CN114478856A - Olefin polymerization catalyst spherical carrier and preparation method and application thereof - Google Patents
Olefin polymerization catalyst spherical carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN114478856A CN114478856A CN202011157112.XA CN202011157112A CN114478856A CN 114478856 A CN114478856 A CN 114478856A CN 202011157112 A CN202011157112 A CN 202011157112A CN 114478856 A CN114478856 A CN 114478856A
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- CN
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- Prior art keywords
- formula
- compound
- alkyl
- olefin polymerization
- polymerization catalyst
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 95
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 17
- -1 phthalate ester compounds Chemical class 0.000 claims description 100
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 33
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910017718 MgXY Inorganic materials 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 26
- 229910052749 magnesium Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical group 0.000 claims description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Chemical group 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- ZVAKZVDJIUFFFP-UHFFFAOYSA-N 2-chlorooxolane Chemical compound ClC1CCCO1 ZVAKZVDJIUFFFP-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 claims description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- ROLDQQDCCSZBNA-UHFFFAOYSA-N oxolane;hydrobromide Chemical compound Br.C1CCOC1 ROLDQQDCCSZBNA-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 25
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 229920000642 polymer Polymers 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- 239000000843 powder Substances 0.000 description 32
- 239000004743 Polypropylene Substances 0.000 description 31
- 229920001155 polypropylene Polymers 0.000 description 30
- 238000011085 pressure filtration Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000155 melt Substances 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000003756 stirring 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
- 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 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 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
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- HPOWOWTVWZELDK-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)cyclohexane Chemical compound COCC(C)(COC)C1CCCCC1 HPOWOWTVWZELDK-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- CELOJHLXFPSJPH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylbenzene Chemical compound COCC(COC)C1=CC=CC=C1 CELOJHLXFPSJPH-UHFFFAOYSA-N 0.000 description 2
- NOWCPSTWMDNKTI-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylcyclohexane Chemical compound COCC(COC)C1CCCCC1 NOWCPSTWMDNKTI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical compound COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 2
- ROSQVPGTZCDBOC-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C)(COC)CC(C)C ROSQVPGTZCDBOC-UHFFFAOYSA-N 0.000 description 2
- XAGXJWYEHBCLPN-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylbutane Chemical compound COCC(C)(CC)COC XAGXJWYEHBCLPN-UHFFFAOYSA-N 0.000 description 2
- SVJCEDKUVMVBKM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylpentane Chemical compound CCCC(C)(COC)COC SVJCEDKUVMVBKM-UHFFFAOYSA-N 0.000 description 2
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 2
- FDLMLTYTOFIPCK-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylpentane Chemical compound CCC(C)C(COC)COC FDLMLTYTOFIPCK-UHFFFAOYSA-N 0.000 description 2
- PPHMKLXXVBJEHR-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)hexane Chemical compound CCCCC(COC)COC PPHMKLXXVBJEHR-UHFFFAOYSA-N 0.000 description 2
- JUJMPCLNRKYKRA-UHFFFAOYSA-N 2,4-dimethoxybutylcyclohexane Chemical compound COCCC(OC)CC1CCCCC1 JUJMPCLNRKYKRA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 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 2
- 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 2
- WAHDOBRAAIQNTA-UHFFFAOYSA-N 3,5-dimethoxypentylcyclohexane Chemical compound COCCC(OC)CCC1CCCCC1 WAHDOBRAAIQNTA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VIJVFTUOJNTXCA-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)octane Chemical compound CCCCC(CC)CC(COC)COC VIJVFTUOJNTXCA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 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
- 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 2
- 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 2
- 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 2
- 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 2
- 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 2
- 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 2
- 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 2
- 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 2
- 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 2
- 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 2
- JXQCBJLNEGKSCN-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]benzene Chemical compound COCC(COC)CCC1=CC=CC=C1 JXQCBJLNEGKSCN-UHFFFAOYSA-N 0.000 description 2
- AWLBWJXVYGYRNY-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]cyclohexane Chemical compound COCC(COC)CCC1CCCCC1 AWLBWJXVYGYRNY-UHFFFAOYSA-N 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IHLOHSVGQFOXTR-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)(CCC)OC(C1=CC=CC=C1)=O Chemical compound C(C1=CC=CC=C1)(=O)OC(C)(CCC)OC(C1=CC=CC=C1)=O IHLOHSVGQFOXTR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001125 extrusion 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 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
- 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
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 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
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
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
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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 provides an olefin polymerization catalyst carrier, a preparation method of the olefin polymerization catalyst carrier and application of the olefin polymerization catalyst carrier. The spherical carrier of the olefin polymerization catalyst comprises a composition shown in a formula (I). The olefin polymerization catalyst carrier prepared by the preparation method of the olefin polymerization catalyst carrier has good particle shape, smooth surface and basically no special-shaped particles, and when the catalyst prepared by the obtained carrier is used for olefin (especially propylene) polymerization, the catalyst has better appearance and the polymer has better appearance.
