CN117467037A - Catalyst carrier for olefin polymerization and preparation method and application thereof - Google Patents
Catalyst carrier for olefin polymerization and preparation method and application thereof Download PDFInfo
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- CN117467037A CN117467037A CN202210864856.8A CN202210864856A CN117467037A CN 117467037 A CN117467037 A CN 117467037A CN 202210864856 A CN202210864856 A CN 202210864856A CN 117467037 A CN117467037 A CN 117467037A
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- olefin polymerization
- catalyst carrier
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- catalyst
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 195
- 239000003054 catalyst Substances 0.000 title claims abstract description 175
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 168
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- -1 magnesium halide Chemical class 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 40
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 36
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011777 magnesium Substances 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 229910017718 MgXY Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 37
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005037 alkyl phenyl group Chemical group 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 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
- 239000002904 solvent Substances 0.000 claims description 3
- WRIPPXUSBFBIRE-UHFFFAOYSA-N CCCCCCCCCCCCN1C=CC(C=C)=CC1.Br Chemical compound CCCCCCCCCCCCN1C=CC(C=C)=CC1.Br WRIPPXUSBFBIRE-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004349 Polyvinylpyrrolidone-vinyl acetate copolymer Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 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
- 238000002156 mixing Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019448 polyvinylpyrrolidone-vinyl acetate copolymer Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims 1
- 230000002159 abnormal effect Effects 0.000 abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- 239000000843 powder Substances 0.000 description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 27
- 239000004743 Polypropylene Substances 0.000 description 23
- 229920001155 polypropylene Polymers 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- 229920000098 polyolefin Polymers 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 4
- 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 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 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
- 238000013019 agitation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 238000004945 emulsification Methods 0.000 description 2
- 239000011521 glass Substances 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 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
- 238000010008 shearing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000005311 nuclear magnetism Effects 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 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
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the field of catalysts, and discloses a catalyst carrier for olefin polymerization, a preparation method and application thereof. The synthetic raw materials of the catalyst carrier for olefin polymerization comprise bismuth source compounds, magnesium halide with the general formula of MgXY, compounds with the general formula of ROH and ethylene oxide compounds; wherein in the general formula MgXY, X is halogen, Y is halogen, C 1 ‑C 14 Alkyl, C of (2) 1 ‑C 14 Alkoxy, C 6 ‑C 14 Aryl or C of (2) 6 ‑C 14 An aryloxy group of (a); in the general formula ROH, R is C 1 ‑C 8 Straight chain alkyl, C 3 ‑C 8 Branched alkyl or C 3 ‑C 8 Cycloalkyl of (c); by a means ofThe structure of the ethylene oxide compound is shown as a formula (II):wherein R is 5 And R is 6 The same or different, each independently hydrogen, C 1 ‑C 5 Straight-chain alkyl or C 3 ‑C 5 Branched alkyl groups wherein the hydrogen on the alkyl group is optionally substituted with a halogen atom; the catalyst carrier for olefin polymerization of the present invention has good particle morphology, smooth surface and substantially no abnormal particles.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst carrier for olefin polymerization and a preparation method thereof, and application of the catalyst carrier for olefin polymerization in preparation of a catalyst for olefin polymerization.
Background
As is well known, the discovery of magnesium chloride supports is one of the important milestones in the development history of coordination polymerization, and up to now, most of the catalysts for olefin polymerization used industrially are prepared based on titanium halide supported on magnesium chloride supports. This is because the magnesium chloride-supported catalyst has superior properties, which are not comparable to those of other supported catalysts, when used for polymerization of olefins, particularly propylene. The magnesium chloride supported spherical catalyst is generally prepared by spherical supports of magnesium chloride alkoxide. Spherical catalysts are favored by markets and manufacturers. Spherical supports can be prepared by spraying, extrusion, emulsification, and supergravity methods, etc., as described in CN1036011C, etc., by first melting magnesium chloride alkoxide at high temperature, then emulsifying the magnesium chloride alkoxide system with high speed stirring, and quenching with a cooling medium to prepare the spherical alkoxide.
The spherical carrier is produced through quenching and solidification of high temperature melt at low temperature, and the switching between high temperature and low temperature results in high power consumption, long technological period and high required reactors. And it is difficult to prepare a carrier having a small particle diameter by this method. In general, small particle size supports not only reduce the fines of the prepared catalyst resulting in polymers but also are widely used in various gas phase polymerization processes. CN102040683a discloses a process for preparing a support by reacting magnesium halide alkoxides with oxiranes without high temperatures and multiple reactors. However, the catalyst carrier prepared by the method has other defects such as insufficient stability, poor carrier molding effect, and no carrier with smaller particle size.
