CN111072808B - Catalyst component, catalyst, application thereof and olefin polymerization method - Google Patents
Catalyst component, catalyst, application thereof and olefin polymerization method Download PDFInfo
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- CN111072808B CN111072808B CN201811223650.7A CN201811223650A CN111072808B CN 111072808 B CN111072808 B CN 111072808B CN 201811223650 A CN201811223650 A CN 201811223650A CN 111072808 B CN111072808 B CN 111072808B
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- catalyst component
- compound
- catalyst
- component according
- olefin polymerization
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 148
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 99
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000009826 distribution Methods 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 4
- -1 Magnesium halide Chemical class 0.000 claims description 99
- 238000002360 preparation method Methods 0.000 claims description 47
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 29
- 239000011777 magnesium Substances 0.000 claims description 26
- 229910052749 magnesium Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Chemical group 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical group 0.000 claims description 7
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004349 Polyvinylpyrrolidone-vinyl acetate copolymer Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 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
- 235000019448 polyvinylpyrrolidone-vinyl acetate copolymer Nutrition 0.000 claims description 3
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 claims description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 2
- ZVAKZVDJIUFFFP-UHFFFAOYSA-N 2-chlorooxolane Chemical compound ClC1CCCO1 ZVAKZVDJIUFFFP-UHFFFAOYSA-N 0.000 claims description 2
- 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229920001400 block 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
- 125000004435 hydrogen atom Chemical group [H]* 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
- 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
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether 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
- 239000007858 starting material Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 description 96
- 239000004743 Polypropylene Substances 0.000 description 51
- 229920001155 polypropylene Polymers 0.000 description 46
- 239000000843 powder Substances 0.000 description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 23
- 238000011085 pressure filtration Methods 0.000 description 19
- 239000000155 melt Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 241000282326 Felis catus Species 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 230000001788 irregular Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JLQNHALFVCURHW-UHFFFAOYSA-N cyclooctasulfur Chemical compound S1SSSSSSS1 JLQNHALFVCURHW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical compound C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000839 emulsion 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant 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
- 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
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- NOAIBMQZUGBONL-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)benzene Chemical compound COCC(C)(COC)C1=CC=CC=C1 NOAIBMQZUGBONL-UHFFFAOYSA-N 0.000 description 1
- HPOWOWTVWZELDK-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)cyclohexane Chemical compound COCC(C)(COC)C1CCCCC1 HPOWOWTVWZELDK-UHFFFAOYSA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- CELOJHLXFPSJPH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylbenzene Chemical compound COCC(COC)C1=CC=CC=C1 CELOJHLXFPSJPH-UHFFFAOYSA-N 0.000 description 1
- NOWCPSTWMDNKTI-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylcyclohexane Chemical compound COCC(COC)C1CCCCC1 NOWCPSTWMDNKTI-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HPFWUWXYBFOJAD-UHFFFAOYSA-N 1-chloro-4-(1,3-dimethoxypropan-2-yl)benzene Chemical compound COCC(COC)C1=CC=C(Cl)C=C1 HPFWUWXYBFOJAD-UHFFFAOYSA-N 0.000 description 1
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical compound COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 1
- ROSQVPGTZCDBOC-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C)(COC)CC(C)C ROSQVPGTZCDBOC-UHFFFAOYSA-N 0.000 description 1
- XAGXJWYEHBCLPN-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylbutane Chemical compound COCC(C)(CC)COC XAGXJWYEHBCLPN-UHFFFAOYSA-N 0.000 description 1
- SVJCEDKUVMVBKM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylpentane Chemical compound CCCC(C)(COC)COC SVJCEDKUVMVBKM-UHFFFAOYSA-N 0.000 description 1
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 1
- FDLMLTYTOFIPCK-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylpentane Chemical compound CCC(C)C(COC)COC FDLMLTYTOFIPCK-UHFFFAOYSA-N 0.000 description 1
- PPHMKLXXVBJEHR-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)hexane Chemical compound CCCCC(COC)COC PPHMKLXXVBJEHR-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- JUJMPCLNRKYKRA-UHFFFAOYSA-N 2,4-dimethoxybutylcyclohexane Chemical compound COCCC(OC)CC1CCCCC1 JUJMPCLNRKYKRA-UHFFFAOYSA-N 0.000 description 1
- NFDBNVLCUDESRU-UHFFFAOYSA-N 2-methoxy-3-(1-methoxyethyl)hexane Chemical compound C(CC)C(C(C)OC)C(C)OC NFDBNVLCUDESRU-UHFFFAOYSA-N 0.000 description 1
- 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
- FXPIHWVISVNIIK-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylheptane Chemical compound CCCC(C)C(COC)(COC)C(C)C FXPIHWVISVNIIK-UHFFFAOYSA-N 0.000 description 1
- HYNSSLXYPGIRFR-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylhexane Chemical compound CCC(C)C(COC)(COC)C(C)C HYNSSLXYPGIRFR-UHFFFAOYSA-N 0.000 description 1
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 description 1
- WAHDOBRAAIQNTA-UHFFFAOYSA-N 3,5-dimethoxypentylcyclohexane Chemical compound COCCC(OC)CCC1CCCCC1 WAHDOBRAAIQNTA-UHFFFAOYSA-N 0.000 description 1
- CWVKCYDPJZCDMC-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)-2-methyloctane Chemical compound CCCCC(CC)CC(C)(COC)COC CWVKCYDPJZCDMC-UHFFFAOYSA-N 0.000 description 1
- VIJVFTUOJNTXCA-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)octane Chemical compound CCCCC(CC)CC(COC)COC VIJVFTUOJNTXCA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- VDZDYDLIDXQASZ-UHFFFAOYSA-N [1-cyclohexyl-3-methoxy-2-(methoxymethyl)propan-2-yl]cyclohexane Chemical compound C1CCCCC1C(COC)(COC)CC1CCCCC1 VDZDYDLIDXQASZ-UHFFFAOYSA-N 0.000 description 1