Description
Technical Field
The invention relates to a spherical carrier of an olefin polymerization catalyst, a preparation method of the carrier of the olefin polymerization catalyst, the carrier prepared by the method and application of the carrier of the olefin polymerization catalyst in preparing the olefin polymerization catalyst.
Background
It is well known that the support is a very important invention in the development history of Ziegler-Natta catalysts, while an effective support is generally a magnesium chloride support, which is derived from magnesium chloride alcoholate, and the performance of the supported catalyst is significantly better than that of catalysts supported by other supports when the supported catalyst is used for olefin (especially propylene) polymerization. Therefore, the catalysts currently used for olefin polymerization are mostly prepared by supporting titanium halide on magnesium chloride alcoholate. In order to obtain better application performance, the magnesium chloride alcoholate can be prepared into spherical shape by spray drying, spray cooling, high-pressure extrusion, high-speed stirring, an emulsifying machine method, a high-gravity rotating bed method and the like, and WO99/44009, US4399054 and the like disclose that the magnesium chloride alcoholate system can be emulsified at high speed at high temperature and then quenched to form the spherical alcoholate.
The magnesium chloride alcoholate is generally prepared by high-temperature melting and then low-temperature quenching and solidification, so that the consumption of energy is high, the preparation process is complex, a plurality of reactors are required for combined preparation, and the particle size distribution of the prepared alcoholate is wide. In order to solve the problem, CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcohol compound with an ethylene oxide compound by chemical molding, and specifically discloses adding the ethylene oxide compound after melting and dispersing the magnesium halide alcohol compound; 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 and poor carrier forming effect.
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 unexpectedly found that by adding the compound B in the preparation process of the carrier, not only a carrier with a novel composition is obtained, but also the adhesion of the carrier can be effectively reduced in the preparation process of the carrier, and the obtained carrier has a good particle shape and a good spherical shape. And the prepared catalyst has better hydrogen regulation sensitivity.
The first object of the present invention is to overcome the above-mentioned drawbacks of the existing olefin polymerization catalyst supports, and to provide a novel spherical support for olefin polymerization catalysts.
The second object of the present invention is to provide a method for preparing a carrier for an olefin polymerization catalyst.
The third object of the present invention is to provide a carrier for olefin polymerization catalyst prepared by the above method.
The fourth object of the present invention is to provide the use of the olefin polymerization catalyst support for the preparation of an olefin polymerization catalyst.
The invention provides a spherical carrier of an olefin polymerization catalyst, which comprises a composition shown in a formula (I),
in the formula (I), R1Is C1-C14Alkyl or C3-C14Cycloalkyl, preferably C1-C8Alkyl or C3-C8A cycloalkyl group; r2And R3Identical or different from hydrogen and C1-C5Alkyl or C1-C5A halogenated alkane; x is halogen, preferably chlorine or bromine; m is 0.1 to 1.9, n is 0.1 to 1.9, and m + n is 2;
B1represents a compound B selected from the group consisting of 1, 3-diether compounds, phthalate ester compounds and glycol ester compounds, 0<q≤0.5。
According to some embodiments of the invention, in formula (I), R1Is C1-C6An alkyl group.
According to some embodiments of the invention, in formula (I), R2And R3Identical or different from hydrogen and C1-C5Alkyl or C1-C5A halogenated alkane.
According to some embodiments of the invention, in formula (I), X is chloro or bromo.
According to the invention, formula (I) represents
With compound B.
According to some embodiments of the invention, the 1, 3-diether compound has the structure of formula (II):
in the formula (II), R21And R22Each independently selected from hydrogen and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl and C7-C20One of the alkylaryl groups of (1), R23And R24Each independently selected from C1-C10Alkyl group of (1).
According to some embodiments of the invention, the phthalate compound has the structure according to formula (III):
in the formula (III), R10And R11Identical or different, independently selected from C1-C10Alkyl and C3-C20A cycloalkyl group.