Therefore, it is important to develop a novel catalyst support for olefin polymerization which can overcome the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The invention aims to solve the technical problems that a catalyst carrier for olefin polymerization in the prior art has the defects of insufficient stability, poor carrier molding effect and the like, can not prepare a carrier with smaller particle size and can not prepare a catalyst with stable activity release, and provides a catalyst carrier for olefin polymerization and a preparation method thereof, and application of the catalyst carrier for olefin polymerization in preparing a catalyst for olefin polymerization.
To solve the above technical problem, a first aspect of the present invention provides a catalyst carrier for olefin polymerization, the catalyst carrier for olefin polymerization comprising a compound represented by structural formula (I):
wherein the bismuth in the catalyst support for olefin polymerization is mainly present in the form of an alkoxybismuth halide OR an alkoxybismuth nitrate OR an alkoxybismuth acetate, such as Bi (OR x ) j (OR y ) k Cl i 、Bi(OR x ) j (OR y ) k (NO 3 ) i 、Bi(OR x ) j (OR y ) k (CH 3 COO) i Wherein Rx is alkyl, ry is alkyl halide, i is 1-2, j is 1 or 0, k is 1 or 0, j and k are not simultaneously 0, i+j+k=3; preferably, rx is a C1-C8 straight chain alkyl group, a C3-C8 branched alkyl group or a C3-C8 cycloalkyl group, and Ry is a C2-C10 halogenated alkyl group.
According to some embodiments of the invention, R in the compound of formula (I) 1 Is a C1-C8 straight chain alkyl group, a C3-C8 branched chain alkyl group or a C3-C8 cycloalkyl group; r is R 2 And R is 3 Identical or different, each independently of the others is hydrogen, C1-C5 straight-chain or C3-C5 branched alkyl, further preferably R 2 And R is 3 Hydrogen on the alkyl group is optionally substituted with a halogen atom; x is halogen, preferably chlorine or bromine; m is 0.1-1.9, n is 0.1-1.9, m+n=2.
According to some embodiments of the present invention, the molar ratio of the compound represented by structural formula (I) (based on Mg molar amount) and bismuth element in the catalyst carrier for olefin polymerization is 1: (0.01 to 1), preferably 1: (0.02 to 0.16), for example, 1:0.1, 1:0.06, 1:0.02, 1:0.15, 1:0.16, 1:0.04.
according to some embodiments of the present invention, the synthetic raw materials of the catalyst support for olefin polymerization include a bismuth source compound, magnesium halide of the general formula MgXY, a compound of the general formula ROH, and an ethylene oxide-based compound.
According to some embodiments of the invention, in the general formula MgXY, X is halogen, Y is halogen, C 1 -C 14 Alkyl, C of (2) 1 -C 14 Alkoxy, C 6 -C 14 Aryl or C of (2) 6 -C 14 An aryloxy group of (a).
According to some embodiments of the invention, in the general formula MgXY, X is chlorine or bromine, Y is chlorine, bromine, C 1 -C 5 Alkyl, C of (2) 1 -C 5 Alkoxy, C 6 -C 10 Aryl or C of (2) 6 -C 10 An aryloxy group of (a); the C is 1 -C 5 The alkyl group of (C) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl group 1 -C 5 The alkoxy group of (C) may be methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy 6 -C 10 The aryl group of (C) may be phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl or naphthyl 6 -C 10 The aryloxy group of (a) may be phenoxy or naphthoxy.
According to some embodiments of the invention, the magnesium halide of the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, phenoxy magnesium chloride, isopropoxy magnesium chloride and n-butoxy magnesium chloride. Magnesium chloride is preferred from the viewpoint of availability of raw materials.
According to some embodiments of the invention, in the general formula ROH, R is C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl or C 3 -C 8 Cycloalkyl groups of (a).
According to some embodiments of the invention, in the general formula ROH, R is C 1 -C 8 Straight-chain alkyl or C 3 -C 8 Branched alkyl of (a); the C is 1 -C 8 Straight-chain alkyl or C 3 -C 8 The branched alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl.
According to some embodiments of the invention, the compound of formula ROH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
According to some embodiments of the invention, the oxirane has a structure according to formula (II):
in the formula (II), R 5 And R is 6 The same or different, each independently hydrogen, C 1 -C 5 Straight-chain alkyl or C 3 -C 5 Branched alkyl groups wherein the hydrogen on the alkyl group is optionally substituted with a halogen atom.
According to some embodiments of the invention, in formula (II), R 5 And R is 6 The same or different, each independently hydrogen, C 1 -C 3 Straight-chain alkyl or C 1 -C 3 Is a haloalkyl group of (2).
According to some embodiments of the invention, the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide, and butylene oxide.
According to some embodiments of the invention, the bismuth source compound is selected from bismuth halides or bismuth nitrate or bismuth acetate.