- AMDVEEKNUQSFMN-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]benzene Chemical compound COCC(COC)(C(C)C)C1=CC=CC=C1 AMDVEEKNUQSFMN-UHFFFAOYSA-N 0.000 description 1
- PQIDFVXMOZQINS-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclohexane Chemical compound COCC(COC)(C(C)C)C1CCCCC1 PQIDFVXMOZQINS-UHFFFAOYSA-N 0.000 description 1
- XMYDKOZNENQEHO-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclopentane Chemical compound COCC(COC)(C(C)C)C1CCCC1 XMYDKOZNENQEHO-UHFFFAOYSA-N 0.000 description 1
- FQRCETUIJFMCNV-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]benzene Chemical compound CCC(C)C(COC)(COC)C1=CC=CC=C1 FQRCETUIJFMCNV-UHFFFAOYSA-N 0.000 description 1
- IHLHFXVNTFWZRQ-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]cyclohexane Chemical compound CCC(C)C(COC)(COC)C1CCCCC1 IHLHFXVNTFWZRQ-UHFFFAOYSA-N 0.000 description 1
- NELZYGXHSKMGPM-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]cyclopentane Chemical compound CCC(C)C(COC)(COC)C1CCCC1 NELZYGXHSKMGPM-UHFFFAOYSA-N 0.000 description 1
- XHGYQNSJWDRDBT-UHFFFAOYSA-N [2,2-bis(methoxymethyl)-3-methylbutyl]benzene Chemical compound COCC(COC)(C(C)C)CC1=CC=CC=C1 XHGYQNSJWDRDBT-UHFFFAOYSA-N 0.000 description 1
- WVEZHRZEAFZJOI-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)-1-phenylpropyl]benzene Chemical compound C=1C=CC=CC=1C(C(COC)COC)C1=CC=CC=C1 WVEZHRZEAFZJOI-UHFFFAOYSA-N 0.000 description 1
- UKEUPAFEWAEVGQ-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)-2-methylpropyl]benzene Chemical compound COCC(C)(COC)CC1=CC=CC=C1 UKEUPAFEWAEVGQ-UHFFFAOYSA-N 0.000 description 1
- JXQCBJLNEGKSCN-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]benzene Chemical compound COCC(COC)CCC1=CC=CC=C1 JXQCBJLNEGKSCN-UHFFFAOYSA-N 0.000 description 1
- AWLBWJXVYGYRNY-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]cyclohexane Chemical compound COCC(COC)CCC1CCCCC1 AWLBWJXVYGYRNY-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([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
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 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
- 238000009776 industrial production Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 238000006772 olefination reaction Methods 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
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 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
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000010008 shearing Methods 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
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
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- 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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the field of catalysts, and relates to a catalyst component, a catalyst, application thereof and an olefin polymerization method. The catalyst component comprises the reaction product of: (1) a solid component which is at least one sulfur-containing magnesium compound represented by formula (I); (2) at least one titanium compound; and (3) an internal electron donor compound, wherein the internal electron donor compound is at least one 1, 3-diether compound. The catalyst with small particle size can be prepared by taking 1, 3-diether as an internal electron donor and combining a sulfur-containing magnesium compound as a carrier, has narrow particle size distribution, high activity and good hydrogen regulation sensitivity, and can improve the bulk density of a polymer when used for olefin polymerization.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, application of the catalyst component and the catalyst, and an olefin polymerization method.
Background
In recent years, the polypropylene industry has been rapidly developed, and the proportion of the polypropylene in general-purpose plastics and even special plastics has been increased, mainly due to the progress of catalyst technology, the development of propylene polymerization process and the further expansion of propylene polymer performance brought by the progress of the propylene polymerization process. Polypropylene catalysts include Ziegler-Natta catalysts, metallocene catalysts and non-metallocene catalysts, with Ziegler-Natta catalysts always being the predominant catalytic system in propylene polymerization production. The Ziegler-Natta catalyst, which started in the 50 th 20 th century, remains one of the main catalysts for industrial production through many generations of renewal, and its research has been one of the hot spots of polypropylene catalysts.
Due to the morphological characteristics of the spherical polypropylene catalyst and the existence of the phenomenon of 'duplication' from the catalyst to the polymer (namely, only the spherical catalyst can obtain the spherical polymer), the spherical catalyst has great advantages in the polymerization production process and the subsequent processing process of the polymer, and is particularly beneficial to the production of high molecular alloy. Therefore, in the polypropylene catalysts currently used in industry, the proportion of spherical catalysts is very large. The spherical carrier and the internal electron donor are two important components of the spherical polypropylene catalyst. The spherical carrier is mainly from a magnesium chloride alcohol compound carrier, magnesium chloride and alcohol react at high temperature to form the magnesium chloride alcohol compound, the magnesium chloride alcohol compound is melted and dispersed in an inert component, then emulsion is formed through high shearing, and the alcohol compound is solidified and formed after the emulsion is transferred into a low-temperature medium to obtain the carrier. In the production process of the carrier, melting at high temperature and solidification at low temperature are required, and thus, a large amount of energy is consumed. In order to solve the problem, CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an oxirane compound, and specifically discloses adding the oxirane compound after melting and dispersing the magnesium halide alcoholate; or the magnesium halide alcoholate is directly added into a reactor containing the ethylene oxide compound after being melted and dispersed. However, the catalyst carrier prepared by the method has the defects of unstable preparation process, easy carrier adhesion, poor carrier forming effect and wide particle size distribution.
