cupport process and contacts with surface hydroxyl, thus changes the activation performance that its surface ligand reaches good.
The object of this research is to prepare a kind of highly active catalyzer be polymerized for isoprene and butylene one.The catalyst isoprene that the method is prepared and butylene one have higher catalytic efficiency when being polymerized, catalyzer good fluidity, polymer morphology is well spherical in class, be suitable for isoprene and butylene one slurry polymerization processes is also suitable for gas-phase polymerization process, and morphology is good.
Summary of the invention
The object of this invention is to provide a kind of silica gel microball/magnesium chloride composite carrier load method for preparing catalyst and catalyzing butene one, isoprene polymerization.
Used silica gel of the present invention is 40 ~ 200 order silica gel microballs.
Composite carrier load catalyzer provided by the invention comprises following component: carrier is silica gel microball and magnesium chloride, and used catalyst is Ziegler-Natta catalyst.
The method of composite carrier load support of the catalyst provided by the invention, comprises the steps:
Described complex carrier, carry out thermal activation treatment to carrier respectively, adopt interim heating schedule, top temperature is no more than 900 DEG C, can adopt the carrier after thermal activation or without chemical activation process, adopt efficient ball mill to carry out original position load Ziegler-Natta catalyst.Ball mill is efficient planetary ball mill, adopts agate jar, the large ball of agate ball m: m bead=1:3; Ball accounts for 1/3rd of tank volume, and material accounts for 1/3rd of ball grinder volume.By catalyst component (generally including magnesium chloride, titanium tetrachloride and Lewis base) with suitable ratio in grinding in ball grinder a few hours.
This method greatly reduces the best catalytic efficiency Ball-milling Time of supported catalyst, simple to operation, is easy to realize suitability for industrialized production.
Described titanium metal compound can one or more preferably in titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tetra iodide, oxyethyl group titanous chloride, diethoxy titanium dichloride, triethoxy monochlor(in)ate titanium, methoxytitanium trichloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, triple phenoxyl titanium chloride, two phenoxy group titanium dichloride and phenoxy group titanous chloride, most preferably are titanium tetrachloride.
In above-mentioned Primary Catalysts, described magnesium-containing compound be selected from magnesium chloride, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium or chlorination phenoxy group magnesium, magnesium ethylate and propoxy-magnesium one or more, be preferably magnesium chloride.
In above-mentioned catalyst composition, described aluminum contained compound is selected from trialkylaluminium, is preferably trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three iso-octyl aluminium, three n-butylaluminum and tri-n-hexyl aluminum, is preferably triisobutyl aluminium.
Described internal electron donor aromatic dicarboxylic acid ester is C
10~ C
30aromatic dicarboxylic acid ester, one or more preferably in dimethyl phthalate, diethyl phthalate, dipropyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate and phthalic acid benzhydrol ester, are more preferably diisobutyl phthalate;
Further, described internal electron donor diether is C
5~ C
30diether, preferably from 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-bicyclopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1, one or more in 3-Propanal dimethyl acetal, 2-ethyl-2-butyl-1,3-Propanal dimethyl acetal and 9,9-dimethoxy fluorenes, be more preferably 9,9-dimethoxy fluorenes.
As one or more organic silane compounds of external electron donor.In above-mentioned catalyst composition, described organic silane compound is indicated by following general formula: R
2xR
3ySi (OR
4) Z or (OR
5) (OR
6) (OR
7) (OR
8) Si; Wherein, R2 ~ R8 is C independently of one another
1-C
20alkyl or cycloalkyl, 0≤X≤2,0≤Y≤2,0 ﹤ Z≤4 and X+Y+Z=4.
In above-mentioned catalyst composition, described organic silane compound can be selected from tetraethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, cyclohexyl trimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, diisopropyldiethoxysilane, dicyclopentyl dimethoxyl silane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, one or more in diphenyl diethoxy silane or aminomethyl phenyl dimethoxysilane, be preferably diisopropyl dimethoxy silane, n-propyl Trimethoxy silane, one or more in Cyclohexylmethyldimethoxysilane and dicyclopentyl dimethoxyl silane.
