CN114149524B - Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof - Google Patents
Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof Download PDFInfo
- Publication number
- CN114149524B CN114149524B CN202010924611.0A CN202010924611A CN114149524B CN 114149524 B CN114149524 B CN 114149524B CN 202010924611 A CN202010924611 A CN 202010924611A CN 114149524 B CN114149524 B CN 114149524B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- formula
- alkyl
- magnesium
- catalyst carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 54
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- -1 magnesium halide Chemical class 0.000 claims description 94
- 239000002245 particle Substances 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 42
- 239000011777 magnesium Substances 0.000 claims description 36
- 229910052749 magnesium Inorganic materials 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000000460 chlorine Chemical group 0.000 claims description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 230000001804 emulsifying effect Effects 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 12
- 229910017718 MgXY Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 229910052740 iodine Chemical group 0.000 claims description 8
- 239000011630 iodine Chemical group 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 claims description 2
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 claims description 2
- CFXDAHURBQNVFG-UHFFFAOYSA-M magnesium;propan-2-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)[O-] CFXDAHURBQNVFG-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 claims 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 29
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 239000002685 polymerization catalyst Substances 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 38
- 239000004743 Polypropylene Substances 0.000 description 36
- 229920001155 polypropylene Polymers 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 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
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- NUFATYMMMZQQCQ-UHFFFAOYSA-N butan-1-olate;titanium(3+) Chemical compound [Ti+3].CCCC[O-].CCCC[O-].CCCC[O-] NUFATYMMMZQQCQ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- NNRZFZBJEDXBPK-UHFFFAOYSA-N ethanolate;titanium(3+) Chemical compound [Ti+3].CC[O-].CC[O-].CC[O-] NNRZFZBJEDXBPK-UHFFFAOYSA-N 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- OAFMYIADTCIEFV-UHFFFAOYSA-N hexane;triethylalumane Chemical compound CCCCCC.CC[Al](CC)CC OAFMYIADTCIEFV-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/28—Metal alcoholates
- C07C31/30—Alkali metal or alkaline earth metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the field of olefin polymerization catalysts, and discloses a catalyst carrier for olefin polymerization, a preparation method and application thereof, a catalyst and application thereof, wherein the carrier has a structure shown in a formula (1); when the catalyst prepared by the catalyst carrier is used for olefin polymerization, the activity and hydrogen regulation sensitivity of the catalyst are good, and the polymer prepared by catalysis has high isotacticity and low polymer fine powder content.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to a catalyst carrier for olefin polymerization, a method for preparing the catalyst carrier for olefin polymerization, the catalyst carrier for olefin polymerization prepared by the method, application of the catalyst carrier in preparing a catalyst for olefin polymerization, a catalyst containing the catalyst carrier and application of the catalyst in olefin polymerization.
Background
It is well known that catalysts currently used for olefin polymerization are mostly prepared by supporting titanium halides on magnesium chloride alkoxides. This is due to the fact that magnesium chloride alkoxide supported Ziegler-Natta (Ziegler-Natta) catalysts have significantly better performance than other supported catalysts when used in the polymerization of olefins, particularly propylene.
Among them, among catalysts for olefin polymerization, spherical catalysts prepared from spherical supports are more popular in the market. Spherical carriers can be prepared by spray drying, spray cooling, high pressure extrusion, high speed stirring, emulsifying machine method, supergravity rotating bed method and the like, for example, WO99/44009, US 43999054 and the like disclose that spherical alcohol compound can be formed by emulsifying magnesium chloride alcohol compound system by high speed stirring at high temperature and then quenching.
However, the magnesium chloride alkoxide is prepared by quenching and solidifying the high-temperature alkoxide melt at a low temperature, so that the energy consumption is high, the preparation process is complex, a plurality of reactors are needed to be combined for preparation, the particle size distribution of the prepared alkoxide is wide, and the content of fine powder in the product obtained when the catalyst prepared from the alkoxide is used for propylene polymerization is high.
At present, polyolefin catalysts using dialkoxy magnesium such as diethoxy magnesium as a carrier have many advantages such as high activity, high isotacticity, sensitive hydrogen regulation performance and the like, but have the defects that spherical carriers and catalysts are difficult to obtain and spherical polymers with good fluidity are difficult to prepare.
Disclosure of Invention
The invention aims to overcome the defects of poor particle morphology and poor fluidity of a catalyst carrier for olefin polymerization in the prior art, and higher content of fine powder in a polymerization product obtained when the prepared catalyst is used for olefin polymerization.
The inventor of the present invention found that a carrier having a novel composition can be obtained by adding a magnesium metal simple substance in the process of preparing an olefin polymerization catalyst carrier, and compounding a specific amount of the magnesium metal simple substance with components such as magnesium halide, an alcohol compound, and an ethylene oxide compound, and also unexpectedly found that the compounding of the magnesium metal simple substance with other components can reduce collision probability between carrier particles of an unshaped catalyst, reduce adhesion between carrier particles, make the obtained carrier particles have good morphology, substantially no abnormal particles, and more noble, and the hydrogen regulation sensitivity of the catalyst prepared from the carrier is good, and the content of fine powder in the product obtained when the catalyst prepared from the carrier is used for olefin polymerization is low, based on the finding that the inventor provided the present invention.