The magnesium chloride alcoholate carrier cannot prepare a spherical carrier having a particle size of less than 20 μm because of its characteristics, and the above method cannot obtain a carrier having the same particle size. In general, small particle size supports not only reduce the fines of polymer from the catalyst produced but are also widely used in various gas phase polymerization processes.
Therefore, it is of great interest to develop a new catalyst support for olefin polymerization that overcomes the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The inventors of the present invention have surprisingly found that the addition of sulphur during the preparation of an olefin polymerisation catalyst support results in a support having a novel composition, which support has a good particle morphology, a smooth surface, is substantially free of irregular particles, and can achieve a particle size of less than 20 microns with a narrow particle size distribution. Particularly, when 1, 3-diether is matched as an internal electron donor, the catalyst prepared from the carrier has higher activity and better hydrogen regulation sensitivity, and can improve the bulk density of a polymer when used for olefin polymerization.
In this regard, a first aspect of the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component comprising the reaction product of:
(1) a solid component which is at least one sulfur-containing magnesium compound represented by formula (I);
(2) at least one titanium compound; and
(3) an internal electron donor compound, wherein the internal electron donor compound is at least one 1, 3-diether compound;
in the formula (I), R 1 Is C 1 -C 8 Linear or branched alkyl of, or C 3 -C 8 Cycloalkyl groups of (a);
R 2 and R 3 Identical or different, each independently of the others, is hydrogen or C 1 -C 5 The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be 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 is 2, 0< q is less than or equal to 0.5.
A second aspect of the present invention provides the use of a catalyst component as described above in the preparation of a catalyst for the polymerisation of olefins.
A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:
(1) the above catalyst components;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
A fourth aspect of the invention provides the use of a catalyst as described above in the polymerisation of olefins.
A fifth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions.
By adopting the technical scheme of the invention, sulfur is added in the preparation process of the olefin polymerization catalyst carrier, so that a spherical carrier with a novel composition can be obtained. The sulfur can reduce the collision probability among unformed particles and reduce the adhesion among carrier particles, so that the obtained carrier particles have small particle size, narrow distribution and good shape. The 1, 3-diether is used as an internal electron donor, and the catalyst prepared by using the carrier has narrow particle size distribution, good activity and good hydrogen regulation sensitivity, and can improve the bulk density of a polymer when used for olefin polymerization.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
FIG. 1 is an optical micrograph of a spherical support of an olefin polymerization catalyst prepared in preparation example 1;
FIG. 2 is an optical micrograph of an olefin polymerization catalyst support prepared in comparative preparation example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component comprising the reaction product of:
(1) a solid component which is at least one sulfur-containing magnesium compound represented by formula (I);
(2) at least one titanium compound; and
(3) an internal electron donor compound, wherein the internal electron donor compound is at least one 1, 3-diether compound;
in the formula (I), R 1 Is C 1 -C 8 Of a straight chain orBranched alkyl, or C 3 -C 8 Cycloalkyl groups of (a);
R 2 and R 3 Identical or different, each independently of the others, is hydrogen or C 1 -C 5 The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be 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 is 2, 0< q is less than or equal to 0.5.
According to the present invention, preferably, the raw material for synthesizing the spherical carrier of the olefin polymerization catalyst comprises elemental sulfur and has a general formula of MgX 1 Magnesium halide of Y, formula R 1 OH compounds, ethylene oxide compounds;
general formula MgX 1 In Y, X 1 Is halogen, Y is halogen, C 1 -C 5 Alkyl of (C) 1 -C 5 Alkoxy group of (C) 6 -C 10 Aryl or C of 6 -C 10 An aryloxy group of (a);
general formula R 1 In OH, R 1 Is C 1 -C 8 Alkyl or C 3 -C 8 Cycloalkyl groups of (a);
the structure of the ethylene oxide compound is shown as the formula (II):
in the formula (II), R 5 And R 6 Each independently of the other is hydrogen, C 1 -C 5 Alkyl or C of 1 -C 5 A haloalkyl group of (a).
According to a preferred embodiment of the present invention, the sulfur-containing magnesium compound is prepared by a method comprising the steps of:
(1) elemental sulfur with the general formula of MgX 1 Magnesium halide of Y, formula R 1 Mixing and heating a compound of OH, an optional inert liquid medium, an optional surfactant to obtain a liquid mixture;
(2) and (2) carrying out contact reaction on the liquid mixture obtained in the step (1) and an ethylene oxide compound.
According to the present invention, the inert liquid medium may be any of various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products. For example: the inert liquid medium may be a silicone oil type solvent and/or a hydrocarbon type solvent. Specifically, the inert liquid medium may be 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. The inert liquid medium according to the invention is particularly preferably white oil. The inert liquid medium may be used in an amount according to the general formula MgX 1 The amount of the magnesium halide of Y is determined. Generally, 1mol of MgX is represented by the formula 1 The inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on the magnesium halide of Y.
According to the present invention, a surfactant such as at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol, polyacrylic acid salt, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkylacrylate copolymer-modified polyethyleneimine, a polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethyleneoxide-propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenylpolyoxyethylene ether, and polyalkylmethacrylate may be used in the reaction, and preferably at least one of polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer, and polyethylene glycol. 1mol of MgX 1 The amount of the surfactant is preferably 1 to 20g based on the magnesium halide of Y.
According to the invention, in step (1), elemental sulfur is reacted with a compound of the general formula MgX 1 Magnesium halide of Y, formula R 1 The conditions under which the compound of OH, optionally in admixture with an inert liquid medium and/or a surfactant, is heated are not particularly limited, provided that the heating conditions are such as to give a compound of formula MgX 1 The magnesium halide of Y is melted and fully reacted with sulfur. Generally, the heated stripThe piece of equipment includes: the temperature is 80-120 ℃, and the time is 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the time is 0.5-3 hours.