According to some embodiments of the invention, the diol ester compound has the structure of formula (IV):
r 'in the formula (IV)'1-R'6Identical or different, independently selected from hydrogen and C1-C10Alkyl radical, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl or arylalkyl, but R'1，R'2，R'5，R'6Not hydrogen at the same time; r'1-R'6Wherein two or more groups may be bonded to each other to form one or more fused ring structures;
R'7and R'8Identical or different, independently selected from C1-C10Alkyl of (C)3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20An aromatic hydrocarbon group in which a hydrogen on a benzene ring in the aryl or alkaryl group or the aromatic hydrocarbon group may be optionally substituted with a halogen atom.
According to the invention, the compound B is a compound 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. Preferably, the diether compound is at least one of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
According to some embodiments of the invention, the olefin polymerization catalyst support synthesis feedstock comprises the compound B, a magnesium halide of the general formula MgXY, a compound of the general formula ROH, and an oxirane;
in the general formula MgXY, X is halogen and Y is halogen or C1-C14An alkyl group;
in the formula ROH, R is C1-C14Alkyl or C3-C14A cycloalkyl group.
According to some embodiments of the invention, the structure of the oxirane is according to formula (V):
in the formula (V), R5And R6Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group.
According to some preferred embodiments, in the general formula MgXY, X is halogen and Y is selected from halogen or C1-C6An alkyl group.
According to some preferred embodiments, in the general formula MgXY, X is chlorine or bromine and Y is chlorine, bromine or C1-C5An alkyl group; more preferably, the magnesium halide of formula MgXY is selected from magnesium chloride.
According to some preferred embodiments, in the general formula ROH, R is C1-C8Alkyl or C3-C8A cycloalkyl group. According to some preferred embodiments, in the general formula ROH, R is C1-C8Alkyl group of (1). According to some preferred embodiments, in formula ROH, R is C1-C6Alkyl group of (1).
More preferably, the compound of formula ROH is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
According to some preferred embodiments, in the oxirane compound, R5And R6Each independently is hydrogen, C1-C3An alkyl or haloalkyl group; more preferably, the oxirane compound is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
According to some embodiments of the present invention, based on 1mol of magnesium halide having a general formula of MgXY, the amount of compound B is 0.0001 to 0.1mol, the amount of compound having a general formula of ROH is 4 to 30mol, and the amount of oxirane compound having a structure represented by formula (V) is 1 to 10 mol; preferably, based on 1mol of magnesium halide with the general formula of MgXY, the dosage of the compound with the general formula of ROH is 6-20mol, and the dosage of the ethylene oxide compound with the structure shown in the formula (V) is 2-6 mol.
According to some embodiments of the invention, the olefin polymerization catalyst support has an average particle diameter of 10 to 100 microns and a particle size distribution of less than 1.2; preferably, the olefin polymerization catalyst support has an average particle diameter of 40 to 60 μm and a particle size distribution of 0.6 to 0.8.
According to the invention, the water contained in the olefin polymerization catalyst support originates from traces of water carried by the synthesis raw materials and the reaction medium.
The preparation method of the olefin polymerization catalyst carrier provided by the invention comprises the following steps:
(1) mixing and heating a compound B, magnesium halide with a general formula of MgXY, a compound with a general formula of ROH and an optional inert liquid medium to obtain a liquid mixture;
(2) emulsifying the liquid mixture obtained in the step (1), and contacting and reacting the emulsified product with an ethylene oxide compound;
wherein, in the step (1), the compound B is selected from 1, 3-diether compounds, phthalate ester compounds and glycol ester compounds;
in the general formula MgXY, X is halogen and Y is halogen or C1-C14An alkyl group;
in the formula ROH, R is C1-C14Alkyl or C3-C14A cycloalkyl group.
According to some embodiments of the invention, the structure of the oxirane is according to formula (V):
in the formula (V), R5And R6Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group.
According to some embodiments of the preparation process of the present invention, in the general formula MgXY, X isIs halogen, Y is selected from halogen and C1-C6An alkyl group.
According to some embodiments of the preparation process of the present invention, in the general formula MgXY, X is chlorine or bromine and Y is chlorine, bromine or C1-C5An alkyl group; preferably, the magnesium halide of formula MgXY is selected from magnesium chloride.
According to the invention, the compound B is a compound 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. Preferably, the diether compound is at least one of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
According to some preferred embodiments, in the general formula ROH, R is C1-C8Alkyl or C3-C8A cycloalkyl group. According to some preferred embodiments, in the general formula ROH, R is C1-C8Alkyl group of (1). According to some preferred embodiments, in the general formula ROH, R is C1-C6Alkyl group of (1).