The first aspect of the present invention provides a catalyst carrier for olefin polymerization, the carrier having a structure represented by formula (1):
wherein, in the formula (1),
R 1 selected from C 1-10 Alkyl of (a);
R 2 and R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; q >0.
In a second aspect, the present invention provides a process for preparing a catalyst support for the polymerization of olefins, the process comprising:
(1) Sequentially heating and emulsifying a component A in the optional presence of an inert liquid medium to obtain an emulsified product, wherein the component A contains a magnesium simple substance, magnesium halide shown as a formula MgXY and a formula R 1 Alcohol compounds represented by OH;
(2) Carrying out contact reaction on the emulsified product and a component B, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (2);
wherein in formula R 1 In OH, R 1 Selected from the group consisting ofC 1-10 Alkyl of (a);
in formula (2), R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C of (2) 1-6 Alkoxy, C 6-14 Aryl and C of (2) 6-14 An aryloxy group of (a);
the component A and the component B are used in such an amount that the resulting catalyst support has a structure represented by formula (1):
in formula (1), m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; q >0;
in the step (1), the amount of the elemental magnesium is 0.0001 to 19mol and the amount of the alcohol compound is 4 to 35mol with respect to 1mol of the magnesium halide.
In a third aspect, the present invention provides a catalyst support for the polymerization of olefins prepared by the process as described in the second aspect above.
A fourth aspect of the present invention provides the use of a catalyst support according to the first or third aspect hereinbefore described for the preparation of a catalyst for the polymerisation of olefins.
A fifth aspect of the present invention provides a catalyst comprising the catalyst support of the first or third aspect.
In a sixth aspect the present invention provides the use of a catalyst according to the fifth aspect in the polymerisation of olefins.
The catalyst carrier provided by the invention has good particle morphology, narrower particle size distribution, smooth surface and basically no special-shaped particles; when the catalyst prepared by the catalyst carrier is used for olefin polymerization, especially propylene polymerization, the activity and hydrogen regulation sensitivity of the catalyst are better, and the prepared polymer has higher isotacticity and lower fine powder content.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the groups are all n-hydrocarbyl groups such as pentyl for n-pentyl and butyl for n-butyl.
As described above, the first aspect of the present invention provides a catalyst carrier for olefin polymerization, the carrier having a structure represented by formula (1):
wherein, in the formula (1),
R 1 selected from C 1-10 Alkyl of (a);
R 2 and R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; q >0.
In the present invention, in the formula (1)Part representation (OC 2 H 2 XR 2 R 3 ) n 。
In the present invention, R 1 Selected from C 1-10 Alkyl of (C), R is 1 Alkyl groups that are linear, branched, or cyclic including, but not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutylA group, a tert-butyl group, a cyclobutyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a n-hexyl group, an isohexyl group, a cyclohexyl group, a 1-ethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2, 2-dimethylpropyl group and the like.
Herein, regarding R 1 The alkyl substituents of (a) have similar definitions to those described above, except for the difference in the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In the present invention, R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 Is a haloalkyl group of (2).
When said R is 2 And R is 3 Selected from C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 The alkyl and haloalkyl groups being straight-chain or branched, e.g. C 1-10 Alkyl groups of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, and the like. In the present invention, C substituted with 1 to 10 halogen atoms 1-10 Haloalkyl of (C) 1-10 The alkyl group of (2) may be a group in which 1 to 10 hydrogen atoms are replaced with halogen atoms, and a plurality of hydrogen atoms on the same carbon atom may be replaced with halogen atoms, or hydrogen atoms on different carbon atoms may be replaced with halogen atoms. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. For example-CF 3 、-CH 2 CF 3 、-CH 2 CF 2 H、-CF 2 CF 3 、-CF 2 CH 2 CF 2 H、-CH 2 CF 2 CF 2 H、-CH 2 CH 2 CH 2 Cl、-CH 2 CH 2 CH 2 Br, etc.
Herein, regarding R 2 And R is 3 The alkyl substituent and the haloalkyl substituent of (a) have similar definitions as described above, except for the difference in the number of carbon atoms, and the present invention will not be described in detail hereinafter.
Preferably, in formula (1), R 1 Selected from C 1-8 Is a hydrocarbon group.
To obtain a catalyst support with better morphology and better performance, R is more preferably 1 Selected from C 1-6 Is a hydrocarbon group.
In order to obtain a catalyst support with better morphology and better performance, R is preferably 2 And R is 3 Each independently selected from H, C 1-5 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-5 Is a haloalkyl group of (2).
In order to obtain a catalyst support with better morphology and better performance, preferably X is chosen from chlorine and bromine.
For use in propylene polymerization, the content of fines in the resulting polymer is preferably 0 < q < 20.
The catalyst carrier particles obtained by the invention are spherical, preferably, the average particle diameter of the catalyst carrier is 10-100 mu m, and the particle size distribution is less than 1.2.
More preferably, the catalyst support has an average particle diameter of 35 to 60 μm and a particle size distribution of 0.6 to 0.9.
In the present invention, the average particle diameter refers to D50.
In the present invention, the size of the particle size distribution is obtained according to (D90-D10)/D50.