According to the present invention, the conditions for contacting the liquid mixture with the ethylene oxide in step (2) may be any of the existing conditions capable of forming a carrier for an olefin polymerization catalyst, for example, the conditions for contacting include: the temperature is 40-120 ℃, and the time is 15-60 minutes; preferably, the conditions of the contact reaction include: the temperature is 60-100 ℃, and the time is 20-50 minutes.
According to the invention, the method can also comprise the steps of carrying out solid-liquid separation on the product obtained by the contact reaction, washing the solid-phase product obtained by the separation and drying the solid-phase product. The solid-liquid separation may be any of various conventional methods for separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation is a pressure filtration method. The conditions for the pressure filtration are not particularly limited in the present invention, and the separation of the solid phase and the liquid phase is achieved as sufficiently as possible. The washing may be carried out by washing the obtained solid phase product by a method known to those skilled in the art, and for example, the obtained solid phase product may be washed by an inert hydrocarbon solvent (e.g., pentane, hexane, heptane, petroleum ether and gasoline). In the present invention, the drying conditions are not particularly limited, and examples thereof include: the drying temperature can be 20-70 ℃, and the drying time can be 0.5-10 hours. According to the invention, the drying can be carried out under atmospheric or reduced pressure.
According to the invention, the content of the above-mentioned components in the spherical support of the olefin polymerization catalyst can be selected and varied within wide limits, preferably 1mol of MgX 1 Based on magnesium halide of Y, the usage of elemental sulfur is 0.0001-0.5mol, and the general formula is R 1 The dosage of OH compound is 4-30mol, and the dosage of ethylene oxide compound is 1-10 mol; further preferably, MgX is present in an amount of 1mol 1 Based on magnesium halide of Y, the general formula is R 1 The dosage of the OH compound is 6-20mol, and the dosage of the ethylene oxide compound is 2-6 mol.
In the present invention, the elemental sulfur may be any subtype of elemental sulfur, including but not limited to: at least one of alpha-sulfur, beta-sulfur, gamma-sulfur, and polymeric sulfur. The elemental sulphur may be anhydrous elemental sulphur or elemental sulphur containing bound water. The above elemental sulphur is commercially available.
According to the invention, of the formula MgX 1 In Y, X 1 Preferably chlorine or bromine, Y is preferably chlorine, bromine, C 1 -C 5 Alkoxy or C 6 -C 10 An aryloxy group of (1). Said C is 1 -C 5 The alkyl group of (A) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl, C 1 -C 5 The alkoxy group of (C) may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, C 6 -C 10 The aryl group of (A) may be, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, an m-ethylphenyl group, a p-ethylphenyl group or a naphthyl group, said C 6 -C 10 The aryloxy group of (b) may be, for example, a phenoxy group or a naphthoxy group. A general formula of MgX 1 The magnesium halide of Y may be one kind of magnesium halide or a mixture of plural kinds of magnesium halides. A general formula of MgX 1 Specific examples of magnesium halides of Y may be, but are not limited to: at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride. Magnesium chloride is preferred from the viewpoint of availability of raw materials.
According to the invention, of the formula R 1 In OH, R 1 Can be C 1 -C 8 Alkyl or C 3 -C 8 Cycloalkyl of (b), wherein, C 3 -C 8 The carbon atoms in the cycloalkyl group(s) may be all or part of them may participate in the ring formation, and C is 3 -C 8 The cycloalkyl group of (b) may be, for example, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexyl group or a cyclohexylmethyl group. R 1 Preferably C 1 -C 8 Alkyl groups of (a); said C is 1 -C 8 The alkyl group of (A) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl groupAn n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl group. Has the general formula R 1 Specific examples of compounds of OH may be, but are not limited to: at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, 2-ethylhexanol, and n-octanol.
According to the invention, in the ethylene oxide compound with the structure shown as the formula (II), R 5 And R 6 Preferably each independently hydrogen, C 1 -C 3 Alkyl or C of 1 -C 3 Haloalkyl of (a); specific examples of the oxirane compound may be, but are not limited to: at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
The average particle size of the spherical support for the olefin polymerization catalyst of the present invention can be controlled in a wide range and may be, for example, 10 to 100 μm. According to a preferred embodiment of the present invention, the average particle diameter (D50) of the spherical support for olefin polymerization catalyst can be controlled to 30 μm or less, preferably to 20 μm or less, and the particle size distribution ((D90-D10)/D50) is less than 1.2; the particle size distribution is preferably 0.8 or less. In the preferred embodiment, the catalyst prepared from the spherical support of the olefin polymerization catalyst can give an olefin polymer having a higher bulk density. In the present invention, the average particle diameter and the particle size distribution of the spherical support for an olefin polymerization catalyst can be measured using a Master Sizer2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).
According to the invention, the spherical support of the olefin polymerization catalyst may contain water originating from traces of water carried by the synthesis starting materials and by the reaction medium. According to the present invention, a slight amount of water in each of the above reactants may also participate in the reaction for forming the spherical support of the olefin polymerization catalyst.
According to the invention, preferably, the structure of the 1,3 diether compound is shown as the formula (III):
wherein R is 21 And R 22 Each independently selected from hydrogen, C 1 -C 20 Linear or branched alkyl of (2), C 3 -C 20 Cycloalkyl of (C) 6 -C 20 Aryl of (C) 7 -C 20 Aralkyl or C 7 -C 20 Alkylaryl of, R 21 And R 22 Optionally bonded to form a ring; r 23 And R 24 Each independently selected from C 1 -C 10 Linear or branched alkyl groups of (1).
