CN116023543B - Catalyst component for olefin polymerization, catalyst for olefin polymerization and application thereof - Google Patents
Catalyst component for olefin polymerization, catalyst for olefin polymerization and application thereof Download PDFInfo
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- CN116023543B CN116023543B CN202111255719.6A CN202111255719A CN116023543B CN 116023543 B CN116023543 B CN 116023543B CN 202111255719 A CN202111255719 A CN 202111255719A CN 116023543 B CN116023543 B CN 116023543B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 48
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 239000011777 magnesium Substances 0.000 claims abstract description 38
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- -1 magnesium halide Chemical class 0.000 claims description 104
- 239000002245 particle Substances 0.000 claims description 63
- 125000000217 alkyl group Chemical group 0.000 claims description 53
- 125000005843 halogen group Chemical group 0.000 claims description 37
- 238000009826 distribution Methods 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 125000001188 haloalkyl group Chemical group 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000000460 chlorine Chemical group 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- ZPYVAEKBXKGWCX-UHFFFAOYSA-N diethyl 2-cyano-2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C#N)(C(C)C)C(=O)OCC ZPYVAEKBXKGWCX-UHFFFAOYSA-N 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910017718 MgXY Inorganic materials 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000003106 haloaryl group Chemical group 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 150000003944 halohydrins Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052740 iodine Chemical group 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011630 iodine Chemical group 0.000 claims description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- XUOLMKJNCVFXJO-UHFFFAOYSA-M C(C)(C)OC[Mg]Cl Chemical compound C(C)(C)OC[Mg]Cl XUOLMKJNCVFXJO-UHFFFAOYSA-M 0.000 claims description 2
- 125000005914 C6-C14 aryloxy group Chemical group 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 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
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000037048 polymerization activity Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 40
- 239000004743 Polypropylene Substances 0.000 description 30
- 229920001155 polypropylene Polymers 0.000 description 30
- 239000000843 powder Substances 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 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 11
- 230000000694 effects Effects 0.000 description 11
- 239000002685 polymerization catalyst Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 238000005507 spraying Methods 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- OAFMYIADTCIEFV-UHFFFAOYSA-N hexane;triethylalumane Chemical compound CCCCCC.CC[Al](CC)CC OAFMYIADTCIEFV-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- APYCNQFSOVJLPN-UHFFFAOYSA-N 1,4-dichlorobutan-1-ol Chemical compound OC(Cl)CCCCl APYCNQFSOVJLPN-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000001681 protective effect Effects 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
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 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
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- QXBDFCZHAAOUBY-UHFFFAOYSA-N 1,2-dichloroethanol Chemical compound OC(Cl)CCl QXBDFCZHAAOUBY-UHFFFAOYSA-N 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
- 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- NYEWDMNOXFGGDX-UHFFFAOYSA-N 2-chlorocyclohexan-1-ol Chemical compound OC1CCCCC1Cl NYEWDMNOXFGGDX-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- QSECPQCFCWVBKM-UHFFFAOYSA-N 2-iodoethanol Chemical compound OCCI QSECPQCFCWVBKM-UHFFFAOYSA-N 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
- WAHDOBRAAIQNTA-UHFFFAOYSA-N 3,5-dimethoxypentylcyclohexane Chemical compound COCCC(OC)CCC1CCCCC1 WAHDOBRAAIQNTA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-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
- DCBJCKDOZLTTDW-UHFFFAOYSA-N 5-chloropentan-1-ol Chemical compound OCCCCCCl DCBJCKDOZLTTDW-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MBMKFKOVXPKXCV-UHFFFAOYSA-N CCO[Ti]OCC Chemical compound CCO[Ti]OCC MBMKFKOVXPKXCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005662 Paraffin oil 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
- 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
- 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
- JMSRBKPMLUGHCR-UHFFFAOYSA-N bromohydrin Chemical compound BrC[C]1CO1 JMSRBKPMLUGHCR-UHFFFAOYSA-N 0.000 description 1
- MTKOCRSQUPLVTD-UHFFFAOYSA-N butan-1-olate;titanium(2+) Chemical compound CCCCO[Ti]OCCCC MTKOCRSQUPLVTD-UHFFFAOYSA-N 0.000 description 1
- NUFATYMMMZQQCQ-UHFFFAOYSA-N butan-1-olate;titanium(3+) Chemical compound [Ti+3].CCCC[O-].CCCC[O-].CCCC[O-] NUFATYMMMZQQCQ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NNRZFZBJEDXBPK-UHFFFAOYSA-N ethanolate;titanium(3+) Chemical compound [Ti+3].CC[O-].CC[O-].CC[O-] NNRZFZBJEDXBPK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalyst component for olefin polymerization, a catalyst for olefin polymerization and application thereof, wherein the catalyst component comprises the following components: titanium element, magnesium element, halogen, a compound shown in a general formula (I) and a 1, 3-diether compound, wherein the magnesium element is from a magnesium-containing compound with a structure shown in a formula (II). When the catalyst provided by the invention is used for olefin polymerization, the polymerization activity is good, no foreign materials appear basically, the hydrogen regulation sensitivity is obviously higher than that of the prior art, and the catalyst has great industrial application prospect.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to a catalyst component for olefin polymerization, a catalyst for olefin polymerization and application thereof.
Background
Catalysts for the polymerization of olefins are mostly prepared by supporting titanium halides on active anhydrous magnesium chloride. One method used to prepare active magnesium chloride is to react anhydrous MgCl 2 with an alcohol to form an adduct and then load the titanium halide with this adduct to prepare the olefin polymerization catalyst solid component.
WO98/44009 discloses a MgCl 2.mROH.nH2 O adduct in which R is C 1-C10 alkyl, m is 2.ltoreq.4.2 and n is 0.ltoreq.0.7, characterised by an X-ray diffraction spectrum which is characterized by: within the range of 2θ diffraction angles of 5 ° -15 °, three major diffraction peaks are located at 2θ=8.8±0.2°, 9.4±0.2° and 9.8±0.2° respectively, with the strongest peak being located at 2θ=8.8±0.2°, and the other two diffraction peaks having intensities at least 0.2 times the intensity of the strongest diffraction peak. In addition to the above X-ray diffraction patterns, the above adducts can be identified by Differential Scanning Calorimetry (DSC) patterns in which no melting peak occurs below 90℃or, if a peak occurs below said temperature, the melting enthalpy associated with said peak is also less than 30% of the total melting enthalpy.
WO 2003/082330 discloses MgCl 2. MEtOH adducts where 2.5.ltoreq.m.ltoreq.3.2, optionally containing 1% by weight of water based on the total weight of the adduct. The X-ray diffraction spectrum is characterized in that: in the range of 5 ° -15 ° of 2-theta diffraction angle, there are three main diffraction lines, the corresponding diffraction angles 2-theta values are 8.8±0.2°, 9.4±0.2° and 9.8±0.2°, the strongest diffraction line is one of 8.8±0.2°, and the other two diffraction lines have an intensity at least 0.2 times the intensity of the strongest diffraction line. The adducts are characterized by a DSC curve having a peak melting temperature of greater than 109 ℃ and an associated melting enthalpy of 103 joules/gram or less.