More preferably, the compound of formula ROH is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
According to some embodiments of the process of the present invention, in the oxirane compound, R5And R6Each independently is hydrogen, C1-C3An alkyl or haloalkyl group; preferably, the oxirane compound is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
According to some embodiments of the preparation method of the present invention, the 1, 3-diether compound has a structure represented by formula (II):
in the formula (II), R21And R22Each independently selected from hydrogen and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl and C7-C20One of the alkylaryl groups of (1), R23And R24Each independently selected from C1-C10Alkyl groups of (a);
according to some embodiments of the method of the present invention, the phthalate compound has a structure represented by formula (III):
in the formula (III), R10And R11Identical or different, independently selected from C1-C10Alkyl and C3-C20A cycloalkyl group;
according to some embodiments of the preparation method of the present invention, the diol ester compound has a structure represented by formula (IV):
r 'in the formula (IV)'1-R'6Identical or different, independently selected from hydrogen and C1-C10Alkyl radical, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl or arylalkyl, but R'1，R'2，R'5，R'6Not hydrogen at the same time; r'1-R'6Wherein two or more groups may be bonded to each other to form one or more fused ring structures;
R'7and R'8Identical or different, independently selected from C1-C10Alkyl of (C)3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20An aromatic hydrocarbon group in which a hydrogen on a benzene ring in the aryl or alkaryl group or the aromatic hydrocarbon group may be optionally substituted with a halogen atom.
According to the invention, traces of water in the above-mentioned reactants may also participate in the reaction for forming the support for the olefin polymerization catalyst.
According to the present invention, in step (1), the conditions for heating the mixture of compound B, the magnesium halide of formula MgXY, the compound of formula ROH, optionally with an inert liquid medium, are not particularly limited, as long as the heating conditions are such that the magnesium halide of formula MgXY melts and reacts sufficiently with compound B. Generally, the conditions of heating include: the temperature can be 80-120 ℃, and the time can be 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the time is 0.5-3 hours.
According to the invention, the amount of said inert liquid medium can be chosen according to the amount of magnesium halide of general formula MgXY. In general, the inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on 1mol of magnesium halide of the formula MgXY. The inert liquid medium may be any of the 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 and/or an inert liquid hydrocarbon solvent. Specifically, the inert liquid medium may be one or more 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.
According to the present invention, 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 emulsified by subjecting it to low or high shear. The low shear agitation rate is typically 400-800 rpm. Such high shear methods are well known to those skilled in the art, such as the high speed stirring method disclosed in CN1151183C (i.e., the solution containing the liquid magnesium halide adduct is stirred at a speed of 2000-5000 rpm). In addition, the liquid mixture may be emulsified by the methods disclosed in the following patents: CN1267508C discloses that a solution containing a liquid magnesium halide adduct is subjected to rotating dispersion in a supergravity bed (the rotating speed can be 100-3000 r/min); CN1463990A discloses that the solution containing the liquid magnesium halide adduct is output at the speed of 1500-8000 rpm in an emulsifying machine; US6020279 discloses emulsifying a solution containing a liquid magnesium halide adduct by spraying.
According to the present invention, the conditions for the contact reaction of the emulsified product with the ethylene oxide in the step (2) may be any of the existing conditions capable of forming a carrier for an olefin polymerization catalyst, for example, the conditions for the contact reaction may include a temperature of 50 to 120 ℃ and a time of 20 to 60 minutes; preferably, the temperature is 60-100 ℃ and the time is 20-50 minutes.
According to the present invention, the method may further comprise subjecting the product obtained by the contact reaction to solid-liquid separation, washing the solid-phase product and drying. 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. In the present invention, the conditions for the pressure filtration are not particularly limited, and it is considered that the separation of the solid phase and the liquid phase is sufficiently achieved as much 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.
The invention also provides an olefin polymerization catalyst carrier prepared by the method. According to the present invention, the olefin polymerization catalyst support may have an average particle diameter of 10 to 100 microns, preferably 40 to 60 microns, and a particle size distribution of less than 1.2, preferably 0.2 to 0.8. In the preferred embodiment, the catalyst prepared from the olefin polymerization catalyst support 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 olefin polymerization catalyst support can be measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).
According to the fourth aspect of the present invention, the olefin polymerization catalyst support is further reacted with a titanium halide and an electron donor compound to obtain a catalyst suitable for olefin (particularly, propylene) polymerization. Thus, the present invention further provides the use of the above olefin polymerization catalyst support in the preparation of an olefin polymerization catalyst.