Catalyst composition of the present invention is not subject to the restriction of wherein each component concentration, should be appreciated that in Ziegler-Natta catalyst system well-known to those skilled in the art, Primary Catalysts, cocatalyst content ratio all can be used for the present invention.
In the present invention, described catalyst composition refers to the described Primary Catalysts and promotor summation that add in the course of the polymerization process.
The invention provides the method for preparation above-mentioned silica gel microball/magnesium chloride composite carried catalyst; Wherein, prepare the method for silica gel microball/magnesium chloride composite carried catalyst, comprise the steps:
1) described silica gel microball is dried removal moisture, carry out thermal activation treatment afterwards, adopt interim heating schedule to carrier, 200 DEG C keep 2h, and 400 DEG C keep 2h, and 600 DEG C keep 2h, and 800 DEG C keep 2h, and top temperature is no more than 900 DEG C.Pre-treatment adopts following two kinds of modes:
A. by silica gel microball vacuum-treat, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free soaks and leaves standstill 10 ~ 50 hours, has reacted rear decompression and has steamed solvent and vacuum-drying;
B. by silica gel microball vacuum-treat, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free stirs 2 ~ 10 hours, has reacted rear decompression and has steamed solvent and vacuum-drying.
Under two kinds of modes, the mass ratio of described pre-treatment medium and Graphene is 0 ~ 5:1; Pre-treatment medium adopts titanium tetrahalide or aluminum contained compound Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10.
2) by described transistion metal compound and described step 1) the silica gel microball support of the catalyst prepared and anhydrous chlorides of rase magnesium carrier adopt efficient ball mill to carry out original position load Ziegler-Natta catalyst.
Obtain silica gel microball/magnesium chloride composite carried catalyst.The transition metal massfraction prepared is 1.0 ~ 3.8% of silica gel microball/magnesium chloride composite carried catalyst;
The present invention prepares silica gel microball/magnesium chloride composite carried catalyst, by the method load polyolefin catalyst of ball milling.This support of the catalyst and catalyzer have following features:
1, granules of catalyst mode of appearance is Powdered, and mobility is better.Include silica gel microball carrier, the particle diameter of silica gel microball is 40 ~ 200 orders;
2, silica gel microball/magnesium chloride load Ziegler-Natta catalyst, catalyst active center's Stable distritation, in silica gel microball/magnesium chloride surface imperfection place, has and enters silica gel microball inside by pore on a small quantity;
3, silica gel microball/magnesium chloride load Ziegler-Natta catalyst, catalyst efficiency is high.
4, this method greatly reduces supported catalyst best catalytic efficiency ball milling load time, simple to operation, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 silica gel microball/magnesium chloride load Ziegler-Natta catalyst causes prepares polyisoprene form
Fig. 2 preprocessing process titanium tetrachloride and the various surface hydroxyl of silica gel microball react
Embodiment
The graphene-supported Catalysts and its preparation method that following specific embodiment is just invented makes detailed explanation.But these embodiments do not limit the scope of the invention, also should not be construed as and only have condition provided by the invention, parameter or numerical value to implement the present invention.
Embodiment 1
1) gram silica gel microball of 25.0 after thermal activation treatment (silica gel microball particle diameter is 40-80 order) is vacuumized 24 hours, after add the analytical pure titanium tetrachloride of 5ml, leave standstill 24 hours, for subsequent use
2) add in a nitrogen environment in the ball grinder of 25.0 grams of Magnesium Chloride Anhydrouss and the extremely dry sealing of above-mentioned pretreated silica gel microball, then inject 2.5ml analytical pure titanium tetrachloride.
3) reinforced complete, ball grinder is put into planetary ball mill, grinding 5h.Derive the catalyzer prepared.