WO2004/026920 discloses a MgCl 2.mEtOH.nH2 O adduct of the formula 3.4.ltoreq.m.ltoreq.4.4 and 0.ltoreq.n.ltoreq.0.7, the X-ray diffraction spectrum of which is characterised in that: at least two diffraction lines exist at diffraction angles of 2θ=9.3±0.2° and 9.9±0.2° within a range of 2θ diffraction angles of 5 ° to 10 °, the most intense diffraction line of which is at 9.3±0.2°, and the other diffraction line has an intensity lower than 0.4 times the intensity of the most intense diffraction line. The DSC curve of the adduct is characterized by only one melting peak in the range of 90-105 ℃.
CN101190953 discloses a magnesium-containing complex with the general formula ClMg (OR) n (ROH), wherein R is selected from alkyl of C 1-C5, and n is 0.1-1.0. The complex can be used for preparing a solid catalyst for propylene polymerization, and has higher activity and stereoregularity. In the examples it is indicated that the melting point of the adduct is around 142℃as measured by DSC.
Different catalysts may be developed based on different supports, e.g., catalysts suitable for different polyolefin processes may be developed based on supports of different particle sizes. Generally, smaller particle size catalysts produce less fines and are more conducive to polyolefin production plant operation. In pursuit of faster processing rates, polyolefin processors tend to be willing to employ higher melt index polyolefin feedstocks. In addition, in order to pursue better product properties, it is sometimes necessary to use polypropylene materials of higher isotactic index. Therefore, it is important to develop a new olefin polymerization catalyst with better hydrogen sensitivity and smaller particle size.
Disclosure of Invention
In view of the problems of the prior art that the particle size of the olefin polymerization catalyst is too large and the hydrogen regulation sensitivity is low when the catalyst prepared from the carrier is used for olefin polymerization, one of the purposes of the invention is to provide a catalyst component for olefin polymerization, wherein an alcohol compound and a halohydrin compound are matched with components such as magnesium halide and ethylene oxide compounds, and a specific spray drying mode is matched, so that a catalyst carrier with good particle shape is obtained, and when the catalyst prepared from the carrier is used for olefin polymerization, the hydrogen regulation sensitivity is high and the isotactic index is high. The wider molecular weight distribution width can increase the rigidity-toughness balance of the olefin polymer, and is beneficial to improving the performance of the resin.
It is a second object of the present invention to provide the use of a catalyst component corresponding to one of the objects in the preparation of a catalyst for the polymerization of olefins.
It is a further object of the present invention to provide a catalyst for olefin polymerization corresponding to the above object.
It is a fourth object of the present invention to provide a process for polymerizing olefins corresponding to the above object.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
A catalyst component for the polymerization of olefins comprising: titanium element, magnesium element, halogen, compound shown in general formula (I) and 1, 3-diether compound,
In the formula (I), R '"1 and R'" 2 are the same or different and are each independently hydrogen or C 1～C14 linear or branched alkyl, C 3-C10 cycloalkyl, C 6-C10 aryl, C 7-C10 alkylaryl or arylalkyl; the R '"1 and R'" 2 groups can be bonded to each other to form one or more fused ring structures; r '"3 and R'" 4 are identical or different and are each independently C 1～C10 straight-chain or branched alkyl, C 3-C10 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl or C 7-C20 aryl hydrocarbon radicals; in R' "1～R"'4, the hydrogen on the benzene ring in the aryl or alkylaryl or aryl hydrocarbon group may be optionally substituted with other atoms, preferably selected from one or more of halogen, O, S and N; and
The magnesium element is from a magnesium-containing compound with a structure shown in a formula (II);
wherein, in the formula (II),
R 1 is selected from the group consisting of C 1-C10 alkyl, preferably from the group consisting of C 1-C8 alkyl, more preferably from the group consisting of C 1-C6 alkyl;
R 2 and R 3 are identical or different and are each independently selected from the group consisting of alkyl of H, C 1-C10 and haloalkyl of C 1-C10 substituted with 1 to 10 halogen atoms, preferably from H, C 1-C5 and haloalkyl of C 1-C5 substituted with 1 to 5 halogen atoms;
R 4 is selected from the group consisting of a haloalkyl group of C 1-C10 substituted with at least one halogen atom and a haloaryl group of C 6-C20 substituted with at least one halogen atom, preferably from the group consisting of a haloalkyl group of C 1-C10 substituted with at least two halogen atoms and a haloaryl group of C 6-C20 substituted with at least two halogen atoms;
R 5 is selected from the group consisting of C 1-C5 alkyl, preferably from the group consisting of C 1-C2 alkyl;
x is selected from fluorine, chlorine, bromine and iodine, preferably from chlorine and bromine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0< q <0.2;0< a <0.1.
In the present invention, in the formula (2)Part of the representation (OC 2H2XR2R3)n).
In the present invention, R 1 is selected from the group consisting of C 1-10 alkyl, and R 1 is a linear, branched or cyclic alkyl group including, but not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, and the like.
The alkyl substituent for R 1 herein has a similar definition as above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In the present invention, R 2 and R 3 are each independently selected from the group consisting of alkyl of H, C 1-10 and haloalkyl of C 1-10 substituted with 1 to 10 halogen atoms.
When the R 2 and R 3 groups are selected from the group consisting of C 1-10 alkyl groups and C 1-10 haloalkyl groups substituted with 1-10 halogen atoms, the alkyl groups are straight or branched chain groups, and the alkyl groups of the C 1-10 groups include, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, and the like. The haloalkyl is a straight-chain or branched-chain group, and the haloalkyl of C 1-10 substituted by 1-10 halogen atoms refers to a group formed by substituting 1-10 hydrogen atoms in an alkyl of C 1-10 with halogen atoms, wherein a plurality of hydrogen atoms on the same carbon atom are substituted by halogen atoms, or hydrogen atoms on different carbon atoms are substituted; when a plurality of halogen atoms are substituted, the halogen atoms may be the same or different, and the halogen atoms are fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. Such as including but not limited to -CF3、-CH2CF3、-CH2CF2H、-CF2CF3、-CF2CH2CF2H、-CH2CF2CF2H、-CH2CH2CH2Cl、-CH2CH2CH2Br, etc.