In the present application, the alkyl group 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 group, an n-pentyl group, an isopentyl group, a tert-pentyl group or a neopentyl group, and the C1-C5The alkoxy group of (a) may be, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group, the aryl group 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, and the aryloxy group may be, for example, a phenoxy group or a naphthyloxy group.
The inventors of the present invention have surprisingly found that by adding the compound B in the preparation process of the olefin polymerization catalyst carrier, a carrier having a novel composition can be obtained, and the compound B can reduce the collision probability between unformed particles, reduce the adhesion between carrier particles, make the obtained carrier particles have a good morphology, exhibit a good spherical shape, and improve the hydrogen response of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
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 Sizer 2000 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. the bulk density of the polyolefin powder was determined by the method specified in GB/T1636-2008.
4. The melt flow index of the polyolefin powder was measured according to ISO1133, 230 ℃ under a load of 2.16 kg.
5. Catalyst activity-weight of polymer obtained/weight of catalyst component used.
Preparation example 1
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
In a 0.6L reactor, 0.08mol of magnesium chloride, 0.96mol of ethanol, 1.8g of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane (0.084mol), and 0.3g of polyvinylpyrrolidone were added, and the temperature was raised to 90 ℃ with stirring. After 2 hours of isothermal reaction. 0.48mol (38ml) of epichlorohydrin is added, the reaction is carried out for half an hour, then, the pressure filtration is carried out, the product obtained after the pressure filtration is washed for 5 times by hexane and dried in vacuum, and the catalyst carrier Z1 for olefin polymerization is obtained.
The olefin polymerization catalyst carrier Z1 is determined to have the following composition by nuclear magnetism, element analysis and chromatographic methods:
the olefin polymerization catalyst carrier Z1 had an average particle diameter (D50) of 46 μm and a particle size distribution ((D90-D10)/D50) of 0.7. The particle observed by an optical microscope has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Preparation example 2
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
In a 0.6L reactor, 0.08mol of magnesium chloride, 0.96mol of ethanol, 2.1g of 9, 9-dimethoxymethylfluorene (0.0084mol), 0.3g of polyvinylpyrrolidone were added, and the temperature was raised to 90 ℃ with stirring. After 2 hours of isothermal reaction. 0.48mol (38ml) of epichlorohydrin is added, the reaction is carried out for half an hour, then, the pressure filtration is carried out, the product obtained after the pressure filtration is washed for 5 times by hexane and dried in vacuum, and the catalyst carrier Z2 for olefin polymerization is obtained.
The olefin polymerization catalyst carrier Z2 is determined to have the following composition by nuclear magnetism, element analysis and chromatographic methods:
the olefin polymerization catalyst carrier Z2 had an average particle diameter (D50) of 45 μm and a particle size distribution ((D90-D10)/D50) of 0.7. The particle observed by an optical microscope has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Comparative preparation example 1
This comparative preparation is intended to illustrate a reference olefin polymerization catalyst support and a process for its preparation.
0.08mol of magnesium chloride and 0.96mol of ethanol are added into a 0.6L reaction kettle, and the temperature is raised to 90 ℃ under stirring. After 2 hours of isothermal reaction. Adding 0.48mol (38ml) of epichlorohydrin, reacting for half an hour, then performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and performing vacuum drying to obtain the catalyst carrier D-Z1 for olefin polymerization.
The average particle diameter (D50) of the olefin polymerization catalyst carrier D-Z1 was 100. mu.m, and the particle size distribution ((D90-D10)/D50) was 1.6. The particle morphology observed by an optical microscope shows that a large number of special-shaped particles exist in the catalyst carrier D-Z1 for olefin polymerization, and the surface is rough.
Example 1
This example illustrates the preparation of a polyolefin 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 1.5mL of diisobutyl phthalate was added during the temperature raising, and the temperature was maintained at 110 ℃ for 30min, after which 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 hexane solution of triethylaluminum (concentration of triethylaluminum is 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. The melt flow index of the polypropylene powder is 8.9g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Example 2
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene polymerization was conducted in the same manner as in example 1 except that 1.5L (standard volume) of hydrogen was substituted for 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The melt flow index of the polypropylene powder is 44.6g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Example 3
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene was polymerized by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier Z2 obtained in preparation example 2, to obtain a polypropylene powder. The melt flow index of the polypropylene powder is 8.9g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Example 4
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene polymerization was conducted in the same manner as in example 3 except that 1.5L (standard volume) of hydrogen was substituted for 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The melt flow index of the polypropylene powder is 46.4g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Comparative example 1
This comparative example serves to illustrate the reference preparation of olefins.