According to some embodiments of the present invention, the content of the above-mentioned components in the catalyst carrier for olefin polymerization may be selected and varied within a wide range. The bismuth source compound is used in an amount of 0.0001mol to 1mol, preferably 0.001mol to 0.5mol, more preferably 0.01mol to 0.5mol, most preferably 0.0625mol to 0.375mol, for example 0.25mol, 0.125mol, 0.0625mol, 0.375mol, based on 1mol of magnesium halide of the formula MgXY; the compound of the formula ROH is used in an amount of 4 to 30mol, preferably 6 to 20mol, more preferably 6 to 12mol, for example 6 to 12mol; the amount of the ethylene oxide compound represented by the formula (II) is 1 to 10mol, preferably 2 to 6mol, for example 2 to 6mol.
According to some embodiments of the invention, the average particle size of the catalyst support for olefin polymerization is 10 to 100 microns, preferably less than 40 microns; the particle size distribution is less than 1.2, preferably the particle size distribution is 0.2 to 0.9.
In the present invention, the average particle diameter and particle diameter distribution of the catalyst carrier for olefin polymerization can be measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd).
According to some embodiments of the invention, the olefin polymerization catalyst support may contain water from the synthesis feedstock and the trace amounts of water carried by the reaction medium.
A second aspect of the present invention provides a method for producing the above-mentioned catalyst carrier for olefin polymerization, comprising the steps of:
(1) Mixing and heating a bismuth source compound, magnesium halide with a general formula of MgXY and a compound with a general formula of ROH to obtain a liquid mixture;
(2) Emulsifying the liquid mixture obtained in the step (1), and carrying out contact reaction on an emulsified product and an ethylene oxide compound;
preferably, the step (1) further comprises adding an inert liquid medium to mix and heat together.
According to some embodiments of the present invention, in step (1), the conditions for heating the bismuth source compound, the magnesium halide of the formula MgXY, the compound of the formula ROH, optionally the mixture with the inert liquid medium are not particularly limited, provided that the heating conditions are such that the magnesium halide of the formula MgXY melts and sufficiently reacts with the bismuth source compound, preferably the heating temperature is 80 ℃ to 120 ℃, preferably 80 ℃ to 100 ℃, for example 90 ℃, 95 ℃, 100 ℃; the heating time is 0.5 to 5 hours, preferably 0.5 to 4 hours, for example 1 hour, 2 hours, 3 hours, 4 hours.
According to some embodiments of the present invention, the inert liquid medium may be various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products; preferably, the inert liquid medium is silicone oil and/or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium is 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 methylphenyl silicone oil; the inert liquid medium according to the invention is particularly preferably white oil;
the amount of the inert liquid medium may be selected based on the amount of magnesium halide of the formula MgXY; preferably, the inert liquid medium is used in an amount of 0.8L to 10L, preferably 2L to 8L, for example 3.75L, based on 1mol of magnesium halide of the formula MgXY.
According to some embodiments of the present invention, in the step (2), the conditions for the contact reaction of the emulsified product with the oxirane may be various existing conditions capable of forming a catalyst support for olefin polymerization, and preferably, the conditions for the contact reaction include: the temperature is 50 to 120 ℃, preferably 60 to 100 ℃, such as 70 ℃, 75 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃; the time is 20 minutes to 60 minutes, preferably 20 minutes to 50 minutes, for example 20 minutes, 30 minutes, 40 minutes, 50 minutes.
According to some embodiments of the present invention, in step (2), the liquid mixture obtained in step (1) may be emulsified by various methods known to those skilled in the art; for example, the liquid mixture may be subjected to low-speed shearing or high-speed shearing to emulsify it. The agitation rate for the low shear is typically 400 rpm to 800 rpm. Such high shear processes are well known to those skilled in the art and are disclosed as high speed agitation processes (i.e., stirring a solution containing a liquid magnesium halide adduct at a rate of 2000 rpm to 5000 rpm) as disclosed in CN 1151183C. Furthermore, the liquid mixture may be emulsified by the methods disclosed in the following patents: CN1267508C discloses that the solution containing the liquid magnesium halide adduct is subjected to rotary dispersion in a hypergravity bed (the rotation speed may be 100 to 3000 rpm); CN1463990a discloses that a solution containing a liquid magnesium halide adduct is output in an emulsifying machine at a speed of 1500 rpm to 8000 rpm; US6020279 discloses emulsifying a solution containing a liquid magnesium halide adduct by spraying.
According to some embodiments of the present invention, in step (2), a method of adding a surfactant is preferably adopted, that is, the method of emulsifying the liquid mixture obtained in step (1) is specifically to contact the liquid mixture obtained in step (1) with the surfactant;
the surfactant is at least one selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyl trimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polyalkylmethacrylate;
the amount of the surfactant is preferably 5g to 60g, preferably 12.5g to 37.5g, for example 12.5g, 15g, 25g, 37.5g, based on 1mol of magnesium halide of the formula MgXY, for adequate emulsification.