Herein, the alkyl substituent and the haloalkyl substituent of R 2 and R 3 have similar definitions as described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In the present invention, R 4 is selected from the group consisting of a haloalkyl group of C 1-10 substituted with at least one halogen atom and a haloaryl group of C 6-20 substituted with at least one halogen atom. The halogenated alkyl group of C 1-10 substituted by at least one halogen atom and the halogenated aryl group of C 6-20 substituted by at least one halogen atom refer to a group formed by substitution of at least one hydrogen atom in the alkyl group of C 1-10 and the aryl group of C 6-20 by a halogen atom, wherein the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Wherein the haloalkyl of C 1-10 may be a linear, branched, or cyclic group, including, for example, but not limited to CF3、-CH2CF3、-CH2CF2H、-CF2CF3、-CF2CH2CF2H、-CH2CF2CF2H、-CH2CH2CH2Cl、-CH2CH2CH2Br, and the like. The halogenated aryl of C 6-20 refers to halogenated aryl containing 6-20 carbon atoms.
Herein, the substituent groups for R 4 have similar definitions as above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In the present invention, R 5 is selected from the group consisting of C 1-5 alkyl, and the alkyl of C 1-5 refers to an alkyl group having 1 to 5 carbon atoms, and includes, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, and the like.
Herein, the substituent groups for R 5 have similar definitions as above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
For better performing catalysts, preferably, R 1 is selected from the group consisting of alkyl groups of C 1-8; more preferably, R 1 is selected from alkyl of C 1-6.
In order to obtain a better performing catalyst, preferably, R 2 and R 3 are each independently selected from the group consisting of alkyl of H, C 1-5 and haloalkyl of C 1-5 substituted with 1-10 halogen atoms.
In order to obtain a catalyst with better performance, preferably, R 4 is selected from the group consisting of a haloalkyl group of C 1-10 substituted with at least two halogen atoms and a haloaryl group of C 6-20 substituted with at least two halogen atoms, and the halogen atoms are preferably selected from at least one of chlorine atoms, bromine atoms and iodine atoms.
In the present invention, the substitution of at least two halogen atoms means that at least two hydrogen atoms in the alkyl group of C 1-10 and the aromatic group of C 6-20 are substituted with halogen atoms, and the hydrogen atoms may be hydrogen atoms on one carbon or hydrogen atoms on different carbons, and the halogen atoms may be the same or different.
For better performing catalysts, preferably, R 5 is selected from the group consisting of alkyl groups of C 1-2.
In order to obtain a catalyst with better performance, preferably X is selected from chlorine and bromine.
In some preferred embodiments of the invention, in formula (I), R '"1 and R'" 2 are the same or different and are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, benzyl, p-toluylmethyl or phenethyl, preferably isopropyl; r '"3 and R'" 4 are identical or different and are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, p-tolyl, o-tolyl, m-tolyl or benzyl, preferably ethyl.
In some preferred embodiments of the present invention, the compound represented by the general formula (I) is selected from one or more of diethyl 2, 3-diisopropyl-2-cyano succinate, diethyl 3-methyl-2-isopropyl-2-cyano succinate, diethyl 3-ethyl-2-isopropyl-2-cyano succinate, diethyl 3-propyl-2-isopropyl-2-cyano succinate, diethyl 3-butyl-2-isopropyl-2-cyano succinate and diethyl 3-phenyl-2-isopropyl-2-cyano succinate.
In some preferred embodiments of the present invention, the compound of formula (I) is preferably a compound of formula (IV).
In some preferred embodiments of the present invention, the molar ratio of the compound represented by the general formula (I) to the 1, 3-diether compound is 1 (0.2 to 8), preferably 1 (0.25 to 5).
In some preferred embodiments of the invention, the magnesium-containing compound has a spherical or spheroid-like structure; preferably, the magnesium-containing compound has an average particle diameter of 2 to 100 μm and a particle size distribution of less than 2; more preferably, the magnesium-containing compound has an average particle diameter of 2 to 19 μm and a particle size distribution of 0.6 to 1.6; further preferably, the magnesium-containing compound has an average particle diameter of 2 to 10 μm and a particle size distribution of 0.6 to 1.
In the present invention, the average particle diameter refers to D50.
In the present invention, the size of the particle size distribution is obtained according to (D90-D10)/D50.
In the present invention, the average particle diameter and particle size distribution of the catalyst support are measured using a laser particle Sizer such as a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd).
In some preferred embodiments of the present invention, the method for preparing a magnesium-containing compound includes:
(1) Sequentially carrying out first contact and emulsification on a component A to obtain a first product, wherein the component A contains magnesium halide with a general formula MgXY and a first alcohol compound with a general formula R 1 OH;
(2) Carrying out second contact on the first product and a component B to obtain a second product, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (III);
(3) Carrying out third contact on the second product and a component C to obtain a third product, wherein the component C contains halogenated alcohol with a general formula of R 4 OH and a second glycol compound with a general formula of R 5 OH;
(4) Subjecting the third product to spray drying;
Wherein R 1、R2、R3、R4 and R 5 have the same definition as in the preceding claims;
In formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C 1-C6 alkyl, C 1-C6 alkoxy, C 6-C14 aryl and C 6-C14 aryloxy, preferably X is selected from chlorine and bromine, Y is selected from chlorine, bromine, C 1-C5 alkyl, C 1-C5 alkoxy, C 6-C10 aryl and C 6-C10 aryloxy; preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymethyl magnesium chloride and n-butoxymagnesium chloride;
The component A, the component B and the component C are used in such an amount that the resulting spherical support has a structure represented by formula (II).
In the method for preparing a magnesium-containing compound of the present invention, the definition of the substituents R 1、R2、R3、R4 and R 5 are the same as those of the first aspect of the present invention, and the present invention will not be described in detail herein.
In the present invention, in formula MgXY, when Y is selected from the group consisting of C 1-C6 alkyl, C 1-C6 alkoxy, said alkyl and said alkoxy are straight or branched alkyl and alkoxy groups, said C 1-C6 alkyl refers to an alkyl group having 1 to 6 carbon atoms, including, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and the like; the alkoxy group of C 1-C6 refers to an alkoxy group having 1 to 6 carbon atoms, and includes, for example, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and the like.
The aryl group of C 6-C14 refers to aryl groups having 6 to 14 carbon atoms and includes, for example, but is not limited to, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl, and the like.
The aryloxy group of C 6-C14 refers to an aryloxy group having 6 to 14 carbon atoms, including, for example, but not limited to, phenoxy, naphthoxy, o-methylphenoxy, o-ethylphenoxy, m-methylphenoxy, and the like.
Herein, in formula MgXY, substituents such as alkyl, alkoxy, aryl and aryloxy for Y have similar definitions as described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
According to another preferred embodiment of the invention, in the formula R 1 OH, R 1 is selected from alkyl groups of C 1-8.
In order to obtain a catalyst carrier with better performance, more preferably, the first alcohol compound is at least one selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
According to yet another preferred embodiment of the present invention, in formula (2), R 2 and R 3 are each independently selected from the group consisting of alkyl of H, C 1-5 and haloalkyl of C 1-5 substituted with 1 to 10 halogen atoms.
In order to obtain a catalyst support having a smaller particle diameter and better performance, more preferably, the oxirane compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide, propylene oxide and butylene oxide.