Propylene was polymerized in the same manner as in example 1 except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier D-Z1 obtained in comparative preparation example 1 to obtain a polypropylene powder. As a result, the activity of the catalyst was 32.2kg PP/g cat, the melt flow index of the polypropylene powder was 7.1g/10min, and further, the polypropylene powder particles were all irregular and had poor flowability.
Comparative example 2
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene polymerization was conducted in the same manner as in comparative example 1 except that 1.5L (standard volume) of hydrogen was substituted for 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The activity of the catalyst is 33.1 kgPP/g. cat, the melt flow index of the polypropylene powder is 35.3g/10min, and in addition, the polypropylene powder has good particle shape and basically no abnormal material exists.
Preparation example 3
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
In a 0.6L reactor, 0.08mol of magnesium chloride, 0.96mol of ethanol, 1.1ml of diisobutyl phthalate (0.0042mol), and 0.3g of polyvinylpyrrolidone were charged, and the temperature was raised to 90 ℃ with stirring. After 2 hours of isothermal reaction. 0.48mol (38ml) of epichlorohydrin is added, and after half an hour of reaction, the mixture is subjected to pressure filtration, and the product obtained after the pressure filtration is washed 5 times with hexane and dried in vacuum, thus obtaining the catalyst carrier Z3 for olefin polymerization.
The composition of Z3 of the olefin polymerization catalyst carrier is determined by nuclear magnetism, element analysis and a chromatographic method as follows:
the olefin polymerization catalyst carrier Z3 had an average particle diameter (D50) of 50 μm and a particle size distribution ((D90-D10)/D50) of 0.9. The particle observed by an optical microscope has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Preparation example 4
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
In a 0.6L reactor, 0.08mol of magnesium chloride, 0.96mol of ethanol, 2.2ml of diisobutyl phthalate (0.0084mol), 0.3g of polyvinylpyrrolidone were charged, and the temperature was raised to 90 ℃ with stirring. After 2 hours of isothermal reaction. 0.48mol (38ml) of epichlorohydrin is added, the reaction is carried out for half an hour, then, the pressure filtration is carried out, the product obtained after the pressure filtration is washed for 5 times by hexane and dried in vacuum, and the catalyst carrier Z4 for olefin polymerization is obtained.
The composition of Z4 of the olefin polymerization catalyst carrier is determined by nuclear magnetism, element analysis and a chromatographic method as follows:
the olefin polymerization catalyst carrier Z4 had an average particle diameter (D50) of 39 μm and a particle size distribution ((D90-D10)/D50) of 0.8. The particle observed by an optical microscope has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Preparation example 5
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
Into a 0.6L reactor, 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 2.1g of 1, 3-dimethylpropanediol dibenzoate (0.0067mol), and 0.3g of polyvinylpyrrolidone were charged, and the temperature was raised to 100 ℃ with stirring. After reacting for 1 hour at constant temperature, adding 0.48mol (38ml) of epichlorohydrin, reacting for 20 minutes, then 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 carrier Z5.
The composition of Z5 of the olefin polymerization catalyst carrier is determined by nuclear magnetism, element analysis and a chromatographic method as follows:
the olefin polymerization catalyst carrier Z5 had an average particle diameter (D50) of 41 μm and a particle size distribution ((D90-D10)/D50) of 0.7. The particle observed by an optical microscope has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Example 5
This example illustrates the preparation of a polyolefin 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 Z3 obtained in preparation example 3 was added thereto and stirred at-20 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 1.5mL of diisobutyl phthalate was added during the temperature raising, and the temperature was maintained at 110 ℃ for 30min, after which 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 C2.
(3) Propylene polymerization
In a 5L stainless steel autoclave, purging was conducted with a nitrogen stream, and then 1mmol of a hexane solution of triethylaluminum (concentration of triethylaluminum is 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, and 10mg of the olefin polymerization catalyst C2 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. The melt flow index of the polypropylene powder is 8.6g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Example 6
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene polymerization was conducted in the same manner as in example 5 except that 1.5L (standard volume) of hydrogen was substituted for 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The melt flow index of the polypropylene powder is 43.7g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Example 7
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene was polymerized by following the procedure of example 5, except that the olefin polymerization catalyst carrier Z3 was replaced with the olefin polymerization catalyst carrier Z4 obtained in preparation example 4, to obtain a polypropylene powder. The melt flow index of the polypropylene powder is 8.7g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
Example 8
This example serves to illustrate the preparation of the polyolefins provided by the present invention.