According to some embodiments of the present invention, the preparation method of the catalyst carrier for olefin polymerization may further include solid-liquid separation of the product obtained by the contact reaction, washing and drying the solid-phase product. The solid-liquid separation may be any of various existing 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 well 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 conditions for the drying are not particularly limited in the present invention, and examples thereof include: the drying temperature may be 20 to 70 ℃, and the drying time may be 0.5 to 10 hours.
According to some embodiments of the invention, the drying may be performed under normal pressure or reduced pressure.
The inventors of the present invention have unexpectedly found that by using a bismuth source compound (for example, bismuth halide, bismuth nitrate, bismuth acetate, etc.) in the preparation of a catalyst carrier for olefin polymerization, a catalyst carrier for olefin polymerization having a novel composition, which has a small particle diameter, a good morphology and is substantially free of irregular particles, can be obtained by the above method; and when the catalyst for olefin polymerization prepared by using the catalyst carrier for olefin polymerization containing bismuth halide is used for olefin polymerization, the activity of the catalyst for olefin polymerization is higher and the activity release is smoother.
The third aspect of the present invention provides the use of the above-mentioned catalyst carrier for olefin polymerization or the catalyst carrier for olefin polymerization prepared by the above-mentioned preparation method for preparing a catalyst for olefin polymerization.
The beneficial effects are that:
according to the invention, the bismuth source compound is added in the preparation process of the catalyst carrier for olefin polymerization, the bismuth source compound can play a role in regulating the particle size, so that the particle size of the catalyst carrier for olefin polymerization precipitated by a system is reduced, the obtained catalyst carrier particle for olefin polymerization with smaller particle size has good morphology, no special-shaped particles basically exist, and the catalyst for olefin polymerization prepared from the catalyst carrier for olefin polymerization containing bismuth halide has good activity release stability.
Drawings
FIG. 1 is a graph showing the morphology of particles of a catalyst carrier for olefin polymerization prepared in example 1 of the present invention;
FIG. 2 is a graph showing the morphology of particles of the catalyst carrier for olefin polymerization prepared in comparative example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following examples. The present invention is not limited by these examples.
In examples and comparative examples:
1. the average particle diameter and particle diameter distribution of the catalyst carrier for olefin polymerization were measured by using a Master Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd);
2. melt flow rate (MFR, melt index) of polyolefin powder: measured according to ISO1133, 230 ℃,2.16kg load;
3. activity calculation of catalyst for olefin polymerization: catalyst activity= (mass of polyolefin produced)/(mass of catalyst solid component) g/g;
4. bulk Density determination of polyolefin powder: the prepared polymer powder is freely dropped into a 100mL container from a height of 10cm in a funnel, and the polymer bulk density is M/100g/cm when the weight of the polymer powder in the container is measured to be Mg 3 ；
5. The apparent morphology of the catalyst support for olefin polymerization was observed by means of an optical microscope commercially available from Nikon under the model Eclipse E200.
1. Preparation of catalyst support for olefin polymerization
Example 1
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
In a 0.6L reactor, 0.08mol of magnesium chloride, 0.96mol of ethanol, 0.02mol of bismuth chloride and 1.2g of polyvinylpyrrolidone as a surfactant were added, the temperature was raised to 95℃under stirring, the reaction was carried out at a constant temperature of 95℃for 2 hours, then 0.48mol (38 ml) of epichlorohydrin was added, the reaction was carried out at a temperature of 95℃for 30 minutes, the pressure filtration was carried out, and the pressure filtration product was washed with hexane for 5 times and then dried under vacuum, thereby obtaining a catalyst carrier Z1 for olefin polymerization.
According to gas chromatographyCharacterized by elemental analysis and nuclear magnetism, Z1 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z1 for olefin polymerization was 1:0.1.
example 2
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
Into a 0.6L reaction vessel, 300mL of white oil, 0.08mol (8.0 g) of magnesium chloride, 0.48mol (28 mL) of ethanol, 0.01mol of bismuth chloride and 2g of polyvinylpyrrolidone as a surfactant were added, the temperature was raised to 100℃under stirring, the reaction was carried out at a constant temperature of 100℃for 1 hour, then 0.16mol (12.5 mL) of epichlorohydrin was added, the reaction was carried out at a temperature of 100℃for 30 minutes, press filtration was carried out, and the press filtration product was washed with hexane for 5 times and then dried under vacuum to obtain a catalyst carrier Z2 for olefin polymerization.