According to the invention, the halohydrin may be a monohalohydrin or a polyhalogenated alcohol, preferably a chlorohydrin, a bromohydrin or an iodinated alcohol, for example 2, 2-trichloroethanol, 2-dichloroethanol, 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1-hexanol, 3-bromo-1-propanol, 5-chloro-1-pentanol, 4-chloro-1-butanol, 2-chlorocyclohexanol, 1, 2-dichloroethanol, 1, 3-dichloropropanol, 1, 4-dichlorobutanol or 2-iodoethanol, etc.
However, in order to be able to obtain a catalyst support with better performance, according to a further preferred embodiment of the present invention, in the formula R 4 OH, R 4 is selected from the group consisting of a haloalkyl group of C 1-10 substituted with at least two halogen atoms and a haloaryl group of C 6-20 substituted with at least two halogen atoms, and the halogen atoms are selected from at least one of chlorine atoms, bromine atoms and iodine atoms.
Preferably, the halogenated alcohol is at least one selected from 2, 2-trichloroethanol, 2-dichloroethanol, 1, 3-dichloropropanol and 1, 4-dichlorobutanol.
According to the invention, the second glycol compound is at least one selected from alcohol compounds of C 1-5, such as ethanol, methanol, n-propanol, isopropanol, n-butanol or isobutanol. However, in order to be able to obtain a catalyst support with better performance, according to a further preferred embodiment of the invention, in the formula R 5 OH, R 5 is selected from the group consisting of C 1-2 alkyl groups, i.e.the second glycol compound is methanol and/or ethanol.
According to the present invention, the inventors have found that when the amounts of the halohydrin compound and the alcohol compound are excessively large, the resulting catalyst carrier is sticky and lump, and thus, it is impossible to carry out the subsequent operations.
Preferably, the first alcohol compound is used in an amount of 1 to 30mol and the ethylene oxide compound is used in an amount of 1 to 10mol, relative to 1mol of the magnesium halide.
More preferably, the amount of the first alcohol compound is 6 to 22 moles, the amount of the ethylene oxide compound is 2 to 6 moles, the amount of the halohydrin is 1 to 5 moles, and the amount of the second alcohol compound is 8 to 80 moles, more preferably 31 to 50 moles, relative to 1 mole of the magnesium halide.
In the present invention, it should be noted that the trace amount of water carried in each of the above reactants may also participate in the reaction for forming the spherical support, and thus, the spherical support may be prepared to contain trace amounts of water carried from the reaction raw materials and the reaction medium, and those skilled in the art should not understand the limitation of the present invention.
In some preferred embodiments of the present invention, in step (1), the first contacting is performed under stirring conditions, the conditions of the first contacting comprising: the temperature is 80-120 ℃ and the time is 0.5-5h; preferably, in step (1), the conditions of the first contact include: the temperature is 80-100deg.C, and the time is 0.5-3h.
In the step (1), the specific operation method of the emulsification is not particularly limited, and may be carried out by methods known to those skilled in the art. For example, emulsification is performed using low-speed shearing or high-speed shearing. Preferably, when low shear is used, the agitation rate of the low shear is 400-800rpm. Such high speed shearing processes are well known to those skilled in the art, for example, using the high speed agitation speeds disclosed in CN1330086 a. In addition, the emulsification operation may be carried out by referring to the method disclosed in patent application publication such as CN1580136a, in which a solution containing a liquid magnesium halide compound is subjected to rotary dispersion in a hypergravity bed (the rotation speed is 100 to 3000 rpm); the solution containing the liquid magnesium halide adduct is then fed out in an emulsifying machine at a speed of 1500-8000rpm as disclosed in CN1463990 a; the solution containing the liquid magnesium halide adducts is emulsified by spraying as disclosed in US6020279 a.
In some preferred embodiments of the present invention, in step (2), the conditions of the second contact include: the temperature is 50-120 ℃ and the time is 20-60min; preferably, in step (2), the conditions of the second contact include: the temperature is 80-100deg.C, and the time is 20-50min.
In some preferred embodiments of the present invention, in step (3), the halogenated alcohol is used in an amount of 0.05 to 6.5mol and the second glycol compound is used in an amount of 5 to 100mol with respect to 1mol of the magnesium halide.
According to a preferred embodiment of the present invention, step (3) further comprises, after washing the second product with an inert solvent, carrying out the third contact with each of the components C, preferably at least one inert solvent selected from pentane, hexane, heptane, petroleum ether and petrol.
The specific conditions of the third contact in step (3) are not particularly limited in the present invention as long as the component C and the second product can be sufficiently contacted to form a fluid, but in order to enable a catalyst support having better performance, preferably, in step (3), the conditions of the third contact include: the process is carried out under the condition of stirring, the temperature is 0-120 ℃, and the time is 0.5-6h.
The specific mode of the third contact in the step (3) is not particularly limited, and the halohydrin and the second glycol compound may be mixed and simultaneously contacted with the second component, or the halohydrin and the second glycol compound may be sequentially contacted with the second component, respectively.
In the present invention, the spray-drying conditions may employ existing conditions capable of forming a catalyst support for olefin polymerization, but in order to obtain a catalyst support having better performance, according to a preferred embodiment of the present invention, the spray-drying is performed in a spray machine having an atomizing nozzle containing a material conduit and a nozzle head, the third product is introduced into the nozzle head through the material conduit and is injected into a column of the spray machine containing an inert medium through the nozzle head to be solidified, preferably, the temperature of the third product in the material conduit is between 0 ℃ and 80 ℃ and the temperature of the third product in the nozzle head is 80-180 ℃; more preferably the temperature of the third product in the nozzle head is 120-180 ℃.
In some preferred embodiments of the present invention, in step (4), the spray drying conditions include: the temperature is 60-200deg.C, preferably 90-150deg.C.
In the present invention, the temperature of the spray drying refers to the temperature of the inert medium in the spraying machine.
In the present invention, the inert medium may include a protective gas medium and/or an inert liquid medium, and the type of the protective gas medium is not particularly limited, and for example, nitrogen gas may be an inert gas medium such as helium gas, or other suitable gas such as carbon dioxide gas, etc.; the inert liquid medium is a variety of liquid mediums commonly used in the art that do not chemically react with the reactants and reaction products, preferably the inert liquid medium is silicone oil and/or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium is 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, and still more preferably is white oil.
In the present invention, the amount of the inert liquid medium in the spraying machine may be selected according to the amount of magnesium halide of the general formula MgXY, preferably 0.8 to 10L, more preferably 2 to 8L.
The method for producing the magnesium-containing compound of the present invention further includes post-treatment means, such as solid-liquid separation, washing, drying, etc., which are conventional in the art, and the present invention is not particularly limited thereto. The solid-liquid separation may be performed by any of various conventional methods capable of separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation method is a pressure filtration method. The conditions for press filtration are not particularly limited in the present invention, so long as the separation of the solid phase and the liquid phase is achieved as sufficiently as possible. The washing may be performed by methods known to those skilled in the art, and for example, the obtained solid phase product may be washed with an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether and gasoline. The specific conditions for the drying are not particularly limited in the present invention, and for example, the temperature of the drying may be 20 to 70 ℃, the time of the drying may be 0.5 to 10 hours, and the drying may be performed under normal pressure or reduced pressure.