More preferably, the 1, 3-diether compound is selected from the group consisting of 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-dimethyl-2-propyl-dimethoxypropane, 2-dimethyl-propyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-2-propyl-dimethoxypropane, 2-propyl-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-dimethyl-1, 2-dimethyl-propyl-dimethyl-propyl, 2, and the same, 2, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
Most preferably, the diether compound is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
According to the present invention, in the catalyst component for olefin polymerization, the weight ratio of the titanium element, the magnesium element and the internal electron donor compound may be 1: 5-15: 2-15, preferably 1: 6-13: 3-12.
A second aspect of the invention provides the use of a catalyst component as described above in the preparation of a catalyst for the polymerisation of olefins.
A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:
(1) the above catalyst components;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
A fourth aspect of the invention provides the use of a catalyst as described above in the polymerisation of olefins.
A fifth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions. The olefin is at least one olefin represented by the formula CH2 ═ CHR, where R is hydrogen or C 1 -C 6 Linear or branched alkyl. The general formula CH 2 Specific examples of olefins represented by ═ CHR may include: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, 4-methyl-1-pentene. Preferably, the general formula CH 2 The olefins represented by CHR are ethylene and propyleneAlkenes, 1-n-butenes, 1-n-hexenes, 4-methyl-1-pentenes. More preferably, the general formula CH 2 The olefin represented by ═ CHR is propylene.
The olefin polymerization method of the present invention may be homopolymerization of a single olefin or copolymerization of a plurality of olefins.
According to the olefin polymerization process of the present invention, the olefin polymerization conditions may be conventional in the art. In general, the olefin polymerization conditions may include: the temperature is 0-150 ℃, the time is 0.1-8 hours, and the pressure is 0.01-10 MPa. Preferably, the olefin polymerization conditions include: the temperature is 50-100 ℃, the time is 0.5-3 hours, and the pressure is 0.5-5 MPa. The olefin polymerization catalyst may be used in various conventional amounts as in the prior art olefin catalysts.
The present invention will be described in detail below by way of examples.
In the examples and comparative examples:
1. the average particle diameter and the particle size distribution of the olefin polymerization catalyst support were measured using a Masters Sizer2000 particle Sizer (manufactured by Malvern Instruments Ltd.).
2. The apparent morphology of the olefin polymerization catalyst support was observed by means of an optical microscope, commercially available from Nikon under the model Eclipse E200.
3. Melt Flow Rate (MFR): measured according to ISO1133, 230 ℃ under a load of 2.16 kg.
4. The bulk density of the polyolefin powder was determined by the method specified in GB/T1636-2008.
Preparation example 1
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 8.0g (0.08mol) of magnesium chloride, 56mL (0.96mol) of ethanol, 1g (0.03mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as surfactants into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epoxy chloropropane, continuing to react at constant temperature of 90 ℃ for half an hour, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z1.
The spherical support Z1 for olefin polymerization catalyst had an average particle diameter (D50) of 15 μm and a particle size distribution ((D90-D10)/D50) of 0.6. As shown in FIG. 1, the spherical support Z1 for olefin polymerization catalyst has regular particle morphology, smooth surface, substantially spherical shape, concentrated particle size distribution and substantially no irregular particles.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z1 is as follows:
preparation example 2
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.3g (0.009mol) of beta-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature of 100 ℃ for 20 minutes, carrying out pressure filtration, washing a pressure filtration product for 5 times by using hexane, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z2.
The spherical carrier Z2 for the olefin polymerization catalyst has an average particle diameter (D50) of 18 microns and a particle size distribution ((D90-D10)/D50) of 0.7. The spherical carrier Z2 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to GC-MS, elemental analysis and nuclear magnetic characterization, the structural formula of Z2 is as follows:
preparation example 3
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.2g (0.006mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature of 100 ℃ for 20 minutes, carrying out pressure filtration, washing a pressure filtration product for 5 times by using hexane, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z3.
The spherical carrier Z3 for the olefin polymerization catalyst has an average particle diameter (D50) of 20 microns and a particle size distribution ((D90-D10)/D50) of 0.8. The spherical carrier Z3 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z3 is as follows:
preparation example 4
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 8.0g (0.08mol) of magnesium chloride, 59mL (0.48mol) of cyclohexylmethanol, 0.3g (0.009mol) of beta-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 60 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature for 20 minutes at 60 ℃, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z4.
The spherical carrier Z4 for the olefin polymerization catalyst had an average particle diameter (D50) of 25 μm and a particle size distribution ((D90-D10)/D50) of 0.9. The spherical carrier Z4 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z4 is as follows:
preparation example 5
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
In a 0.6L reaction kettle, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.3g (0.009mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant are added, the temperature is raised to 70 ℃ under stirring, after 1 hour of constant temperature reaction, 11.2mL (0.16mol) of propylene oxide is added, the constant temperature reaction is continued for 20 minutes at 70 ℃, then, the pressure filtration is carried out, the pressure filtration product is washed 5 times by hexane, and finally, the product is dried in vacuum, thus obtaining the olefin polymerization catalyst spherical carrier Z5.
The spherical support Z5 for olefin polymerization catalyst had an average particle diameter (D50) of 26 μm and a particle size distribution ((D90-D10)/D50) of 0.9. The optical microscope is adopted to observe that the particle shape of the spherical carrier Z5 of the olefin polymerization catalyst is regular, the surface is smooth, the spherical carrier Z5 is basically spherical, the particle size distribution is concentrated, and no irregular particles exist basically.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z5 is as follows:
comparative preparation example 1
This comparative preparation example is intended to illustrate a reference olefin polymerization catalyst support and a method for preparing the same.
Adding 0.08mol of magnesium chloride, 0.96mol of ethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epoxy chloropropane, continuing reacting at constant temperature of 90 ℃ for half an hour, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally drying the product in vacuum to obtain the catalyst carrier DZ1 for olefin polymerization.
The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ1 was 60 μm, and the particle size distribution ((D90-D10)/D50) was 1.3. The particle morphology observed with an optical microscope is shown in fig. 2. As can be seen from fig. 2, the olefin polymerization catalyst support DZ1 has irregular particles and a rough surface.