Z2 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z2 for olefin polymerization was 1:0.06.
example 3
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
Into a 0.6L reaction vessel, 0.08mol (8.0 g) of magnesium chloride, 0.48mol (28 mL) of ethanol, 0.005mol of bismuth chloride and 3g of polyvinylpyrrolidone as a surfactant were added, the temperature was raised to 100℃under stirring, the reaction was carried out at a constant temperature of 100℃for 1 hour, then 0.16mol (12.5 mL) of epichlorohydrin was added, the reaction was carried out at a temperature of 100℃for 20 minutes, press filtration was carried out, and the press filtration product was washed with hexane 5 times and dried under vacuum to obtain a catalyst carrier Z3 for olefin polymerization.
Z3 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z3 for olefin polymerization was 1:0.02.
comparative example 1
The preparation was carried out as described in example 1, except that bismuth chloride was not added, and finally, a catalyst support DZ1 for olefin polymerization was obtained.
DZ1 comprises a structural formula ofIs a compound of (a).
Example 4
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
In a 0.6L reactor, 0.08mol (8.0 g) of magnesium chloride, 0.96mol (56 mL) of ethanol, 0.03mol of bismuth nitrate and 1g of polyvinylpyrrolidone were added as a surfactant, the temperature was raised to 90℃with stirring, and the reaction was carried out at a constant temperature of 90℃for 4 hours, then 0.48mol (38 mL) of epichlorohydrin was added, the reaction was carried out at a constant temperature of 90℃for 30 minutes, and then press filtration was carried out, and the press filtration product was washed with hexane for 5 times, and then dried under vacuum, to obtain a catalyst carrier Z4 for olefin polymerization.
Z4 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z4 for olefin polymerization was 1:0.15.
example 5
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
Into a 0.6L reaction vessel, 300mL of white oil, 0.08mol (8.0 g) of magnesium chloride, 0.48mol (28 mL) of ethanol, 0.03mol of bismuth nitrate and 1g of polyvinylpyrrolidone were added as a surfactant, the temperature was raised to 100℃under stirring, the reaction was allowed to proceed at a constant temperature of 100℃for 3 hours, then 0.16mol (12.5 mL) of epichlorohydrin was added, the reaction was allowed to proceed at a constant temperature of 100℃for 20 minutes, press filtration was performed, and the press filtration product was washed with hexane for 5 times and then dried under vacuum, thereby obtaining a catalyst carrier Z5 for olefin polymerization.
Z5 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z5 for olefin polymerization was 1:0.15.
example 6
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
Into a 0.6L reaction vessel, 300mL of white oil, 0.08mol (8.0 g) of magnesium chloride, 0.48mol (28 mL) of ethanol, 0.03mol of bismuth acetate and 1g of polyvinylpyrrolidone were added as a surfactant, the temperature was raised to 100℃under stirring, the reaction was allowed to proceed at a constant temperature of 100℃for 3 hours, then 0.16mol (12.5 mL) of epichlorohydrin was added, the reaction was continued at a constant temperature of 100℃for 20 minutes, and then press filtration was carried out, and the press filtration product was washed with hexane for 5 times and then dried under vacuum to obtain a catalyst carrier Z6 for olefin polymerization.
Z6 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z6 for olefin polymerization was 1:0.16.
example 7
This example is for explaining the catalyst carrier for olefin polymerization and the method for producing the same.
In a 0.6L reaction vessel, 0.08mol (8.0 g) of magnesium chloride, 0.96mol (56 mL) of ethanol, 0.01mol of bismuth nitrate and 1g of polyvinylpyrrolidone were added as surfactants, the temperature was raised to 90℃under stirring, the reaction was carried out at a constant temperature of 90℃for 4 hours, then 0.48mol (38 mL) of epichlorohydrin was added, the constant temperature reaction was continued at a temperature of 90℃for 30 minutes, press filtration was carried out, and the press filtration product was washed with hexane for 5 times and dried under vacuum to obtain a catalyst carrier Z7 for olefin polymerization.
Z7 comprises a structural formula ofAnd bismuth element:
the molar ratio of the compound (based on the molar amount of Mg) and bismuth element in the catalyst carrier Z7 for olefin polymerization was 1:0.04.
comparative example 2
The preparation was carried out as described in example 4, except that bismuth nitrate was not added, and finally, a catalyst carrier DZ2 for olefin polymerization was obtained.
DZ2 comprises a structural formula ofIs a compound of (a).
The average particle diameter (D50) and the particle diameter distribution ((D90-D10)/D50) of the catalyst supports for olefin polymerization prepared in examples 1 to 7 and comparative examples 1 to 2 were measured and observed for the apparent morphology, and the results were shown in Table 1 below:
TABLE 1
From the results of table 1, it can be seen that when the catalyst carrier for olefin polymerization of the present invention is prepared, the catalyst carrier for olefin polymerization having a novel composition can be prepared by the above-described method using the bismuth source compound, has smaller average particle diameter and particle diameter distribution than those of the catalyst carrier for olefin polymerization containing no bismuth source compound, and the prepared catalyst carrier for olefin polymerization has a good particle morphology and is substantially free of foreign particles.