According to the present invention, the titanium element is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tri-n-butoxide, titanium di-n-butoxide, titanium tri-chloride, titanium triethoxide, titanium di-ethoxide, titanium tri-monoethoxide and titanium trichloride.
In some preferred embodiments of the present invention, the weight ratio of the titanium element, the magnesium element, and the compound represented by the general formula (I) to the total weight of the 1, 3-diether compound is 1:5-15:2-15, preferably 1:6-13:3-12.
According to the invention, the compound shown in the general formula (I) and the 1, 3-diether compound are both internal electron donors, so that the weight ratio of the titanium element to the magnesium element to the internal electron donors is 1:5-15:2-15, preferably 1:6-13:3-12.
In some preferred embodiments of the present invention, the diether compound has a structure represented by formula (IV);
wherein, in the formula (IV),
R '1、R'2、R'3、R'4、R'5 and R' 6 are the same or different and are each independently selected from hydrogen, halogen, C 1-C20 straight or branched alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 aralkyl, or C 7-C20 alkaryl, wherein two or more of R '1、R'2、R'3、R'4、R'5 and R' 6 may optionally be bonded to form a ring;
R '5 and R' 6 are identical or different and are each independently selected from C 1-C20 linear or branched alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 aralkyl or C 7-C20 alkylaryl, preferably from C 1-C10 linear or branched alkyl.
In some preferred embodiments of the present invention, the diether compound is selected from 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, 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-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-isopentyl-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-sec-butyl-1, 3-dimethoxypropane, at least one of 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.
In some preferred embodiments of the present invention, the diether compound is 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.
In order to achieve the second purpose, the technical scheme adopted by the invention is as follows:
use of the catalyst component according to any of the above embodiments for the preparation of a catalyst for the polymerization of olefins.
The preparation method of the catalyst is not particularly limited, and may be prepared by methods of preparing an olefin polymerization catalyst existing in the art, and the present invention is exemplified in the examples hereinafter to be used as a specific procedure, and the person skilled in the art should not be construed as limiting the present invention.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
a catalyst for olefin polymerization, comprising;
(1) A catalyst component according to any one of the above embodiments;
(2) An alkyl aluminum compound; and
(3) Optionally an external electron donor compound.
In some preferred embodiments of the present invention, the alkyl aluminum compound is selected from the group consisting of alkyl aluminum compounds represented by formula AlR 'mX'3-m, wherein R' is selected from any one of hydrogen, C 1-C20 alkyl, and C 6-C20 aryl; x' is halogen, and m is an integer of 1-3.
In some preferred embodiments of the present invention, the external electron donor compound is an organosilicon compound represented by the formula R 1 pR2 qSi(OR3)4-p-q, wherein R 1 and R 2 are the same or different and are each independently selected from any one of halogen, a hydrogen atom, an alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, an aryl group of C 6-C20, and a haloalkyl group of C 1-C20, and R 3 is selected from any one of an alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, an aryl group of C 6-C20, and a haloalkyl group of C 1-C20; p and q are integers from 0 to 3, respectively, and p+q <4.
In some preferred embodiments of the invention, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is from (5 to 5000): 1, preferably from (20 to 1000): 1, more preferably from (50 to 500): 1; and/or the molar ratio of aluminum in the alkyl aluminum compound to the external electron donor compound is (0.1 to 500): 1, preferably (1 to 300): 1, more preferably (3 to 100): 1.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
An olefin polymerization process comprising contacting an olefin, at least one of which is represented by the general formula CH 2 =chr, wherein R is any one of hydrogen and an alkyl group of C 1-C6, with the catalyst of any one of the above embodiments under olefin polymerization conditions; preferably, the olefin polymerization conditions are: the temperature is 0-150deg.C, preferably 60-130deg.C; the time is 0.1-5h, preferably 0.5-4h; the pressure is 0.01-10MPa, preferably 0.5-5MPa.
The olefin polymerization method of the present invention can be used for homo-polymerization of olefins, and can also be used for copolymerizing a plurality of olefins. Specific examples of the α -olefin represented by the general formula CH 2 =chr are ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene, and more preferably, the olefin represented by the general formula CH 2 =chr is at least one selected from ethylene, propylene and 1-butene.
The beneficial effects of the invention are at least the following aspects:
The catalyst provided by the invention has smaller particle size, for example, the average particle size can reach 2-19 microns, the particle size distribution is 0.6-1.6, and the application range of the catalyst and the polymer is widened.
Secondly, when the catalyst is used for olefin polymerization, such as propylene polymerization, good polymerization activity, higher hydrogen regulation sensitivity and high isotactic index, and has great industrial application prospect.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
1, 3-Dichloropropanol was purchased from carbofuran corporation;
Epichlorohydrin was purchased from belvedere corporation;
Diisobutyl phthalate was purchased from belowder company;
Titanium tetrachloride was purchased from carbofuran corporation;
Triethylaluminum was purchased from belowder company;
methylcyclohexyl dimethoxy silane was purchased from carbofuran corporation.
In the examples below, the properties referred to were tested as follows:
1. average particle diameter and particle size distribution of catalyst support: the measurement was carried out by using a Master Sizer 2000 particle Sizer manufactured by Malvern Instruments company;
2. Morphology of the catalyst support: observation was performed by an XL-30 type field emission electron microscope manufactured by FEI company of America;
3. Structure and composition of the catalyst support: carrying out 1H-NMR test on the carrier by using an AVANCE 300 nuclear magnetic resonance spectrometer of Bruker company, switzerland, and carrying out test on the carrier by using a PY-2020iD type cracker of Fronteerlab company, a TraceGC Ultra type chromatograph of Thermo Fisher company and a DSQ II type mass spectrometer;
4. catalyst activity: evaluating the ratio of the weight of the product obtained after polymerization to the weight of the catalyst dosage;
5. Bulk density of polyolefin powder: the method specified in GB/T1636-2008 is adopted for measurement;
6. Melt flow rate index of polyolefin powder: measured according to ISO1133, 230℃under a load of 2.16 kg.
Specific surface area of catalyst: testing by a specific surface area analyzer;
in the examples below, the emulsification was carried out with stirring at 600rpm during the preparation of the catalyst support, unless otherwise specified.