Comparative preparation example 2
Adding 8.0g (0.08mol) of magnesium chloride, 59mL (0.48mol) of cyclohexylmethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 60 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature for 20 minutes at 60 ℃, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier DZ 2.
The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ2 was 80 μm, and the particle size distribution ((D90-D10)/D50) was 1.5. The particle appearance is observed by adopting an optical microscope, special-shaped particles exist in DZ2, and the surface is rough.
Comparative preparation example 3
Adding 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 70 ℃ under stirring, reacting at constant temperature for 1 hour, adding 11.2mL (0.16mol) of propylene oxide, continuing to react at constant temperature of 70 ℃ for 20 minutes, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier DZ 3.
The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ3 was 88 μm, and the particle size distribution ((D90-D10)/D50) was 1.7. The particle morphology is observed by an optical microscope, and special-shaped particles exist in DZ3, and the surface is rough.
Example 1
This example serves to illustrate the catalyst components and catalyst preparation and propylene polymerization process provided by the present invention.
(1) Preparation of olefin polymerization catalyst
In a 300mL glass reaction vessel, 100mL of titanium tetrachloride was added, cooled to-20 ℃, and 40 g of the olefin polymerization catalyst support Z1 obtained in preparation example 1 was added thereto and stirred at-20 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 1.6mL of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane was added during the temperature raising, and the mixture was maintained at 110 ℃ for 30min, and then the liquid was filtered off. Then, titanium tetrachloride was added and the mixture was washed 2 times, finally, 3 times with hexane and dried to obtain an olefin polymerization catalyst C1.
(3) Propylene polymerization
In a 5L stainless steel autoclave, purging was conducted with a nitrogen stream, and then 1mmol of a triethylaluminum in hexane solution (triethylaluminum concentration 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, and 10mg of the olefin polymerization catalyst C1 obtained in step (1), 1.5L (standard volume) of hydrogen, and 2.5L of liquid propylene were introduced into the nitrogen stream. Heating to 70 ℃, reacting for 1 hour at the temperature, cooling, releasing pressure, discharging and drying to obtain the polypropylene powder P1.
The olefin polymerization catalyst C1 had an average particle diameter (D50) of 14 μm, a particle size distribution of 0.6, an activity of 59.9kg PP/g cat, a melt flow rate index of 15.0g/10min for the polypropylene powder P1, and a bulk density of 0.46g/cm 3 In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 2
This example serves to illustrate the catalyst components and catalyst preparation and propylene polymerization process provided by the present invention.
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in accordance with the procedure of example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier Z2 obtained in production example 2 to obtain an olefin polymerization catalyst C2 and a polypropylene powder P2.
The average particle diameter (D50) of the olefin polymerization catalyst C2 is 17 micrometers, the particle size distribution is 0.6, the activity of the catalyst is 57.6 kgPP/g-cat, the melt flow rate index of polypropylene powder P2 is 15.0g/10min, and the bulk density is 0.46g/cm 3 In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 3
This example serves to illustrate the catalyst components and catalyst preparation and propylene polymerization process provided by the present invention.
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in accordance with the procedure in example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier Z3 obtained in production example 3, to obtain an olefin polymerization catalyst C3 and a polypropylene powder P3.
The olefin polymerization catalyst C3 had an average particle diameter (D50) of 19 μm, a particle size distribution of 0.7, an activity of 57.1kg PP/g cat, a melt flow rate index of polypropylene powder P3 of 15.0g/10min, and a bulk density of 0.46g/cm 3 In addition, the polypropylene powder has good particle shape and basically has no profile.
Examples 4 to 6
This example serves to illustrate the catalyst components and catalyst preparation and propylene polymerization process provided by the present invention.
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in the same manner as in examples 1-3 except that 6.5L instead of 1.5L (standard volume) of hydrogen was added to obtain polypropylene powders P4, P5 and P6, respectively. The activity of olefin polymerization catalysts C1, C2 and C3 is 60.8kg PP/g cat, 58.2kg PP/g cat and 58.0kg PP/g cat in sequence, and the bulk density of polypropylene powder materials P4, P5 and P6 is 0.46g/cm in sequence 3 、0.46g/cm 3 、0.46g/cm 3 The melt flow rate index is 65.0g/10min, 64.8g/10min and 64.7g/10min in sequence, and in addition, the polypropylene powder P4, P5 and P6 have good particle forms and basically have no profile.
Example 7
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in accordance with the procedure of example 1, except that the olefin polymerization catalyst spherical support Z1 was replaced with the olefin polymerization catalyst spherical support Z4 obtained in production example 4 to obtain an olefin polymerization catalyst C7 and a polypropylene powder P7.
The olefin polymerization catalyst C7 had an average particle diameter (D50) of 23 μm, a particle size distribution of 0.8, an activity of 57.8 kgPP/g. cat, a melt flow rate index of polypropylene powder P5 of 14.2g/10min and a bulk density of 0.46g/cm 3 In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 8
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in accordance with the procedure in example 1, except that the spherical support for an olefin polymerization catalyst Z1 was replaced with the spherical support for an olefin polymerization catalyst Z5 obtained in preparation example 5, to obtain an olefin polymerization catalyst C8 and a polypropylene powder P8.
The olefin polymerization catalyst C8 had an average particle diameter (D50) of 25 μm, a particle size distribution of 0.8, an activity of 56.9kg PP/g cat, a melt flow rate index of 14.8g/10min for the polypropylene powder P7 and a bulk density of 0.46g/cm 3 In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 9
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in the same manner as in example 1 except that 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was replaced with an equal amount of 9, 9-dimethoxymethylfluorene to obtain an olefin polymerization catalyst C9 and a polypropylene powder material P9.