2. Preparation of catalyst component for olefin polymerization and propylene polymerization reaction
Example 8
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
(1) Preparation of catalyst components for olefin polymerization
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added, cooled to-20 ℃, then 8 g of the catalyst carrier Z1 for olefin polymerization obtained in example 1 was added thereto and stirred at a temperature of-20℃for 30 minutes, then a slow temperature rise to 110℃was started, 1.6mL of diisobutyl phthalate was added during the temperature rise, then a liquid was filtered off after maintaining at a temperature of 110℃for 30 minutes, then titanium tetrachloride was added, washed 2 times, finally washed 3 times with hexane, and dried to obtain a catalyst component for olefin polymerization.
(3) Propylene polymerization
In a 5L stainless steel autoclave, purging was performed with a nitrogen gas stream, then 1mmol of triethylaluminum in hexane (triethylaluminum concentration 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane and 10mg of the catalyst component for olefin polymerization obtained in the above step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene were introduced into the nitrogen gas stream, and the temperature was raised to 70℃and polymerization was carried out at that temperature for 1 hour (or polymerization reaction for 2 hours), followed by cooling, pressure release, discharge drying to obtain polypropylene powder.
Example 9
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Propylene polymerization was conducted in the same manner as in example 8 except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain a catalyst component for olefin polymerization and a polypropylene powder.
Example 10
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Propylene polymerization was conducted in the same manner as in example 8 except that the catalyst carrier for olefin polymerization Z1 was replaced with the catalyst carrier for olefin polymerization Z2 obtained in example 2, to obtain a catalyst component for olefin polymerization and a polypropylene powder.
Example 11
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Propylene polymerization was conducted in the same manner as in example 10 except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen, to obtain a catalyst component for olefin polymerization and a polypropylene powder.
Example 12
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Propylene polymerization was conducted in the same manner as in example 8 except that the catalyst carrier for olefin polymerization Z1 was replaced with the catalyst carrier for olefin polymerization Z3 obtained in example 3, to obtain a catalyst component for olefin polymerization and a polypropylene powder.
Example 13
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Propylene polymerization was conducted in the same manner as in example 12 except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen, to obtain a catalyst component for olefin polymerization and a polypropylene powder.
Comparative example 3
Propylene polymerization was conducted in the same manner as in example 8 except that the catalyst carrier for olefin polymerization Z1 was replaced with the catalyst carrier for olefin polymerization DZ1 obtained in comparative example 1 to obtain a catalyst component for olefin polymerization and a polypropylene powder.
Comparative example 4
Propylene polymerization was conducted in the same manner as in comparative example 3 except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen, to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 14
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
(1) Preparation of catalyst components for olefin polymerization
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added, cooled to-20 ℃, 8 g of the catalyst carrier Z4 for olefin polymerization obtained in example 4 was added thereto and stirred at a temperature of-20℃for 30 minutes, then, a slow temperature rise was started to 110℃and 1.5mL of diisobutyl phthalate was added during the temperature rise, then, the liquid was filtered off after maintaining at a temperature of 110℃for 30 minutes, and then, titanium tetrachloride was added for 2 times, finally, hexane was used for 3 times, and a catalyst component for olefin polymerization was obtained after drying.
(2) Propylene polymerization
In a 5L stainless steel autoclave, purging was performed with a nitrogen gas stream, then 1mmol of triethylaluminum in hexane (triethylaluminum concentration 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane and 10mg of the catalyst component for olefin polymerization obtained in step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene were introduced into the nitrogen gas stream, and then the temperature was raised to 70℃and polymerization was carried out at this temperature for 1 hour, and then the polypropylene powder was obtained by cooling, pressure release and discharge drying.
Example 15
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were conducted in the same manner as in example 14 except that 6.5L (standard volume) of hydrogen was added instead of 1.5L (standard volume) to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 16
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were carried out in the same manner as in example 14 except that the catalyst carrier for olefin polymerization Z4 was replaced with the catalyst carrier for olefin polymerization Z5 obtained in example 5 to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 17
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were carried out in the same manner as in example 16 except that 6.5L (standard volume) of hydrogen was added instead of 1.5L (standard volume) to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 18
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were carried out in the same manner as in example 14 except that the catalyst carrier for olefin polymerization Z4 was replaced with the catalyst carrier for olefin polymerization Z6 obtained in example 6 to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 19
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were conducted in the same manner as in example 18 except that 6.5L (standard volume) of hydrogen was added instead of 1.5L (standard volume) to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 20
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were carried out in the same manner as in example 14 except that the catalyst carrier for olefin polymerization Z4 was replaced with the catalyst carrier for olefin polymerization Z7 obtained in example 7 to obtain a catalyst component for olefin polymerization and polypropylene powder.