Preparation example 1
(1) Adding 0.08mol of magnesium chloride and 1.7mol of ethanol (first alcohol compound) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, performing constant-temperature reaction for 1h to perform first contact, and then performing emulsification to obtain a first product;
(2) Second contacting the first product with 0.48mol of epichlorohydrin to obtain a second product, wherein the second contacting conditions comprise: the temperature is 90 ℃ and the time is 30min;
(3) After the second product is subjected to filter pressing, the second product is fully mixed and stirred with 2.5mol of ethanol (second glycol compound) and 0.35mol of 1, 3-dichloropropanol (halogenated alcohol) to form fluid, and a third product is obtained;
(4) Spray drying is carried out by spraying the third product into circulating nitrogen at 100 ℃ in a spray tower by using a spray machine B-290 comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain a spherical carrier Z1.
Through testing, the structure and the composition of the obtained catalyst spherical carrier Z1 are as follows:
The catalyst spherical support Z1 was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.9.
The catalyst spherical carrier Z1 has regular particle morphology, smooth surface, basically spherical shape, centralized particle size distribution and basically no abnormal particle.
In the process of preparing the catalyst spherical carrier Z1, no clogging phenomenon occurred at the nozzle head of the spraying machine, and 11.8g of carrier Z1 was obtained in total.
Preparation example 2
(1) Adding 0.08mol of magnesium chloride and 1.4mol of ethanol (first alcohol compound) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 1.5h for first contact, and emulsifying to obtain a first product;
(2) Second contacting the first product with 0.35mol of epichlorohydrin to obtain a second product, wherein the conditions of the second contact include: the temperature is 90 ℃ and the time is 30min;
(3) After the second product is subjected to filter pressing, the second product is fully mixed and stirred with 2.5mol of ethanol (second glycol compound) and 0.25mol of 1, 3-dichloropropanol (halogenated alcohol) to form fluid, and a third product is obtained;
(4) Spraying and drying the third product into circulating nitrogen with the temperature of 100 ℃ in a sprayer tower by using a sprayer B-290 comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain the catalyst spherical carrier Z2.
Through testing, the structure and the composition of the obtained catalyst spherical carrier Z2 are as follows:
the catalyst spherical support Z2 was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The spherical support Z2 for olefin polymerization was observed to have a relatively regular particle morphology, a smooth surface, a relatively concentrated particle size distribution, and substantially no irregular particles.
In the process of preparing the catalyst spherical support Z2, no clogging phenomenon occurred at the nozzle head of the atomizer, and 11.9g of the catalyst spherical support Z2 was obtained in total.
Preparation example 3
(1) Adding 0.08mol of magnesium chloride and 1.4mol of ethanol (first alcohol compound) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 1.5h for first contact, and then emulsifying to obtain a first product;
(2) And carrying out second contact on the first product and 0.35mol of epichlorohydrin to obtain a second product, wherein the second contact conditions comprise: the temperature is 90 ℃ and the time is 30min;
(3) Filter-pressing the second product, and stirring the second product with 2.5mol of ethanol (a second glycol compound) and 0.1mol of 1, 3-dichloropropanol (halogenated alcohol) until third contact is carried out to form a fluid, so as to obtain a third product;
(4) Spraying the third product into circulating nitrogen at 100 ℃ in a sprayer tower by using a sprayer B-290 comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain a spherical carrier Z3.
Through testing, the structure and the composition of the obtained catalyst spherical carrier Z3 are as follows:
The catalyst spherical support Z3 was tested to have an average particle diameter (D50) of 5 μm and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst spherical carrier Z3 has regular particle morphology, smooth surface, basically spherical shape, centralized particle size distribution and basically no abnormal particle.
In the process of preparing the catalyst spherical carrier Z3, no clogging phenomenon occurred at the nozzle head of the spraying machine, and 12.0g of the catalyst spherical carrier Z3 was obtained in total.
Example 1-1
(1) Preparation of catalyst for olefin polymerization
In a 300mL reaction flask, 100mL of titanium tetrachloride was added, cooled to-20℃and 8 g of the catalyst spherical support Z1 obtained in example 1 was added thereto, and stirred at-20℃for 30 minutes. Then, the temperature was slowly raised to 110℃and 5.5mmol of diethyl 2, 3-diisopropyl-2-cyano succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (the mass ratio of diethyl 2, 3-diisopropyl-2-cyano succinate to 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane: 8:2) were added during the temperature rise, and after maintaining at 110℃for 30min, the liquid was filtered off. Then, the catalyst was washed with titanium tetrachloride for 2 times, finally, with hexane for 3 times, and dried to obtain a catalyst C1 for olefin polymerization.
(2) Propylene polymerization
In a 5L stainless steel high-pressure reaction kettle, under the protection of nitrogen, adding 1mmol of triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane, 10mg of the olefin polymerization catalyst C1 obtained in the step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene monomer, heating to 70 ℃, reacting for 1h at the temperature, then cooling, decompressing, discharging and drying to obtain polypropylene powder.
The spherical catalyst was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst prepared in this example had an activity of 36.1 KgPP/g.Cat and a specific surface area of 311m 2/g.
The melt flow rate index of the obtained polypropylene powder is 8.9g/10min, the isotactic index is 97.8%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 9.1.
Examples 1 to 2
Polypropylene was prepared in a similar manner to example 1-1, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in example 1-1.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The catalyst prepared in this example had an activity of 36.5 KgPP/g.Cat;
The melt flow rate index of the obtained polypropylene powder is 28.3g/10min, the isotactic index is 96.8%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 9.1.
Example 2-1
Polypropylene was prepared in a similar manner to example 1-1, except that: the mass ratio of the diethyl 2, 3-diisopropyl-2-cyano succinate to the 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane is 5:5.
The spherical catalyst was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst prepared in this example had an activity of 39.2 KgPP/g.Cat and a specific surface area of 300m 2/g.
The melt flow rate index of the obtained polypropylene powder is 9.2g/10min, the isotactic index is 98.1%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 8.0.
Example 2-2
Polypropylene was prepared in a similar manner as in example 2-1, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in example 2-1.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The catalyst prepared in this example had an activity of 39.5 KgPP/g.Cat;
The melt flow rate index of the obtained polypropylene powder is 38.3g/10min, the isotactic index is 97.0%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 8.1.
Example 3-1
Polypropylene was prepared in a similar manner to example 1-1, except that: in the step (1), the mass ratio of the diethyl 2, 3-diisopropyl-2-cyano succinate to the 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane is 2:5.
The spherical catalyst was tested to have an average particle diameter (D50) of 5 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst prepared in this example had an activity of 44.5 KgPP/g.Cat and a specific surface area of 289m 2/g.
The melt flow rate index of the obtained polypropylene powder is 9.7g/10min, the isotactic index is 98.3%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 5.8.
Example 3-2
Polypropylene was prepared in a similar manner as in example 3-1, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in example 3-1.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The catalyst prepared in this example had an activity of 45.6 KgPP/g.Cat;
The melt flow rate index of the obtained polypropylene powder is 50.6g/10min, the isotactic index is 97.2%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 5.8.