The activity of the olefin polymerization catalyst C9 was 59.7 kgPP/g. cat, the melt flow rate index of the polypropylene powder P9 was 15.3g/10min, and the bulk density was 0.46g/cm 3 In addition, the polypropylene powder has good particle shape and basically has no profile.
Comparative example 1
This comparative example serves to illustrate the catalyst components and a reference preparation of the catalyst.
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in accordance with the procedure of example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier DZ1 obtained in comparative preparation example 1 to obtain an olefin polymerization catalyst DC1 and a polypropylene powder DP 1.
The olefin catalyst DC1 had an average particle diameter (D50) of 58 microns, a particle size distribution of 1.2, an activity of 53.0 kgPP/g-cat, a melt flow rate index of 14.0g/10min for the polypropylene powder DP3, and a bulk density of 0.38g/cm 3 In addition, the polypropylene powder particles have profile materials, and the flowability is poor.
Comparative example 2
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in the same manner as in comparative example 1 except that 6.5L of hydrogen gas was added instead of 1.5L (standard volume) to obtain polypropylene powder DP 2.
The activity of the olefin polymerization catalyst DC1 was 59.1 kgPP/g. cat, and the bulk density of the polypropylene powder DP2 was 0.38g/cm 3 The melt flow rate index was 57.0g/10min, and further, the polypropylene powder particles had a profile and had poor flowability.
Comparative example 3
This comparative example serves to illustrate the catalyst components and the reference preparation of the catalyst.
Preparation of an olefin polymerization catalyst and polymerization of propylene were carried out in the same manner as in comparative example 1 except that diisobutylphthalate was used in place of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to obtain an olefin polymerization catalyst DC3 and a polypropylene powder DP 3.
The activity of the olefin polymerization catalyst DC3 is 32.0 kgPP/g-cat, the melt flow rate index of the polypropylene powder DP1 is 7.0g/10min, and the bulk density is 0.39g/cm 3 In addition, the polypropylene powder particles have profile materials, and the flowability is poor.
Comparative example 4
Preparation of an olefin polymerization catalyst and propylene polymerization were conducted in the same manner as in comparative example 3 except that 6.5L of hydrogen gas was added instead of 1.5L (standard volume) to obtain polypropylene powder DP 4.
The activity of the olefin polymerization catalyst DC3 was 33.1 kgPP/g. cat, polypropyleneThe bulk density of the olefin powder DP4 was 0.39g/cm 3 The melt flow rate index was 37.0g/10min, and further, the polypropylene powder particles had a profile and had poor flowability.
Comparative example 5
This comparative example serves to illustrate the preparation of a reference olefin polymerization catalyst.
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in accordance with the method of comparative example 3 except that the olefin polymerization catalyst spherical support Z1 was replaced with the olefin polymerization catalyst support DZ2 obtained in comparative example 2 to obtain an olefin polymerization catalyst DC5 and a polypropylene powder DP 5.
The olefin polymerization catalyst DC5 had an average particle diameter of 66 μm, a particle size distribution of 1.4, an activity of 32.3 kgPP/g-cat, a melt flow rate index of 7.4g/10min for the polypropylene powder DP5, and a bulk density of 0.39g/cm 3 In addition, the polypropylene powder particles have profile materials, and the flowability is poor.
Comparative example 6
This comparative example serves to illustrate the preparation of a reference olefin polymerization catalyst.
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in accordance with the procedure of comparative example 3 except that the olefin polymerization catalyst spherical support Z1 was replaced with the olefin polymerization catalyst support DZ3 obtained in comparative preparation example 3 to obtain an olefin polymerization catalyst DC6 and a polypropylene powder DP 6.
The olefin polymerization catalyst DC6 had an average particle diameter of 83 microns, a particle size distribution of 1.6, an activity of 32.8 kgPP/g-cat, a melt flow rate index of 7.8g/10min for the polypropylene powder DP6, and a bulk density of 0.38g/cm 3 In addition, the polypropylene powder particles have profile materials, and the flowability is poor.
From the above results, it can be seen that the olefin polymerization catalyst carrier having a novel composition used in the present invention has a good particle morphology, a smooth surface, substantially no occurrence of irregular particles, and a narrow particle size distribution. The catalyst prepared by taking the carrier as a solid component and combining the 1, 3-diether compound as an internal electron donor has small particle size, higher activity and good hydrogen regulation sensitivity. When the catalyst is used for olefin (particularly propylene) polymerization, the bulk density of a polymerization product can be improved, and no foreign materials exist in the polymerization product. Therefore, the catalyst component of the invention has great industrial application prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (27)
1. A catalyst component for the polymerization of olefins comprising the reaction product of:
(1) a solid component which is at least one sulfur-containing magnesium compound represented by formula (I);
(2) at least one titanium compound; and
(3) the internal electron donor compound is at least one 1, 3-diether compound;
In the formula (I), R 1 Is C 1 -C 8 Linear or branched alkyl of, or C 3 -C 8 Cycloalkyl groups of (a);
R 2 and R 3 Identical or different, each being independentThe place is hydrogen or C 1 -C 5 The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be optionally substituted with a halogen atom;
x is halogen;
m is 0.1-1.9, n is 0.1-1.9, m + n =2, 0< q ≤ 0.5.
2. The catalyst component according to claim 1 in which X is chlorine or bromine.
3. The catalyst component according to claim 1 in which the starting material for the synthesis of the sulphur-containing magnesium compound comprises elemental sulphur, of general formula MgX 1 Magnesium halide of Y, formula R 1 OH compounds, ethylene oxide compounds;
general formula MgX 1 In Y, X 1 Is halogen, Y is halogen, C 1 -C 5 Alkyl of (C) 1 -C 5 Alkoxy group of (C) 6 -C 10 Aryl or C of 6 -C 10 An aryloxy group of (1);
general formula R 1 In OH, R 1 Is C 1 -C 8 Alkyl or C 3 -C 8 Cycloalkyl groups of (a);
the structure of the ethylene oxide compound is shown as the formula (II):
in the formula (II), R 5 And R 6 Each independently is hydrogen, C 1 -C 5 Alkyl or C of 1 -C 5 A haloalkyl group of (a).