In the present invention, the average particle diameter and particle size distribution of the catalyst support are measured using a laser particle sizer such as a MasterSizer 2000 laser particle sizer (manufactured by Malvern Instruments Ltd).
According to a preferred embodiment of the present invention, the catalyst support is selected from at least one of the following structural materials;
the inventors of the present invention found that the catalyst carrier having the above preferred embodiments has a better particle morphology and a smaller particle size distribution.
As previously described, a second aspect of the present invention provides a method of preparing a catalyst support for olefin polymerization, the method comprising:
(1) Sequentially heating and emulsifying a component A in the optional presence of an inert liquid medium to obtain an emulsified product, wherein the component A contains a magnesium simple substance, magnesium halide shown as a formula MgXY and a formula R 1 Alcohol compounds represented by OH;
(2) Carrying out contact reaction on the emulsified product and a component B, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (2);
wherein in formula R 1 In OH, R 1 Selected from C 1-10 Alkyl of (a);
in formula (2), R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C of (2) 1-6 Alkoxy, C 6-14 Aryl and C of (2) 6-14 An aryloxy group of (a);
the component A and the component B are used in such an amount that the resulting catalyst support has a structure represented by formula (1):
in formula (1), m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; q >0;
in the step (1), the amount of the elemental magnesium is 0.0001 to 19mol and the amount of the alcohol compound is 4 to 35mol with respect to 1mol of the magnesium halide.
In a second aspect of the invention, the R 1 、R 2 And R is 3 Substituent groups such as alkyl and haloalkyl groups and the definition of the sameThe definition of the first aspect of the invention is the same, and the present invention is not repeated here.
In the present invention, in the formula MgXY, when Y is selected from C 1-6 Alkyl, C of (2) 1-6 The alkyl and the alkoxy are straight or branched alkyl and alkoxy groups, the C 1-6 Alkyl of (a) refers to an alkyl group having 1 to 6 carbon atoms including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and the like; the C is 1-6 Alkoxy of (c) refers to an alkoxy group having 1 to 6 carbon atoms and includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and the like.
The C is 6-14 Aryl of (c) refers to aryl groups having 6 to 14 carbon atoms and includes, but is not limited to, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl, and the like.
The C is 6-14 Aryloxy of (c) refers to an aryloxy group having 6 to 14 carbon atoms, including, for example, but not limited to, phenoxy, naphthoxy, o-methylphenoxy, o-ethylphenoxy, m-methylphenoxy, and the like.
Herein, in the formula MgXY, substituents such as alkyl, alkoxy, aryl and aryloxy for Y have similar definitions as described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
According to a preferred embodiment of the invention, in the formula MgXY, X is selected from fluorine and bromine; y is selected from chlorine, bromine and C 1-5 Alkyl, C of (2) 1-5 Alkoxy, C 6-10 Aryl and C of (2) 6-10 An aryloxy group of (a).
In order to obtain a catalyst support having a better morphology and better performance, the magnesium halide is preferably at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxy magnesium chloride and n-butoxymagnesium chloride, and more preferably magnesium chloride.
According to another preferred embodiment of the invention, the compounds of formula (I)R 1 In OH, R 1 Selected from C 1-8 Is a hydrocarbon group.
In order to obtain a catalyst support having a better morphology and better performance, the alcohol compound is preferably at least one selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
In the present invention, the propanol and the pentanol refer to n-propanol and n-pentanol, respectively, unless otherwise specified.
According to still another preferred embodiment of the present invention, in formula (2), R 2 And R is 3 Each independently selected from H, C 1-5 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-5 Is a haloalkyl group of (2).
In order to obtain a catalyst support having a better morphology and a better performance, it is preferable that the ethylene oxide-based compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide, propylene oxide and butylene oxide.
In the invention, the magnesium simple substance can be magnesium scraps, magnesium strips or magnesium powder, and preferably magnesium powder.
Preferably, step (1) is carried out in the presence of a surfactant according to the method of the second aspect of the present invention, the present invention is not particularly limited in the kind of the surfactant, but polyvinylpyrrolidone (PVP) is particularly preferred in order to obtain a catalyst support having better performance.
Preferably, the surfactant is used in an amount of 1 to 40g relative to 1mol of the magnesium halide.
In the method according to the second aspect of the present invention, preferably, the ethylene oxide-based compound is used in an amount of 1 to 10mol with respect to 1mol of the magnesium halide.
In order to obtain a catalyst support having a better morphology and better performance, it is more preferable that the amount of the magnesium element is 0.0001 to 13mol, preferably 0.1 to 13mol, the amount of the alcohol compound is 6 to 32mol, and the amount of the ethylene oxide compound is 2 to 6mol, relative to 1mol of the magnesium halide.
In the present invention, the amount of the inert liquid medium to be used may be selected depending on the amount of the magnesium halide, and preferably, the amount of the inert liquid medium to be used is 0.8L to 10L, more preferably, 2 to 8L, with respect to 1mol of the magnesium halide.
Preferably, the inert liquid medium is a silicone oil and/or an inert liquid hydrocarbon solvent, more preferably, the inert liquid medium is at least one selected from kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil, and particularly preferably is white oil.