Example 4-1
(1) Preparation of catalyst for olefin polymerization
In a 300mL reaction flask, 100mL of titanium tetrachloride was added, cooled to-20℃and 8g of the catalyst spherical support Z2 obtained in example 1 was added thereto, and stirred at-20℃for 30 minutes. Then, the temperature was slowly raised to 110℃and 5.5mmol of diethyl 2, 3-diisopropyl-2-cyano succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (the mass ratio of diethyl 2, 3-diisopropyl-2-cyano succinate to 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane: 5:5) were added thereto during the temperature rise, and after maintaining at 110℃for 30 minutes, the liquid was filtered off. Then, the catalyst was washed with titanium tetrachloride for 2 times, and finally, with hexane for 3 times, and dried to obtain a catalyst C2 for olefin polymerization.
(2) Propylene polymerization
In a 5L stainless steel high-pressure reaction kettle, under the protection of nitrogen, adding 1mmol of triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane, 10mg of the olefin polymerization catalyst C2 obtained in the step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene monomer, heating to 70 ℃, reacting for 1h at the temperature, then cooling, decompressing, discharging and drying to obtain polypropylene powder.
The spherical catalyst was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst prepared in this example had an activity of 39.1 KgPP/g.Cat and a specific surface area of 297m 2/g.
The melt flow rate index of the obtained polypropylene powder is 9.1g/10min, the isotactic index is 98.1%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 8.0.
Example 5-1
(1) Preparation of catalyst for olefin polymerization
In a 300mL reaction flask, 100mL of titanium tetrachloride was added, cooled to-20℃and 8g of the spherical catalyst support Z3 obtained in example 1 was added thereto, and stirred at-20℃for 30 minutes. Then, the temperature was slowly raised to 110℃and 5.5mmol of diethyl 2, 3-diisopropyl-2-cyano succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (the mass ratio of diethyl 2, 3-diisopropyl-2-cyano succinate to 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane: 5:5) were added thereto during the temperature rise, and after maintaining at 110℃for 30 minutes, the liquid was filtered off. Then, the catalyst was washed with titanium tetrachloride for 2 times, finally, with hexane for 3 times, and dried to obtain a catalyst C3 for olefin polymerization.
(2) Propylene polymerization
In a 5L stainless steel high-pressure reaction kettle, under the protection of nitrogen, adding 1mmol of triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane, 10mg of the olefin polymerization catalyst C3 obtained in the step (1), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene monomer, heating to 70 ℃, reacting for 1h at the temperature, then cooling, decompressing, discharging and drying to obtain polypropylene powder.
The spherical catalyst was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst prepared in this example had an activity of 38.8 KgPP/g.Cat and a specific surface area of 290m 2/g.
The melt flow rate index of the obtained polypropylene powder is 8.9g/10min, the isotactic index is 98.1%, the polypropylene powder has good particle morphology and the molecular weight distribution width is 8.0.
Comparative example 1
This comparative example is used to illustrate the catalyst components and the reference preparation of the catalyst.
Preparation of an olefin polymerization catalyst and propylene polymerization were carried out in the same manner as in example 1 except that diisobutyl phthalate was used in place of diethyl 2, 3-diisopropyl-2-cyano succinate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to obtain olefin polymerization catalyst DC1 and polypropylene powder DP3.
The olefin polymerization catalyst DC1 had an average particle diameter (D50) of 4. Mu.m, a particle size distribution of 0.6, an activity of 38.9 kgPP/g.cat, a melt flow rate index of 12.0g/10min for the polypropylene powder DP3, a bulk density of 0.46g/cm 3 and a molecular weight distribution width of 4.8.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (24)
1. A catalyst component for the polymerization of olefins comprising: titanium element, magnesium element, halogen, a compound shown in a general formula (I) and a 1, 3-diether compound, wherein the molar ratio of the compound shown in the general formula (I) to the 1, 3-diether compound is 1 (0.2-1);
The compound of formula (I),
In the formula (I), R '' '1 and R' '' 2 are the same or different and are each independently hydrogen or C 1~C14 linear or branched alkyl, C 3-C10 cycloalkyl, C 6-C10 aryl, C 7-C10 alkylaryl or arylalkyl; the R '"1 and R'" 2 groups can be bonded to each other to form one or more fused ring structures; r '"3 and R'" 4 are identical or different and are each independently C 1~C10 straight-chain or branched alkyl, C 3-C10 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl or C 7-C20 aryl hydrocarbon radicals; in R' "1~R'''4, the hydrogen on the benzene ring in the aryl or alkylaryl or aryl hydrocarbon group can be optionally substituted with other atoms; and
The magnesium element is from a magnesium-containing compound with a structure shown in a formula (II);
the compound of formula (II),
Wherein, in the formula (II),
R 1 is selected from alkyl of C 1-C10;
R 2 and R 3 are the same or different and are each independently selected from the group consisting of alkyl of H, C 1-C10 and haloalkyl of C 1-C10 substituted with 1 to 10 halogen atoms;
R 4 is selected from the group consisting of a haloalkyl group of C 1-C10 substituted with at least one halogen atom and a haloaryl group of C 6-C20 substituted with at least one halogen atom;
R 5 is selected from alkyl of C 1-C5;
X is selected from fluorine, chlorine, bromine and iodine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0< q <0.2;0< a <0.1;
The preparation method of the magnesium-containing compound comprises the following steps:
(1) Sequentially carrying out first contact and emulsification on a component A to obtain a first product, wherein the component A contains magnesium halide with a general formula MgXY and a first alcohol compound with a general formula R 1 OH;
(2) Carrying out second contact on the first product and a component B to obtain a second product, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (III);
(3) Carrying out third contact on the second product and a component C to obtain a third product, wherein the component C contains halogenated alcohol with a general formula of R 4 OH and a second glycol compound with a general formula of R 5 OH;
(4) Subjecting the third product to spray drying;
formula (III),
Wherein R 1、R2、R3、R4 and R 5 have the same definition as above;
In formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from the group consisting of fluorine, chlorine, bromine, iodine, C 1-C6 alkyl, C 1-C6 alkoxy, C 6-C14 aryl, and C 6-C14 aryloxy.
2. The catalyst component according to claim 1 in which R 1 is selected from the group consisting of alkyl groups of C 1-C8; and/or
R 2 and R 3 are selected from the group consisting of alkyl of H, C 1-C5 and haloalkyl of C 1-C5 substituted with 1-5 halogen atoms; and/or
R 4 is selected from the group consisting of a haloalkyl group of C 1-C10 substituted with at least two halogen atoms and a haloaryl group of C 6-C20 substituted with at least two halogen atoms; and/or
R 5 is selected from alkyl of C 1-C2; and/or
X is selected from chlorine and bromine.
3. The catalyst component according to claim 2 in which R 1 is selected from the group consisting of alkyl groups of C 1-C6.
4. A catalyst component according to any one of claims 1 to 3 in which in formula (I), R '1 and R' 2 are the same or different and are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, benzyl, p-toluylmethyl or phenethyl; r '"3 and R'" 4 are identical or different and are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, p-tolyl, o-tolyl, m-tolyl or benzyl.