This catalyzer can be used to prepare polyisoprene, specifically can be prepared in the steps below:
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.2 gram of silica gel microball/magnesium chloride load Ziegler-Natta catalyst successively, through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 30 DEG C, polyreaction 6h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains 106 grams of polyisoprenes provided by the invention.In this reaction, product catalyst efficiency is 4417g/g.Ti.h, and pattern is comparatively regular, sees accompanying drawing 1.
Embodiment 2
1) will join in 250ml polymerization flask under gram silica gel microball of 25.0 after thermal activation treatment (silica gel microball particle diameter is 40-80 order) nitrogen environment, normal temperature high vacuum 24 hours, 40 DEG C of waters bath with thermostatic control put into by reaction flask after high pure nitrogen replaces three times.After add 75ml anhydrous hexane, stir after 5 minutes, add 5ml titanium tetrachloride, at 40 DEG C, constant temperature stirs 24 hours, after having reacted, solvent steams at reduced pressure conditions, further under a high vacuum 100 DEG C keep stirring drying in 30 minutes after obtain the pre-treatment thing of silica gel microball support of the catalyst.
2) add in a nitrogen environment in the ball grinder of 25 grams of Magnesium Chloride Anhydrouss and the extremely dry sealing of above-mentioned pretreated silica gel microball, then inject 2.5ml analytical pure titanium tetrachloride.
3) reinforced complete, grinding 5h.Derive the catalyzer prepared.
This catalyzer can be used to prepare polybutene one resin, specifically can be prepared in the steps below:
Under vacuum state, butylene one monomer is filled with in reactor, be equipped with in the polymeric kettle of stirring and register what fully replace through butylene one, 1mmol/ml triisobutyl aluminium hexane solution 2ml is added under room temperature, add catalyzer 18mg prepared by embodiment 2, liquid butylene 1L is added under stirring, keep hydrogen partial pressure 0.02MPa, be warming up to 40 DEG C, maintain 6 hours, obtain polymkeric substance 240g polybutene one material provided by the invention, in this reaction, product catalyst efficiency is 111111g/g.Ti.h, obtains polybutene one elastomer material.
Embodiment 3
1) silica gel microball 25.0 grams (silica gel microball particle diameter is 40-80 order) through thermal activation treatment is prepared.
2) add in a nitrogen environment in the ball grinder of Magnesium Chloride Anhydrous 25.0 grams and the extremely dry sealing of above-mentioned pretreated silica gel microball, then inject 2.5ml analytical pure titanium tetrachloride.
3) reinforced complete, grinding 5h.Derive the catalyzer prepared.
This catalyzer can be used to prepare polybutene one resin, specifically can be prepared in the steps below:
Under vacuum state, butylene one monomer is filled with in reactor, be equipped with in the polymeric kettle of stirring and register what fully replace through butylene one, 1mmol/ml triisobutyl aluminium hexane solution 2ml is added under room temperature, add catalyzer 18mg prepared by embodiment 3, liquid butylene 1L is added under stirring, keep hydrogen partial pressure 0.02MPa, be warming up to 40 DEG C, maintain 6 hours, obtain polymkeric substance 180g polybutene one material provided by the invention, in this reaction, product catalyst efficiency is 83333g/g.Ti.h, obtains polybutene one elastomer material.
Embodiment 4
1) silica gel microball 25.0 grams (silica gel microball particle diameter is 100-200 order) through thermal activation treatment is prepared.
2) add Magnesium Chloride Anhydrous 25 grams in a nitrogen environment in the ball grinder of dry sealing, add 2.5ml analytical pure titanium tetrachloride simultaneously.
3) pre-grinding 4h, after add above-mentioned pretreated silica gel microball, grinding 1h.Derive the catalyzer prepared.