In the present invention, it should be noted that the trace amount of water carried in each of the above reactants may also participate in the reaction for forming the spherical support, and thus, the spherical support may be prepared to contain trace amounts of water carried from the reaction raw materials and the reaction medium, and those skilled in the art should not understand the limitation of the present invention.
Preferably, in step (1), the heating conditions include: the heating temperature is 60-120 ℃, and the heating time is 0.5-5h.
More preferably, in step (1), the heating conditions include: the heating temperature is 60-100deg.C, and the heating time is 0.5-3h.
The specific method of operation of the emulsification in step (1) is not particularly limited and may be carried out by methods known in the art. For example, emulsification is performed using low-speed shearing or high-speed shearing. Preferably, when low shear is used, the agitation rate of the low shear is 400-800rpm. Such high speed shearing processes are well known to those skilled in the art, and are carried out, for example, using the high speed agitation process disclosed in CN1330086 a. In addition, the emulsification operation may be carried out by referring to the method disclosed in the following patent application, such as the method disclosed in CN1580136a in which a solution containing a liquid magnesium halide compound is subjected to rotary dispersion in a hypergravity bed (the rotation speed is 100 to 3000 rpm); the solution containing the liquid magnesium halide adduct is then discharged in an emulsifying machine at a speed of 1500-8000rpm as disclosed in CN1463990 a; the solution containing the liquid magnesium halide adducts is emulsified by spraying as disclosed in US6020279 a.
Preferably, in step (2), the conditions of the contact reaction include: the temperature is 60-120deg.C, and the time is 20-60min.
More preferably, in step (2), the conditions of the contact reaction include: the temperature is 60-100deg.C, and the time is 20-50min.
The method according to the second aspect of the present invention further includes a post-treatment means, which is conventional in the art, such as solid-liquid separation, washing, drying, etc., of the product obtained by the contact reaction, and the present invention is not particularly limited thereto. The solid-liquid separation may be performed by any of various conventional methods capable of separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation method is a pressure filtration method. The conditions for press filtration are not particularly limited in the present invention, so long as the separation of the solid phase and the liquid phase is achieved as sufficiently as possible. The washing may be performed by methods known to those skilled in the art, and for example, the obtained solid phase product may be washed with an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether and gasoline. The specific conditions for the drying are not particularly limited in the present invention, and for example, the temperature of the drying may be 20 to 70 ℃, the time of the drying may be 0.5 to 10 hours, and the drying may be performed under normal pressure or reduced pressure.
In a second aspect of the present invention, according to a preferred embodiment of the present invention, the method of the present invention comprises:
(1) In the presence of an optional inert liquid medium, in the presence of a surfactant, a magnesium element, a magnesium halide represented by the formula MgXY and a compound represented by the formula R 1 Mixing alcohol compounds shown as OH, and then sequentially heating and emulsifying to obtain an emulsified product;
(2) Carrying out contact reaction on the emulsified product and an ethylene oxide compound with a structure shown in a formula (2);
the amount of the magnesium element is 0.0001 to 19mol and the amount of the alcohol compound is 4 to 35mol relative to 1mol of the magnesium halide.
By adopting the method provided by the invention, the catalyst carrier prepared by adopting the specific dosage of magnesium metal simple substance and components such as magnesium halide, alcohol compound and ethylene oxide compound is good in particle morphology, narrow in particle size distribution, smooth in surface and basically free of special-shaped particles.
As previously described, a third aspect of the present invention provides a catalyst support for olefin polymerization prepared by the method of the second aspect described above.
The catalyst carrier prepared by the method has good particle morphology, narrow particle size distribution, smooth surface and basically no special-shaped particles.
As previously described, a fourth aspect of the present invention provides the use of the catalyst support of the first or third aspect described above in the preparation of a catalyst for the polymerisation of olefins.
As described above, the fifth aspect of the present invention provides a catalyst comprising the catalyst support of the first or third aspect.
In the present invention, the composition of the catalyst is not particularly limited, and may be a composition of a catalyst for olefin polymerization existing in the art, but in order to be able to obtain a catalyst suitable for olefin polymerization, particularly propylene polymerization, it is preferable that the catalyst contains the carrier, a titanium halide compound and an electron donor compound. Preferably, the titanium halide compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tri-n-butoxide, titanium di-n-butoxide dichloride, titanium mono-n-butoxide trichloride, titanium tri-ethoxide, titanium di-ethoxide dichloride, titanium mono-ethoxide trichloride, and titanium trichloride. Preferably, the electron donor compound is selected from at least one of diisobutyl phthalate, carboxylic acid glycol esters and phosphoric acid esters. Meanwhile, the content of each component in the catalyst is not particularly limited, and a person skilled in the art can reasonably adjust and design according to actual needs.
The preparation method of the catalyst is not particularly limited, and may be prepared by methods of preparing an olefin polymerization catalyst existing in the art, and the present invention is exemplified in the examples hereinafter to be used as a specific procedure, and the person skilled in the art should not be construed as limiting the present invention.
As previously mentioned, a sixth aspect of the present invention provides the use of a catalyst according to the fifth aspect of the present invention in the polymerisation of olefins.