Propylene polymerization was conducted in the same manner as in example 7 except that 1.5L (standard volume) of hydrogen was substituted for 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The melt flow index of the polypropylene powder is 45.5g/10min, and in addition, the polypropylene powder has good particle shape and basically has no profile.
TABLE 1
From the above results, it can be seen that the olefin polymerization catalyst carrier prepared by the method of the present invention has good particle morphology, smooth surface and substantially no irregular particles, and when the catalyst prepared by the obtained carrier is used for olefin (especially propylene) polymerization, the morphology of the catalyst is good, and the morphology of the polymer is good.
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.
Claims (10)
1. A spherical support for an olefin polymerization catalyst, comprising a composition represented by formula (I):
in the formula (I), R1Is C1-C14An alkyl group; r2And R3Identical or different from hydrogen and C1-C5Alkyl or C1-C5A halogenated alkane; x is halogen; m is 0.1 to 1.9, n is 0.1 to 1.9, and m + n is 2;
B1represents a compound B selected from the group consisting of 1, 3-diether compounds, phthalate ester compounds and glycol ester compounds, 0<q≤0.5。
2. The olefin polymerization catalyst support according to claim 1, wherein R is1Is C1-C6An alkyl group; r2And R3Identical or different from hydrogen and C1-C5Alkyl or C1-C5A halogenated alkane; x is chlorine or bromine.
3. The olefin polymerization catalyst support according to claim 1 or 2, wherein the 1, 3-diether compound has a structure represented by formula (II):
in the formula (II), R21And R22Each independently selected from hydrogen and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl and C7-C20One of the alkylaryl groups of (1), R23And R24Each independently selected from C1-C10Alkyl groups of (a);
the structure of the phthalate ester compound is shown as the formula (III):
in the formula (III), R10And R11Identical or different, independently selected from C1-C10Alkyl and C3-C20A cycloalkyl group;
the structure of the diol ester compound is shown as the formula (IV):
r 'in the formula (IV)'1-R'6Same or different, independently selected from hydrogen, C1-C10Alkyl radical, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl or arylalkyl, but R'1，R'2，R'5，R'6Not hydrogen at the same time; r'1-R'6Wherein two or more groups may be bonded to each other to form one or more fused ring structures;
R'7and R'8Identical or different, independently selected from C1-C10Alkyl of (C)3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20An aryl or alkaryl group or an aryl group wherein the hydrogens on the phenyl ring may optionally be replaced by halogen atoms.
4. The olefin polymerization catalyst carrier according to any one of claims 1 to 3, wherein the olefin polymerization catalyst carrier synthesis raw material comprises a compound B, a magnesium halide having a general formula of MgXY, a compound having a general formula of ROH, and an oxirane compound;
in the general formula MgXY, X is halogen and Y is halogen or C1-C14An alkyl group;
preferably, in the formula MgXY, X is halogen and Y is selected from halogen or C1-C6Alkyl, more preferably, in the formula MgXY, X is chlorine or bromine and Y is chlorine, bromine or C1-C5An alkyl group; more preferably, the magnesium halide of formula MgXY is magnesium chloride;
in the formula ROH, R is C1-C14Alkyl or C3-C14Cycloalkyl, preferably C1-C8Alkyl or C3-C8Cycloalkyl, preferably in the formula ROH, R is C1-C8Alkyl groups of (a); more preferably, the compound of formula ROH is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol;
the structure of the ethylene oxide compound is shown as the formula (V):
in the formula (V), R5And R6Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group; preferably, in the oxirane compound, R5And R6Each independently is hydrogen, C1-C3An alkyl or haloalkyl group; more preferably, the oxirane is selected from ethylene oxide, epoxyethaneOne or more of propane, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene and butylene oxide bromide.
5. The olefin polymerization catalyst carrier of claim 4, wherein based on 1mol of magnesium halide with the general formula of MgXY, the amount of the compound B is 0.0001-0.1 mol, the amount of the compound with the general formula of ROH is 4-30mol, and the amount of the oxirane compound with the structure shown in the formula (V) is 1-10 mol; preferably, based on 1mol of magnesium halide with the general formula of MgXY, the dosage of the compound with the general formula of ROH is 6-20mol, and the dosage of the ethylene oxide compound with the structure shown in the formula (V) is 2-6 mol.