Example 21
This example is intended to illustrate that the catalyst support for olefin polymerization of the present invention is useful for the preparation of polyolefins.
Preparation of a catalyst component for olefin polymerization and propylene polymerization were conducted in the same manner as in example 20 except that 6.5L (standard volume) of hydrogen was added instead of 1.5L (standard volume) to obtain a catalyst component for olefin polymerization and polypropylene powder.
Comparative example 5
Preparation of a catalyst component for olefin polymerization and propylene polymerization were carried out in the same manner as in example 14 except that the catalyst carrier for olefin polymerization Z4 was replaced with the catalyst carrier for olefin polymerization DZ2 obtained in comparative example 2 to obtain a catalyst component for olefin polymerization and polypropylene powder.
Comparative example 6
The preparation of the catalyst component for olefin polymerization and propylene polymerization were carried out in the same manner as in comparative example 5 except that 6.5L (standard volume) of hydrogen was added instead of 1.5L (standard volume) to obtain the catalyst component for olefin polymerization and polypropylene powder.
Test one: the catalyst components for olefin polymerization prepared in examples 8 to 13 and comparative examples 3 to 4 above were used for propylene polymerization, the catalytic activities of the catalysts for olefin polymerization in examples 8 to 13 and comparative examples 3 to 4 were calculated at polymerization time of 1 hour and 2 hours, respectively, and the appearance of the prepared polypropylene powder was observed, and the results were shown in Table 2 below:
TABLE 2
As can be seen from the results of Table 2, when the catalysts prepared by using the catalyst supports for olefin polymerization according to examples 1 to 3 of the present invention (examples 8 to 13) were used for olefin (particularly propylene) polymerization, the prepared polypropylene powder had a good morphology, substantially no profile, good fluidity, and good process stability and the transfer of the polymer during the production process, and the catalysts for olefin polymerization according to examples 8 to 13 of the present invention had a relatively balanced activity release, a ratio of 2h/1h of substantially between 1.55 and 1.80, and the catalysts for olefin polymerization according to comparative examples 3 and 4 had an unbalanced activity release, and a ratio of 2h/1h of substantially between 1.40 and 1.45.
And II, testing: the catalyst components for olefin polymerization prepared in examples 14 to 21 and comparative examples 5 to 6 above were used for propylene polymerization, the catalytic activities of the catalysts for olefin polymerization in examples 14 to 21 and comparative examples 5 to 6 at polymerization time of 1 hour were calculated, the bulk densities of the polypropylene powder were measured and the appearance of the prepared polypropylene powder was observed, and the results were as shown in Table 3 below:
TABLE 3 Table 3
As can be seen from the results of Table 3, when the catalysts prepared with the catalyst supports for olefin polymerization according to examples 4 to 7 of the present invention (examples 14 to 21) were used for olefin (particularly propylene) polymerization, the prepared polypropylene powder particles were excellent in morphology, substantially free of the abnormal material, good in fluidity, favorable for process stabilization and transportation of the polymer during the production flow, and the catalysts for olefin polymerization according to examples 14 to 21 of the present invention were higher in bulk density, and compared with the catalysts for olefin polymerization according to comparative examples 5 and 6, lower in bulk density, unfavorable for improving productivity of the same apparatus.
In summary, the catalyst carrier for olefin polymerization prepared by the invention has good particle morphology, smooth surface and basically no abnormal particles, the activity of the catalyst for olefin polymerization prepared by using the catalyst carrier for olefin polymerization containing bismuth halide or bismuth nitrate or bismuth acetate is obviously improved compared with the comparative example, and when the catalyst for olefin polymerization is used for olefin (especially propylene) polymerization, the bulk density of a polymerization product can be improved, and basically no abnormal material exists in the polymerization product; the catalyst carrier for olefin polymerization has great industrial application prospect.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A catalyst carrier for olefin polymerization, characterized in that the catalyst carrier for olefin polymerization comprises a compound represented by structural formula (I):
preferably, R in the compound represented by formula (I) 1 Is a C1-C8 straight chain alkyl group, a C3-C8 branched chain alkyl group or a C3-C8 cycloalkyl group; r is R 2 And R is 3 The same or different are each independently hydrogen, C1-C5 straight chain alkyl or C3-C5 branched alkyl, further preferably R 2 And R is 3 Hydrogen on the alkyl group is optionally substituted with a halogen atom; x is halogen, preferably chlorine or bromine; m is 0.1-1.9, n is 0.1-1.9, m+n=2;
preferably, the molar ratio of the compound shown in the structural formula (I) and bismuth element in the catalyst carrier for olefin polymerization is 1: (0.01 to 1), preferably 1: (0.02-0.16), wherein the compound represented by the structural formula (I) is based on the molar amount of Mg.