The specific method of operation of the application is not particularly limited, and one skilled in the art can operate using methods of olefin polymerization that are known in the art, and the invention is not described in detail herein, and the invention hereinafter sets forth a specific course of operation, which should not be construed as limiting the invention.
The invention will be described in detail below by way of examples.
In the following examples, all the raw materials used were commercially available ones unless otherwise specified.
Wherein, the magnesium powder is purchased from the carbofuran company;
epichlorohydrin was purchased from belvedere corporation;
diisobutyl phthalate was purchased from belowder company;
titanium tetrachloride was purchased from carbofuran corporation;
triethylaluminum was purchased from belowder company;
methylcyclohexyl dimethoxy silane was purchased from carbofuran corporation.
In the examples below, the properties referred to were tested as follows:
1. average particle diameter and particle size distribution of catalyst support: the measurement was carried out by using a Master Sizer 2000 particle Sizer manufactured by Malvern Instruments company;
2. appearance of the catalyst support: observations were made by means of an optical microscope model Eclipse E200 from Nikon corporation;
3. structure and composition of the catalyst support: carrying out 1H-NMR test on the carrier by using an AVANCE 300 nuclear magnetic resonance spectrometer of Bruker, switzerland, and carrying out test on the carrier by using a PY-2020iD type cracker of front tellab, a traceGCultra type chromatograph of Thermo Fisher and a DSQ II type mass spectrometer;
4. polymer isotactic index: obtained through GBT 2412-2008 test;
5. polymer melt index: measured according to ISO1133, 230 ℃,2.16kg load;
6. polymerization activity: the evaluation was carried out by the method in which the weight of the polymerization product obtained after polymerization was compared with the weight of the catalyst used.
In the examples below, the emulsification was carried out with stirring at 600rpm during the preparation of the catalyst support, unless otherwise specified.
The following examples and comparative examples serve to illustrate the preparation of catalyst supports.
Example 1
(1) Adding 0.08mol of magnesium chloride, 0.96mol of ethanol, 0.01mol of metal magnesium powder and 2g of surfactant PVP into a 0.6L reaction kettle, heating to 70 ℃ under stirring, heating at constant temperature for 2 hours, and emulsifying to obtain an emulsified product;
(2) Carrying out contact reaction on the emulsified product obtained in the step (1) and 0.48mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 70 ℃ and the time is 30min, then the filter pressing is carried out, the filter pressing product is washed by hexane for 5 times, and the catalyst carrier Z1 is obtained by vacuum drying.
The catalyst support Z1 was tested to have an average particle diameter (D50) of 38. Mu.m, and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst support Z1 was observed to have a relatively regular particle morphology, a smooth surface, a relatively concentrated particle size distribution, and substantially no irregular particles.
Through testing, the structure and the composition of the obtained catalyst carrier Z1 are as follows:
example 2
(1) Adding 0.08mol of magnesium chloride, 1.96mol of ethanol, 0.1mol of metal magnesium powder and 2g of surfactant PVP into a 0.6L reaction kettle, heating to 70 ℃ under stirring, heating at constant temperature for 2 hours, and emulsifying to obtain an emulsified product;
(2) Carrying out contact reaction on the emulsified product obtained in the step (1) and 0.48mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 90 ℃ and the time is 30min, then the filter pressing is carried out, the filter pressing product is washed by hexane for 5 times, and the catalyst carrier Z2 is obtained by vacuum drying.
The catalyst support Z2 was tested to have an average particle diameter (D50) of 41. Mu.m, and a particle size distribution ((D90-D10)/D50) of 0.7.
The catalyst support Z2 was observed to have a relatively regular particle morphology, a smooth surface, a relatively concentrated particle size distribution, and substantially no irregular particles.
Through testing, the structure and the composition of the obtained catalyst carrier Z2 are as follows:
example 3
(1) Adding 0.08mol of magnesium chloride, 2.5mol of ethanol, 1mol of metal magnesium powder and 3g of PVP into a 0.6L reaction kettle, heating to 70 ℃ under stirring, heating at constant temperature for 1h, and emulsifying to obtain an emulsified product;
(2) Carrying out contact reaction on the emulsified product obtained in the step (1) and 0.16mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 70 ℃ and the time is 20min, then the filter pressing is carried out, the filter pressing product is washed by hexane for 5 times, and finally the product is dried in vacuum, thus obtaining the catalyst carrier Z3.
The catalyst support Z3 was tested to have an average particle diameter (D50) of 44. Mu.m, and a particle size distribution ((D90-D10)/D50) of 0.9.
The catalyst support Z3 was observed to have a relatively regular particle morphology, a smooth surface, a relatively concentrated particle size distribution, and substantially no irregular particles.
Through testing, the structure and the composition of the catalyst carrier Z3 are as follows:
example 4
(1) Adding 0.08mol of magnesium chloride, 5mol of ethanol, 1.8mol of metal magnesium powder and 2g of surfactant PVP into a 0.6L reaction kettle, heating to 70 ℃ under stirring, heating at constant temperature for 2 hours, and emulsifying to obtain an emulsified product;
(2) Carrying out contact reaction on the emulsified product obtained in the step (1) and 0.48mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 70 ℃ and the time is 30min, then the filter pressing is carried out, the filter pressing product is washed by hexane for 5 times, and the catalyst carrier Z4 is obtained by vacuum drying.