6. The olefin polymerization catalyst support according to any of claims 1 to 5, wherein the olefin polymerization catalyst support has an average particle diameter of 10 to 100 μm and a particle size distribution of less than 1.2; preferably, the olefin polymerization catalyst support has an average particle diameter of 40 to 60 μm and a particle size distribution of 0.6 to 0.8.
7. A method for preparing an olefin polymerization catalyst support, the method comprising the steps of:
(1) mixing and heating a compound B, magnesium halide with a general formula of MgXY, a compound with a general formula of ROH and an optional inert liquid medium to obtain a liquid mixture;
(2) emulsifying the liquid mixture obtained in the step (1), and contacting and reacting the emulsified product with an ethylene oxide compound;
wherein, in the step (1), the compound B is selected from 1, 3-diether compounds, phthalate ester compounds and glycol ester compounds;
in the general formula MgXY, X is halogen and Y is halogen or C1-C14An alkyl group;
in the formula ROH, R is C1-C14Alkyl or C3-C14Cycloalkyl, preferably C1-C8Alkyl or C3-C8A cycloalkyl group;
preferably, the structure of the ethylene oxide compound is shown as the formula (V):
in the formula (V), R5And R6Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group.
8. A process according to claim 7, wherein in the formula MgXY, X is chlorine or bromine and Y is chlorine, bromine or C1-C5An alkyl group; preferably, the magnesium halide of formula MgXY is magnesium chloride; and/or
In the formula ROH, R is C1-C8An alkyl group; more preferably, the compound of formula ROH is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol; and/or
In the oxirane compound, R5And R6Each independently is hydrogen, C1-C3An alkyl or haloalkyl group; preferably, the ethylene oxide compound is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide,
the structure of the 1, 3-diether compound is shown as the formula (II):
in the formula (II), R21And R22Each independently selected from hydrogen and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl and C7-C20One of the alkylaryl groups of (1), R23And R24Each independently selected from C1-C10Alkyl groups of (a);
the structure of the phthalate ester compound is shown as the formula (III):
in the formula (III), R10And R11Same or different and independently selected from C1-C10Alkyl and C3-C20A cycloalkyl group;
the structure of the diol ester compound is shown as the formula (IV):
r 'in the formula (IV)'1-R'6Identical or different, independently selected from hydrogen and C1-C10Alkyl radical, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl or arylalkyl, but R'1，R'2，R'5，R'6Not hydrogen at the same time; r'1-R'6Wherein two or more groups may be bonded to each other to form one or more fused ring structures;
R'7and R'8Identical or different, independently selected from C1-C10Alkyl of (C)3-C20Cycloalkyl, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20An aromatic hydrocarbon group in which a hydrogen on a benzene ring in the aryl or alkaryl group or the aromatic hydrocarbon group may be optionally substituted with a halogen atom.
9. The method of claim 7 or 8, wherein the compound B is used in an amount of 0.0001 to 0.1mol, the compound of formula ROH is used in an amount of 4 to 30mol, and the oxirane compound is used in an amount of 1 to 10mol, based on 1mol of the magnesium halide of formula MgXY; preferably, the compound with the general formula of ROH is used in an amount of 6-20mol and the oxirane compound is used in an amount of 2-6mol based on 1mol of magnesium halide with the general formula of MgXY; and/or
In the step (1), the heating temperature is 80-120 ℃ and the time is 0.5-5 hours; preferably, the heating temperature is 80-100 ℃ and the time is 0.5-3 hours; in the step (2), the contact reaction conditions comprise that the temperature is 80-120 ℃ and the time is 20-60 minutes; preferably, the conditions of the contact reaction include a temperature of 80-100 ℃ and a time of 20-50 minutes; and/or
Based on 1mol of magnesium halide with the general formula of MgXY, the dosage of the optional inert liquid medium is 0.8-10L; the inert liquid medium is silicone oil and/or an inert liquid hydrocarbon solvent; preferably, the inert liquid medium is one or more 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.
10. Use of the spherical olefin polymerization catalyst support according to any one of claims 1 to 6 and/or the olefin polymerization catalyst support prepared by the preparation method according to any one of claims 7 to 9 for the preparation of an olefin polymerization catalyst.
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| CN104558283A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Solid composition as well as preparation method and application thereof |
| CN107522800A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522799A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
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| CN104558283A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Solid composition as well as preparation method and application thereof |
| CN107522800A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107522799A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
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