5. The catalyst component according to claim 4, characterized in that,
The R '"1 and R'" 2 are isopropyl; and/or
The R '"3 and R'" 4 are ethyl; and/or
The compound shown in the general formula (I) is selected from one or more of diethyl 2, 3-diisopropyl-2-cyano succinate, diethyl 3-methyl-2-isopropyl-2-cyano succinate, diethyl 3-ethyl-2-isopropyl-2-cyano succinate, diethyl 3-propyl-2-isopropyl-2-cyano succinate, diethyl 3-butyl-2-isopropyl-2-cyano succinate and diethyl 3-phenyl-2-isopropyl-2-cyano succinate.
6. A catalyst component according to any one of claims 1 to 3 in which the magnesium-containing compound has a spherical or spheroidal structure.
7. The catalyst component according to claim 6 in which the magnesium-containing compound has an average particle diameter of 2 to 100 microns and a particle size distribution of less than 2.
8. The catalyst component according to claim 7 in which the magnesium-containing compound has an average particle diameter of 2 to 19 μm and a particle size distribution of 0.6 to 1.6.
9. A catalyst component according to any of claims 1-3 in which X is selected from chlorine and bromine and Y is selected from chlorine, bromine, alkyl of C 1-C5, alkoxy of C 1-C5, aryl of C 6-C10 and aryloxy of C 6-C10; and/or the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymethyl magnesium chloride and n-butoxymagnesium chloride;
The component A, the component B and the component C are used in such an amount that the resulting spherical support has a structure represented by formula (II).
10. A catalyst component according to any one of claims 1 to 3 in which in step (1) the first contacting is carried out under stirring conditions comprising: the temperature is 80-120 ℃ and the time is 0.5-5h; and/or
In step (2), the conditions of the second contact include: the temperature is 50-120 ℃ and the time is 20-60min; and/or
In the step (3), the amount of the halohydrin is 0.05 to 6.5mol and the amount of the second glycol compound is 5 to 100mol with respect to 1mol of the magnesium halide; and/or
In step (4), the spray drying conditions include: the temperature is 60-200 ℃.
11. The catalyst component according to claim 10 in which in step (1) the conditions of the first contact comprise: the temperature is 80-100 ℃ and the time is 0.5-3h; and/or
In step (2), the conditions of the second contact include: the temperature is 80-100deg.C, and the time is 20-50min; and/or
In step (4), the spray drying conditions include: the temperature is 90-150 ℃.
12. A catalyst component according to any one of claims 1 to 3, characterized in that the weight ratio of the titanium element, the magnesium element and the compound of formula (I) to the total weight of the 1, 3-diether compound is 1:5-15:2-15.
13. The catalyst component according to claim 12, wherein the weight ratio of the titanium element, the magnesium element and the compound represented by the general formula (I) to the total weight of the 1, 3-diether compound is 1:6-13:3-12.
14. A catalyst component according to any one of claims 1 to 3 in which the 1, 3-diether compound has the structure shown in formula (IV);
formula (IV);
wherein, in the formula (IV),
R '1、R'2、R'3、R'4、R'5 and R' 6 are the same or different and are each independently selected from hydrogen, halogen, C 1-C20 straight or branched alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 aralkyl, or C 7-C20 alkaryl, wherein two or more of R '1、R'2、R'3、R'4、R'5 and R' 6 may optionally be bonded to form a ring.
15. The catalyst component according to claim 14 in which R '5 and R' 6 are selected from the group consisting of linear or branched alkyl groups of C 1-C10.
16. Use of a catalyst component according to any one of claims 1 to 15 for the preparation of a catalyst for the polymerization of olefins.
17. A catalyst for olefin polymerization, comprising;
(1) A catalyst component according to any one of claims 1 to 15;
(2) An alkyl aluminum compound; and
(3) Optionally an external electron donor compound.
18. The catalyst of claim 17, wherein the alkyl aluminum compound is selected from the group consisting of alkyl aluminum compounds of formula AlR 'mX'3-m, wherein R' is selected from any one of alkyl of C 1-C20 and aryl of C 6-C20; x' is halogen, m is an integer from 1 to 3; and/or
The external electron donor compound is an organosilicon compound shown in a formula R 1 pR2 qSi(OR3)4-p-q, wherein R 1 and R 2 are the same or different and are each independently selected from any one of halogen, hydrogen atom, alkyl of C 1-C20, cycloalkyl of C 3-C20, aryl of C 6-C20 and halogenated alkyl of C 1-C20, and R 3 is selected from any one of alkyl of C 1-C20, cycloalkyl of C 3-C20, aryl of C 6-C20 and halogenated alkyl of C 1-C20; p and q are integers from 0 to 3, respectively, and p+q <4.
19. The catalyst according to claim 17 or 18, characterized in that the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is (5-5000): 1; and/or the molar ratio of aluminum in the alkyl aluminum compound to the external electron donor compound is (0.1-500): 1.
20. The catalyst of claim 19 wherein the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is (20-1000): 1; and/or the molar ratio of aluminum in the alkyl aluminum compound to the external electron donor compound is (1-300): 1.
21. The catalyst of claim 20 wherein the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is (50-500): 1; and/or the molar ratio of aluminum in the alkyl aluminum compound to the external electron donor compound is (3-100): 1.
22. A process for the polymerization of olefins comprising contacting an olefin, at least one of which is represented by the general formula CH 2 =chr, wherein R is any one of hydrogen and an alkyl group of C 1-C6, with the catalyst of any one of claims 17-21 under olefin polymerization conditions.
23. The polymerization process of claim 22 wherein the olefin polymerization conditions are: the temperature is 0-150 ℃; the time is 0.1-5h; the pressure is 0.01-10MPa.
24. The polymerization process of claim 23 wherein the olefin polymerization conditions are: the temperature is 60-130 ℃; the time is 0.5-4h; the pressure is 0.5-5 MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580136A (en) * | 2003-08-08 | 2005-02-16 | 中国石油化工股份有限公司 | Magnesium halide/alcohol addition compound and its preparing method and use |
| CN102603932A (en) * | 2011-01-19 | 2012-07-25 | 中国石油化工股份有限公司 | Solid catalyst component and catalyst for olefinic polymerization |
| CN109206541A (en) * | 2017-07-01 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
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| CN101811983B (en) * | 2009-02-19 | 2013-02-06 | 中国石油化工股份有限公司 | Preparation method of 2,3-diisopropyl-2-cyano diethyl succinate compound |
| CN102432716B (en) * | 2010-09-29 | 2013-08-14 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization, preparation method and application |
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| CN102603932A (en) * | 2011-01-19 | 2012-07-25 | 中国石油化工股份有限公司 | Solid catalyst component and catalyst for olefinic polymerization |
| CN109206541A (en) * | 2017-07-01 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
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