The catalyst support Z4 has, as tested, an average particle diameter (D50) of 45. Mu.m, and a particle size distribution ((D90-D10)/D50) of 0.9.
The catalyst support Z4 was observed to have a relatively regular particle morphology, a smooth surface, substantially spherical shape, and substantially no irregular particles present.
Through testing, the structure and the composition of the obtained catalyst carrier Z4 are as follows:
comparative example 1
(1) Adding 0.08mol of magnesium chloride, 0.96mol of ethanol and 1g of PVP as a surfactant into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, and emulsifying to obtain an emulsified product;
(2) And (3) reacting the emulsified product obtained in the step (1) with 0.48mol of epichlorohydrin at a constant temperature of 90 ℃ for half an hour, then performing pressure filtration, washing the pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the catalyst carrier DZ1.
The catalyst support DZ1 has, as tested, an average particle diameter (D50) of 60. Mu.m, and a particle size distribution ((D90-D10)/D50) of 1.3.
It was observed that shaped particles were present in the catalyst support DZ1.
Comparative example 2
6.4g of magnesium powder, 400ml of ethanol and 0.11g of iodine are added into a 0.6L reaction kettle, and the reaction temperature is 78 ℃ until no gas is discharged. Washing with ethanol for three times, filtering, and drying to obtain the alkoxy magnesium carrier DZ2.
The catalyst carrier DZ2 for olefin polymerization was tested to have an average particle diameter (D50) of 45 μm and a particle size distribution ((D90-D10)/D50) of 1.1.
The catalyst support DZ2 was observed to be non-spherical and had a rough surface.
Through testing, the structure and the composition of the obtained catalyst carrier DZ2 are as follows: mg (OC) 2 H 5 ) 2 。
The following test examples and comparative test examples are provided to illustrate the preparation of olefin polymerization catalysts and olefin polymers using the above catalyst supports.
Test example 1-1
(1) Preparation of olefin polymerization catalyst
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added, cooled to-20℃and 40g of the catalyst carrier Z1 obtained in example 1 was then added, stirred at-20℃for 30 minutes, then slowly warmed to 110℃and 1.5mL of diisobutylphthalate was added during warming, stirred at 110℃for 30 minutes, and then the liquid was filtered off. Then washing with titanium tetrachloride for 2 times, finally washing with hexane for 3 times, and drying to obtain the olefin polymerization catalyst C1.
(2) Preparation of Polypropylene
Under the protection of nitrogen, 1mmol of triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane, 10mg of olefin polymerization catalyst C1 obtained in the step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene monomer are added into a 5L stainless steel high-pressure reaction kettle, the temperature is raised to 70 ℃, the reaction is carried out for 1h, and then the polypropylene is obtained after cooling, pressure release, discharging and drying.
The polypropylene powder has good particle morphology and basically no special-shaped material.
Test examples 1 to 2
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (2), the volumes of hydrogen used are different,
specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The polypropylene powder has good particle morphology and basically no special-shaped material.
Test example 2-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the types of the catalyst carriers used are different,
specific: the catalyst carrier Z1 was replaced with the catalyst carrier Z2 prepared in example 2 of the same weight to obtain an olefin polymerization catalyst C2; then, a polypropylene powder was prepared in accordance with step (2) of test example 1-1 using an olefin polymerization catalyst C2.
The polypropylene powder has good particle morphology and basically no special-shaped material.
Test example 2-2
Polypropylene was prepared in a similar manner to test example 2-1, except that: in the step (2), the volumes of hydrogen used are different,
specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The polypropylene powder has good particle morphology and basically no special-shaped material.
Test example 3-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the types of the catalyst carriers used are different,
specific: replacing the catalyst carrier Z1 with the catalyst carrier Z3 prepared in example 3 with the same weight to obtain an olefin polymerization catalyst C3; then, a polypropylene powder was prepared in accordance with step (2) of test example 1-1 using an olefin polymerization catalyst C3.
The polypropylene powder has good particle morphology and basically no special-shaped material.
Test example 3-2
Polypropylene was prepared in a similar manner to test example 3-1, except that: in the step (2), the volumes of hydrogen used are different,
specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The polypropylene powder has good particle morphology and basically no special-shaped material.
Test example 4-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the types of the catalyst carriers used are different,
specific: replacing the catalyst carrier Z1 with the catalyst carrier Z4 prepared in example 4 with the same weight to obtain an olefin polymerization catalyst C4; then, a polypropylene powder was prepared in accordance with step (2) of test example 1 using an olefin polymerization catalyst C4.
The polypropylene powder has good particle morphology and less special-shaped materials.
Test example 4-2
Polypropylene was prepared in a similar manner to test example 4-1, except that: in the step (2), the volumes of hydrogen used are different,
specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The polypropylene powder has good particle morphology and less special-shaped materials.
Comparative test example 1-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the types of the catalyst carriers used are different,
specific: replacing the catalyst carrier Z1 with the catalyst carrier DZ1 prepared in comparative example 1 with the same weight to obtain an olefin polymerization catalyst DC1; then, a polypropylene powder was prepared in accordance with step (2) of test example 1-1 using an olefin polymerization catalyst DC 1.