2. The catalyst carrier for olefin polymerization according to claim 1, wherein the synthetic raw materials of the catalyst carrier for olefin polymerization comprise a bismuth source compound, magnesium halide of the general formula MgXY, a compound of the general formula ROH, and an ethylene oxide-based compound;
preferably, in the general formula MgXY, X is halogen, Y is halogen, C 1 -C 14 Alkyl, C of (2) 1 -C 14 Alkoxy, C 6 -C 14 Aryl or C of (2) 6 -C 14 An aryloxy group of (a); preferably, X is chlorine or bromine, Y is chlorine, bromine, C 1 -C 5 Alkyl, C of (2) 1 -C 5 Alkoxy, C 6 -C 10 Aryl or C of (2) 6 -C 10 An aryloxy group of (a); more preferably, the magnesium halide of the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, phenoxy magnesium chloride, isopropoxy magnesium chloride and n-butoxy magnesium chloride;
and/or, in the general formula ROH, R is C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl or C 3 -C 8 Cycloalkyl of (c); preferably, in the formula ROH, R is C 1 -C 8 Straight-chain alkyl or C 3 -C 8 Branched alkyl of (a); more preferably, the compound of formula ROH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol;
and/or the structure of the ethylene oxide compound is shown as a formula (II):
in the formula (II), R 5 And R is 6 The same or different, each independently hydrogen, C 1 -C 5 Straight-chain alkyl or C 3 -C 5 Branched alkyl groups wherein the hydrogen on the alkyl group is optionally substituted with a halogen atom; preferably, R 5 And R is 6 The same or different, each independently hydrogen, C 1 -C 3 Straight-chain alkyl or C 1 -C 3 A haloalkyl group of (2); more preferably, the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, bromopropane, and butylene oxide;
and/or the bismuth source compound is selected from bismuth halide or bismuth nitrate or bismuth acetate.
3. The catalyst carrier for olefin polymerization according to claim 2, wherein the bismuth source compound is used in an amount of 0.0001mol to 1mol, preferably 0.001mol to 0.5mol, more preferably 0.01mol to 0.5mol, most preferably 0.0625mol to 0.375mol, based on 1mol of magnesium halide of the general formula MgXY; the amount of the compound of the formula ROH is 4 to 30mol, preferably 6 to 20mol, more preferably 6 to 12mol; the amount of the ethylene oxide compound represented by the formula (II) is 1 to 10mol, preferably 2 to 6mol.
4. A catalyst support for olefin polymerization according to any one of claims 1 to 3, characterized in that the average particle diameter of the catalyst support for olefin polymerization is 10 to 100 micrometers, preferably 10 to 40 micrometers;
and/or the catalyst carrier for olefin polymerization has a particle size distribution of less than 1.2, preferably a particle size distribution of less than or equal to 0.9.
5. A process for preparing a catalyst carrier for olefin polymerization as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Mixing and heating a bismuth source compound, magnesium halide with a general formula of MgXY and a compound with a general formula of ROH to obtain a liquid mixture;
(2) Emulsifying the liquid mixture obtained in the step (1), and carrying out contact reaction on an emulsified product and an ethylene oxide compound;
preferably, the step (1) further comprises adding an inert liquid medium to mix and heat together.
6. The method of claim 5, wherein in step (1), the heating is performed at a temperature of 80 ℃ to 120 ℃, preferably 80 ℃ to 100 ℃; and/or the heating time is 0.5 to 5 hours, preferably 0.5 to 4 hours;
and/or the inert liquid medium is silicone oil and/or inert liquid hydrocarbon solvent; preferably, the inert liquid medium is 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;
and/or the inert liquid medium is used in an amount of 0.8L to 10L, preferably 2L to 8L, for example 3.75L, based on 1mol of magnesium halide of the formula MgXY.
7. The method according to claim 5 or 6, wherein in the step (2), the conditions of the contact reaction include: the temperature is 50-120 ℃, preferably 60-100 ℃; the time is 20 minutes to 60 minutes, preferably 20 minutes to 50 minutes.
8. The preparation method according to any one of claims 5 to 7, wherein in the step (2), the method for emulsifying the liquid mixture obtained in the step (1) is specifically that the liquid mixture obtained in the step (1) is emulsified by contacting with a surfactant;
preferably, the surfactant is at least one selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkylacrylate copolymer modified polyethyleneimine, polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyl trimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkylmethacrylate.
9. The preparation method according to claim 8, wherein the surfactant is used in an amount of preferably 5g to 60g, preferably 12.5g to 37.5g, based on 1mol of magnesium halide of the general formula MgXY.
10. Use of the catalyst carrier for olefin polymerization according to any one of claims 1 to 4 or the catalyst carrier for olefin polymerization prepared by the preparation method according to any one of claims 5 to 8 for preparing a catalyst for olefin polymerization.
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