This catalyzer can be used to prepare polybutene one resin, specifically can be prepared in the steps below: under vacuum state, butylene one monomer is filled with in reactor, be equipped with in the polymeric kettle of stirring and register what fully replace through butylene one, 1mmol/ml triisobutyl aluminium hexane solution 2ml is added under room temperature, add catalyzer 18mg prepared by embodiment 4, liquid butylene 1L is added under stirring, keep hydrogen partial pressure 0.02MPa, be warming up to 40 DEG C, maintain 6 hours, obtain polymkeric substance 220g polybutene one resin provided by the invention, in this reaction, product catalyst efficiency is 97222g/g.Ti.h, obtain polybutene one elastomer material.
Embodiment 5
1) silica gel microball 25.0 grams (silica gel microball particle diameter is 100-200 order) through thermal activation treatment is prepared.
2) add Magnesium Chloride Anhydrous 25 grams in a nitrogen environment in the ball grinder of dry sealing, add 2.5ml analytical pure titanium tetrachloride and 0.8ml diisobutyl phthalate simultaneously.
3) pre-grinding 4h, after add above-mentioned pretreated silica gel microball, grinding 1h.Derive the catalyzer prepared.
This catalyzer can be used to prepare polybutene one resin, specifically can be prepared in the steps below: under vacuum state, butylene one monomer is filled with in reactor, be equipped with in the polymeric kettle of stirring and register what fully replace through butylene one, 1mmol/ml triisobutyl aluminium hexane solution 2ml and diisopropyl dimethoxy silane 0.64 microlitre is added under room temperature, add catalyzer 18mg prepared by embodiment 5, liquid butylene 1L is added under stirring, keep hydrogen partial pressure 0.02MPa, be warming up to 40 DEG C, maintain 6 hours, obtain polymkeric substance 190g polybutene one resin provided by the invention, in this reaction, product catalyst efficiency is 87963g/g.Ti.h, obtaining insolubles content by ether extraction is 94%, namely isotactic polybutene one content is 94%.
Embodiment 6
1) silica gel microball 10.0 grams (silica gel microball particle diameter is 100-200 order) through thermal activation treatment is prepared.
2) Magnesium Chloride Anhydrous 40 grams is added in a nitrogen environment in the ball grinder of dry sealing.
3) pre-grinding 4h, after add above-mentioned pretreated silica gel microball, grinding 1h.Derive the catalyzer prepared.
This catalyzer can be used to prepare polyisoprene, specifically can be prepared in the steps below:
Under vacuum state, 750ml isoprene monomer is added in reactor, add silica gel microball/magnesium chloride load Ziegler-Natta catalyst in 2ml triisobutyl aluminium (removal of impurities) and 0.2 gram of embodiment 6 successively, through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 30 DEG C, polyreaction 6h, add acidic ethanol after being polymerized and stop polyreaction, vacuum-drying at 30 DEG C, obtain 120 grams and the invention provides polyisoprene, in this reaction, product catalyst efficiency is 5000g/g.Ti.h.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (11)
1. one kind with silica gel microball/magnesium chloride load Ziegler-Natta polyolefin catalyst and preparation method thereof.
2. silica gel microball/magnesium chloride load Ziegler-Natta catalyst, comprises following component: silica gel microball carrier, anhydrous chlorides of rase magnesium carrier, Ziegler-Natta catalyst and ester class or ether compound internal electron donor.
3. carrier according to claim 1 and 2, is characterized in that: for silica gel microball carrier, and the particle diameter of silica gel microball is 40 ~ 200 orders, and its form is creamy white transparent or semitransparent shape carrier.
4. catalyzer according to claim 1 and 2, is characterized in that: in described Ziegler-Natta catalyst, titanium tetrahalide used is TiCl
4, TiBr
4or TiI
4; Described aluminum contained compound is Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10, preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane.
5. the carrier according to claim 1-3, its preparation method comprise the steps: described silica gel microball dried remove moisture, afterwards thermal activation treatment is carried out to carrier, adopt interim heating schedule: 200 DEG C keep 2h, 400 DEG C keep 2h, 600 DEG C keep 2h, and 800 DEG C keep 2h, and top temperature is no more than 900 DEG C.Directly can use the carrier after thermal activation treatment and also can use after pre-treatment, pre-treatment adopts following two kinds of mode: a. by silica gel microball vacuum-treat, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free soaks and leaves standstill 10 ~ 50 hours, has reacted rear decompression and has steamed solvent and vacuum-drying; B. by silica gel microball vacuum-treat, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free stirs 2 ~ 10 hours, has reacted rear decompression and has steamed solvent and vacuum-drying.
Under two kinds of modes, the mass ratio of described pre-treatment medium and Graphene is 0 ~ 5:1; Pre-treatment medium adopts titanium tetrahalide or aluminum contained compound Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10.
6., according to the arbitrary described catalyzer of claim 1-3, it is characterized in that: mass percentage shared by silica gel microball is 1 ~ 50%, mass percentage shared by catalytic active component is 1.0 ~ 20.0%.
7. prepare a method for the arbitrary described silica gel microball/magnesium chloride load transition-metal catalyst of claim 1-6, comprise the steps:
1) described silica gel microball is dried removal moisture, carry out thermal activation treatment afterwards, adopt interim heating schedule to carrier: 200 DEG C keep 2h, 400 DEG C keep 2h, and 600 DEG C keep 2h, and 800 DEG C keep 2h, and top temperature is no more than 900 DEG C.Directly can use the carrier after thermal activation treatment and also can use after pre-treatment, pre-treatment adopts following two kinds of mode: a. by silica gel microball vacuum-treat, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free soaks and leaves standstill 10 ~ 50 hours, has reacted rear decompression and has steamed solvent and vacuum-drying; B. by silica gel microball vacuum-treat, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free stirs 2 ~ 10 hours, has reacted rear decompression and has steamed solvent and vacuum-drying.
Under two kinds of modes, the mass ratio of described pre-treatment medium and silica gel microball is 0 ~ 5:1; Pre-treatment medium adopts titanium tetrahalide or aluminum contained compound Al (OR ') nR
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10.
2) by described transistion metal compound and described step 1) the silica gel microball support of the catalyst prepared and anhydrous chlorides of rase magnesium carrier adopt efficient ball mill to carry out original position load Ziegler-Natta catalyst, obtains silica gel microball/magnesium chloride composite carried catalyst.The titanium elements total mass mark prepared is 1.0 ~ 3.8% of silica gel microball/magnesium chloride composite carried catalyst.
8. method according to claim 7, is characterized in that: described step 2) in granules of catalyst mode of appearance be Powdered, mobility is better, includes silica gel microball carrier; 2) silica gel microball/magnesium halide load Ziegler-Natta catalyst, catalyst active center's Stable distritation is surperficial in silica gel microball/magnesium chloride, silica gel microball inside and defectiveness place; 3) silica gel microball/magnesium chloride load Ziegler-Natta catalyst, catalyst efficiency is high.4) this method greatly reduces supported catalyst best catalytic efficiency ball milling load time, simple to operation, is easy to realize suitability for industrialized production.Described step 2) in also can add auxiliary agent in reaction system; Described auxiliary agent is internal electron donor compound, preferred diether and/or carbonate, at least one more preferably in 9,9-bis-(methoxymethyl) fluorenes and dibutyl phthalate.
9. method according to claim 8, is characterized in that: described step 2) in, described auxiliary agent and described step 1) mol ratio of carrier is 0.05 ~ 0.6 in silica gel microball/magnesium chloride catalyst of preparing.
10. the preparation method of olefin polymerization catalysis according to claim 7, it is characterized in that described high-energy ball milling adopts planetary ball mill, drum's speed of rotation is 300 ~ 500r/min, and milling time is 4 ~ 24h, and ratio of grinding media to material is 2:1 ~ 5:1.
The magnesium-supported Ziegler-Natta catalyst of 11. silica gel microball/anhydrous chlorides of rase according to claim 10 is preparing the application in polyisoprene or butylene one material, it is characterized in that, described isoprene or butylene one material and aluminum contained compound composite for catalysis isoprene or butylene one monomer polymerization.
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