The catalyst DC1 has non-spherical particles, has rough surface, and the obtained polypropylene powder particles have more abnormal materials and poor fluidity.
Comparative test examples 1-2
Polypropylene was prepared in a similar manner to comparative test example 1-1, except that: in the step (2), the volumes of hydrogen used are different,
specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The polypropylene powder particles have more special-shaped materials and have poor fluidity.
Comparative test example 2
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the types of the catalyst carriers used are different,
specific: replacing the catalyst carrier Z1 with the catalyst carrier DZ2 prepared in comparative example 2 with the same weight to obtain an olefin polymerization catalyst DC2; then, a polypropylene powder was prepared in accordance with step (2) of test example 1-1 using an olefin polymerization catalyst DC 2.
The polypropylene powder particles have more special-shaped materials and have poor fluidity.
The performance of the catalysts and polypropylene obtained in the above test examples and comparative test examples was tested in the present invention, and the specific results are shown in Table 1.
TABLE 1
Note that: in Table 1 "<120 mesh content" means the content (wt%) of particles having a particle diameter smaller than 120 mesh in the polypropylene powder, and the polypropylene powder is obtained by sieving with a 120 mesh sieve and weighing.
From the results, the catalyst carrier prepared by the method has good particle morphology, narrow particle size distribution, smooth surface and basically no special-shaped particles.
When the catalyst prepared by the catalyst carrier is used for olefin polymerization, such as propylene, the polymerization activity and the hydrogen regulation sensitivity are good, the prepared polymer has high isotacticity and melt index, the polymer particle morphology is good, and the polymer fine powder content is low.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (22)
1. A catalyst carrier for olefin polymerization, characterized in that the carrier has a structure represented by formula (1):
wherein, in the formula (1),
R 1 selected from C 1-10 Alkyl of (a);
R 2 and R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; q is more than 0 and less than or equal to 22.
2. The catalyst carrier according to claim 1, wherein in the formula (1),
R 1 selected from C 1-8 Alkyl of (a);
and/or R 2 And R is 3 Each independently selected from H, C 1-5 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-5 A haloalkyl group of (2);
and/or X is selected from chlorine and bromine;
and/or 0 < q < 20.
3. The catalyst carrier according to claim 2, wherein in the formula (1),
R 1 selected from C 1-6 Is a hydrocarbon group.
4. The catalyst carrier according to claim 1, wherein the catalyst carrier is selected from at least one of the following structural substances;
5. the catalyst carrier according to any one of claims 1 to 4, wherein the catalyst carrier has an average particle diameter of 10 to 100 μm and a particle size distribution of less than 1.2.
6. The catalyst carrier according to claim 5, wherein the catalyst carrier has an average particle diameter of 35 to 60 μm and a particle size distribution of 0.6 to 0.9.
7. A process for preparing a catalyst support for the polymerization of olefins, characterized in that it comprises:
(1) Sequentially heating and emulsifying a component A in the optional presence of an inert liquid medium to obtain an emulsified product, wherein the component A contains a magnesium simple substance, magnesium halide shown as a formula MgXY and a formula R 1 Alcohol compounds represented by OH;
(2) Carrying out contact reaction on the emulsified product and a component B, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (2);
wherein in formula R 1 In OH, R 1 Selected from C 1-10 Alkyl of (a);
in formula (2), R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C of (2) 1-6 Alkoxy, C 6-14 Aryl and C of (2) 6-14 An aryloxy group of (a);
the component A and the component B are used in such an amount that the resulting catalyst support has a structure represented by formula (1):
in formula (1), m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; q is more than 0 and less than or equal to 22;
in the step (1), the amount of the elemental magnesium is 0.0001 to 19mol and the amount of the alcohol compound is 4 to 35mol with respect to 1mol of the magnesium halide.
8. The method of claim 7, wherein, in formula MgXY, X is selected from fluorine and bromine; y is selected from chlorine, bromine and C 1-5 Alkyl, C of (2) 1-5 Alkoxy, C 6-10 Aryl and C of (2) 6-10 An aryloxy group of (a).
9. The method of claim 7, wherein the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxy magnesium chloride, isopropoxy magnesium chloride, and n-butoxy magnesium chloride.
10. The method of claim 7, wherein in formula R 1 In OH, R 1 Selected from C 1-8 Is a hydrocarbon group.
11. The method of claim 7, wherein the alcohol compound is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
12. The method according to claim 7, wherein in formula (2), R 2 And R is 3 Each independently selected from H, C 1-5 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-5 Is a haloalkyl group of (2).
13. The method of claim 7, wherein the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, bromopropane, and oxybutylene oxide.
14. The method according to any one of claims 7 to 13, wherein the amount of the elemental magnesium is 0.0001 to 13mol, the amount of the alcohol compound is 6 to 32mol, and the amount of the ethylene oxide compound is 2 to 6mol, relative to 1mol of the magnesium halide;
and/or the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
15. The method according to any one of claims 7-13, wherein in step (1), the heating conditions include: the heating temperature is 60-120 ℃, and the heating time is 0.5-5h.
16. The method of claim 15, wherein in step (1), the heating conditions include: the heating temperature is 60-100deg.C, and the heating time is 0.5-3h.