4. The catalyst component according to claim 3 in which the sulphur-containing magnesium compound is obtained by a process comprising the steps of:
(1) elemental sulfur with the general formula of MgX 1 Magnesium halide of Y, formula R 1 A compound of OH, optionally an inert liquid medium, optionally a surfactant, is mixed and heated,obtaining a liquid mixture;
(2) and (2) carrying out contact reaction on the liquid mixture obtained in the step (1) and an ethylene oxide compound.
5. The catalyst component according to claim 4 in which the inert liquid medium is a silicone-oil type solvent and/or a hydrocarbon type solvent; 1mol of the general formula MgX 1 The amount of the inert liquid medium is 0.8-10L based on magnesium halide of Y.
6. The catalyst component according to claim 5 in which 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.
7. The catalyst component according to claim 4 in which the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid salts, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, modified polyethyleneimine, polymers of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethyleneoxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenylpolyoxyethylene ether, and polyalkylmethacrylates; 1mol of MgX 1 The dosage of the surfactant is 1-20g based on magnesium halide of Y.
8. The catalyst component according to claim 4 in which in step (1) the heating is carried out at a temperature of from 80 to 120 ℃ for a time of from 0.5 to 5 hours; in the step (2), the contact reaction conditions include: the temperature is 40-120 ℃ and the time is 15-60 minutes.
9. The catalyst component according to claim 8 in which in step (1) the heating is carried out at a temperature of from 80 to 100 ℃ for a time of from 0.5 to 3 hours; in the step (2), the contact reaction conditions include: the temperature is 60-100 ℃, and the time is 20-50 minutes.
10. The catalyst component according to any of claims 3 to 9 in which 1mol of formula MgX is present 1 The magnesium halide of Y is taken as a reference, the dosage of the elemental sulfur is 0.0001 to 0.5mol, and the general formula is R 1 The dosage of the OH compound is 4-30mol, and the dosage of the ethylene oxide compound is 1-10 mol.
11. The catalyst component according to claim 10 in which MgX is present in 1mol 1 Based on magnesium halide of Y, the general formula is R 1 The dosage of the OH compound is 6-20mol, and the dosage of the ethylene oxide compound is 2-6 mol.
12. The catalyst component according to any of claims 3 to 9 in which the elemental sulphur is selected from at least one of alpha sulphur, beta sulphur, gamma sulphur and polymeric sulphur.
13. The catalyst component according to any of claims 3 to 9 in which the general formula MgX 1 In Y, X 1 Is chlorine or bromine, Y is chlorine, bromine, C 1 -C 5 Alkoxy or C 6 -C 10 An aryloxy group of (1).
14. The catalyst component according to claim 13 in which the general formula is MgX 1 The magnesium halide of Y is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.
15. The catalyst component according to any of claims 3 to 9 in which R is of the general formula 1 In OH, R 1 Is C 1 -C 8 The alkyl group of (1).
16. The catalyst component according to claim 15 which isIn the general formula R 1 The compound of OH is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, 2-ethylhexanol, and n-octanol.
17. The catalyst component according to any of claims 3 to 9 in which in the oxirane compound of formula (II), R is 5 And R 6 Each independently is hydrogen, C 1 -C 3 Alkyl or C 1 -C 3 The haloalkyl group of (1).
18. The catalyst component according to claim 17 in which the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
19. The catalyst component according to claim 1 in which the sulphur-containing magnesium compound has an average particle diameter of less than or equal to 30 microns and a particle size distribution of less than 1.2.
20. The catalyst component according to claim 19 in which the sulphur-containing magnesium compound has an average particle diameter of 20 microns or less and a particle size distribution of 0.8 or less.
21. The catalyst component according to claim 1 in which the 1,3 diether compound has the structure shown in formula (iii):
Wherein R is 21 And R 22 Each independently selected from hydrogen and C 1 -C 20 Linear or branched alkyl of (2), C 3 -C 20 Cycloalkyl of, C 6 -C 20 Aryl of (C) 7 -C 20 Aralkyl or C 7 -C 20 Alkylaryl of, R 21 And R 22 Optionally bonded to form a ring; r is 23 And R 24 Each independently selected from C 1 -C 10 Linear or branched alkyl groups of (1).
22. The catalyst component according to claim 1 in which the weight ratio of titanium element, magnesium element and internal electron donor compound in the catalyst component for olefin polymerization is 1: 5-15: 2-15.
23. The catalyst component according to claim 22 in which the weight ratio of titanium element, magnesium element and internal electron donor compound in the catalyst component for the polymerization of olefins is 1: 6-13: 3-12.
24. Use of the catalyst component according to any one of claims 1 to 23 in the preparation of a catalyst for the polymerization of olefins.
25. A catalyst for the polymerization of olefins, the catalyst comprising:
(1) the catalyst component of any one of claims 1 to 23;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
26. Use of the catalyst of claim 25 in olefin polymerization reactions.
27. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of claim 25 under olefin polymerization conditions.
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| CN106478850A (en) * | 2015-09-01 | 2017-03-08 | 中国石油化工股份有限公司 | Preparation method and ethylene rolymerization catalyst for the catalytic component of vinyl polymerization |
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| CN106478850A (en) * | 2015-09-01 | 2017-03-08 | 中国石油化工股份有限公司 | Preparation method and ethylene rolymerization catalyst for the catalytic component of vinyl polymerization |
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