17. The method according to any one of claims 7 to 13, wherein in step (2), the conditions of the contact reaction include: the temperature is 60-120deg.C, and the time is 20-60min.
18. The method of claim 17, wherein in step (2), the contacting reaction conditions comprise: the temperature is 60-100deg.C, and the time is 20-50min.
19. A catalyst support for the polymerization of olefins prepared by the process of any of claims 7 to 18.
20. Use of the catalyst support according to any one of claims 1 to 6 and 19 for the preparation of a catalyst for the polymerization of olefins.
21. A catalyst comprising the catalyst support of any one of claims 1 to 6 and 19.
22. Use of the catalyst of claim 21 in olefin polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010924611.0A CN114149524B (en) | 2020-09-05 | 2020-09-05 | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010924611.0A CN114149524B (en) | 2020-09-05 | 2020-09-05 | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114149524A CN114149524A (en) | 2022-03-08 |
| CN114149524B true CN114149524B (en) | 2023-07-21 |
Family
ID=80460586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010924611.0A Active CN114149524B (en) | 2020-09-05 | 2020-09-05 | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114149524B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040683A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Spherical carriers for olefin polymerization catalyst and preparation method |
| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
| CN103788259A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Polypropylene with narrow distribution of molecular weight |
| CN104558289A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application thereof, and polypropylene and polymerization method thereof |
| CN105440181A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Propylene polymer and preparation method thereof |
| CN105440175A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof and catalyst used for olefin polymerization and application |
| CN110498874A (en) * | 2018-05-18 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of alkoxyl magnesium particle, and its preparation method and application |
| CN110498872A (en) * | 2018-05-18 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of alkoxyl magnesium particle, and its preparation method and application |
-
2020
- 2020-09-05 CN CN202010924611.0A patent/CN114149524B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040683A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Spherical carriers for olefin polymerization catalyst and preparation method |
| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
| CN103788259A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Polypropylene with narrow distribution of molecular weight |
| CN104558289A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application thereof, and polypropylene and polymerization method thereof |
| CN105440181A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Propylene polymer and preparation method thereof |
| CN105440175A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof and catalyst used for olefin polymerization and application |
| CN110498874A (en) * | 2018-05-18 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of alkoxyl magnesium particle, and its preparation method and application |
| CN110498872A (en) * | 2018-05-18 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of alkoxyl magnesium particle, and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Liu Tao，Li Weili，Xia Xianzhi，Mao Bingquan.A Facile One-Step Method for Spherical Support Preparation of Ziegler-Natta Catalyst.Journal of Applied Polymer Science.2014,第131卷(第21期),41014. * |
| 周 倩，秦亚伟，李化毅，张辽云，董金勇.Ziegler-Natta催化剂的载体技术研究进展.《高分子通报》.2016,(第209期),126-139. * |
| 王帆，张润聪，李红明，南枫，于洪超，程璐，黄启谷.烯烃配位聚合Ziegler-Natta催化剂烷氧基镁载体的研制.《弹性体》.2017,第27卷(第6期),1-11. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114149524A (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111072797B (en) | Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application | |
| CN111072802B (en) | Olefin polymerization catalyst carrier, preparation method and application thereof | |
| CN111072804B (en) | Olefin polymerization catalyst component and application thereof, olefin polymerization catalyst and olefin polymerization method | |
| CN111072803B (en) | Olefin polymerization catalyst carrier, preparation method and application thereof | |
| CN106608941B (en) | A kind of carrier and preparation method thereof for olefin polymerization catalysis | |
| CN111072806B (en) | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method | |
| CN111072811A (en) | Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application thereof | |
| CN111072810A (en) | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method | |
| CN114149524B (en) | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof | |
| CN111072808B (en) | Catalyst component, catalyst, application thereof and olefin polymerization method | |
| CN114149518B (en) | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof | |
| CN114149523B (en) | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof | |
| CN114478864B (en) | Spherical catalyst carrier for olefin polymerization and preparation method and application thereof | |
| CN112694550B (en) | Olefin polymerization catalyst carrier, preparation method thereof, catalyst component and application | |
| CN114478860B (en) | Catalyst carrier for olefin polymerization, preparation method and application thereof, olefin polymerization catalyst and application thereof | |
| CN114478863B (en) | Catalyst component for olefin polymerization and preparation method thereof, catalyst and application thereof, and polyolefin and preparation method thereof | |
| CN114478847B (en) | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof | |
| CN116023543B (en) | Catalyst component for olefin polymerization, catalyst for olefin polymerization and application thereof | |
| CN115975075B (en) | Catalyst component for olefin polymerization, catalyst and application | |
| CN116041586B (en) | Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method | |
| CN114478846B (en) | Carrier of catalyst with olefin polymerization catalyzing function, preparation method and application thereof, olefin polymerization catalyst and application thereof | |
| CN115975078B (en) | Catalyst component for olefin polymerization, catalyst and application | |
| CN112759687B (en) | Catalyst component for olefin polymerization and preparation method thereof, catalyst and olefin polymerization method | |
| CN116041581B (en) | Olefin polymerization catalyst component, preparation method and application thereof | |
| CN111072813B (en) | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |