CN116041585A - Spherical magnesium halide adduct and preparation method and application thereof - Google Patents
Spherical magnesium halide adduct and preparation method and application thereof Download PDFInfo
- Publication number
- CN116041585A CN116041585A CN202111266445.0A CN202111266445A CN116041585A CN 116041585 A CN116041585 A CN 116041585A CN 202111266445 A CN202111266445 A CN 202111266445A CN 116041585 A CN116041585 A CN 116041585A
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- CN
- China
- Prior art keywords
- compound
- formula
- magnesium halide
- spherical
- magnesium
- Prior art date
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- Pending
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- -1 magnesium halide Chemical class 0.000 title claims abstract description 180
- 239000011777 magnesium Substances 0.000 title claims abstract description 137
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 61
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 41
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 229910017718 MgXY Inorganic materials 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 23
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 21
- 239000002609 medium Substances 0.000 claims description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052794 bromium Chemical group 0.000 claims description 15
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 14
- 239000005049 silicon tetrachloride Substances 0.000 claims description 14
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 235000011147 magnesium chloride Nutrition 0.000 claims description 10
- 229960004889 salicylic acid Drugs 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 8
- 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 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 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 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 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 4
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 3
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 claims description 3
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 claims description 2
- CFXDAHURBQNVFG-UHFFFAOYSA-M magnesium;propan-2-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)[O-] CFXDAHURBQNVFG-UHFFFAOYSA-M 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- URFIZJRFOOZIBS-UHFFFAOYSA-N tetrakis(2-hydroxyethyl) silicate Chemical compound OCCO[Si](OCCO)(OCCO)OCCO URFIZJRFOOZIBS-UHFFFAOYSA-N 0.000 claims description 2
- ORLXDXZPQASBRG-UHFFFAOYSA-N tetrakis(3-hydroxypropyl) silicate Chemical compound OCCCO[Si](OCCCO)(OCCCO)OCCCO ORLXDXZPQASBRG-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 150000005166 2-hydroxybenzoic acids Chemical class 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 41
- 238000007334 copolymerization reaction Methods 0.000 abstract description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 20
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 69
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- 235000019441 ethanol Nutrition 0.000 description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000002826 coolant Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 description 2
- AZQCCVRUAHDLCS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxy-3-methylbenzoate Chemical compound CC(C)COC(=O)C1=CC=CC(C)=C1O AZQCCVRUAHDLCS-UHFFFAOYSA-N 0.000 description 2
- VYSFLRWDOKEIMR-UHFFFAOYSA-N 2-methylpropyl 2-hydroxy-4-methylbenzoate Chemical compound CC(C)COC(=O)C1=CC=C(C)C=C1O VYSFLRWDOKEIMR-UHFFFAOYSA-N 0.000 description 2
- WDTCYMNXOJZWGM-UHFFFAOYSA-N 2-methylpropyl 2-hydroxy-5-methylbenzoate Chemical compound CC(C)COC(=O)C1=CC(C)=CC=C1O WDTCYMNXOJZWGM-UHFFFAOYSA-N 0.000 description 2
- RANVDUNFZBMTBK-UHFFFAOYSA-N Amyl salicylate Chemical compound CCCCCOC(=O)C1=CC=CC=C1O RANVDUNFZBMTBK-UHFFFAOYSA-N 0.000 description 2
- YFDUWSBGVPBWKF-UHFFFAOYSA-N Butyl salicylate Chemical compound CCCCOC(=O)C1=CC=CC=C1O YFDUWSBGVPBWKF-UHFFFAOYSA-N 0.000 description 2
- BUDDMZMSYUJQFJ-UHFFFAOYSA-N C(C)OC(C1=C(C(=CC=C1)CC)O)=O Chemical compound C(C)OC(C1=C(C(=CC=C1)CC)O)=O BUDDMZMSYUJQFJ-UHFFFAOYSA-N 0.000 description 2
- DUKPKQFHJQGTGU-UHFFFAOYSA-N Hexyl salicylic acid Chemical compound CCCCCCOC(=O)C1=CC=CC=C1O DUKPKQFHJQGTGU-UHFFFAOYSA-N 0.000 description 2
- PTXDBYSCVQQBNF-UHFFFAOYSA-N Isobutyl salicylate Chemical compound CC(C)COC(=O)C1=CC=CC=C1O PTXDBYSCVQQBNF-UHFFFAOYSA-N 0.000 description 2
- YNMSDIQQNIRGDP-UHFFFAOYSA-N Phenethyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCCC1=CC=CC=C1 YNMSDIQQNIRGDP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NSRLIMVWJNHWJW-UHFFFAOYSA-N ethyl 2-hydroxy-3-methylbenzoate Chemical compound CCOC(=O)C1=CC=CC(C)=C1O NSRLIMVWJNHWJW-UHFFFAOYSA-N 0.000 description 2
- GAZGVYSKTXBHCV-UHFFFAOYSA-N ethyl 2-hydroxy-3-propylbenzoate Chemical compound OC1=C(C(=O)OCC)C=CC=C1CCC GAZGVYSKTXBHCV-UHFFFAOYSA-N 0.000 description 2
- QABFSRANYBCWPK-UHFFFAOYSA-N ethyl 2-hydroxy-4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1O QABFSRANYBCWPK-UHFFFAOYSA-N 0.000 description 2
- XYFGEVOFUDNFGW-UHFFFAOYSA-N ethyl 2-hydroxy-4-propan-2-ylbenzoate Chemical compound OC1=C(C(=O)OCC)C=CC(=C1)C(C)C XYFGEVOFUDNFGW-UHFFFAOYSA-N 0.000 description 2
- ZGYXABNSOOACGL-UHFFFAOYSA-N ethyl 2-hydroxy-5-methylbenzoate Chemical compound CCOC(=O)C1=CC(C)=CC=C1O ZGYXABNSOOACGL-UHFFFAOYSA-N 0.000 description 2
- NWVIEXMVXLHMPO-UHFFFAOYSA-N ethyl 4-ethyl-2-hydroxybenzoate Chemical compound CCOC(=O)c1ccc(CC)cc1O NWVIEXMVXLHMPO-UHFFFAOYSA-N 0.000 description 2
- PDKGDFVCWQSRDX-UHFFFAOYSA-N ethyl 5-ethyl-2-hydroxybenzoate Chemical compound CCOC(=O)C1=CC(CC)=CC=C1O PDKGDFVCWQSRDX-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- YEULQIJMIOWCHB-UHFFFAOYSA-N isopropyl salicylate Chemical compound CC(C)OC(=O)C1=CC=CC=C1O YEULQIJMIOWCHB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SUHLUMKZPUMAFP-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbenzoate Chemical compound COC(=O)C1=CC=CC(C)=C1O SUHLUMKZPUMAFP-UHFFFAOYSA-N 0.000 description 2
- UITFCFWKYAOJEJ-UHFFFAOYSA-N methyl 2-hydroxy-4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1O UITFCFWKYAOJEJ-UHFFFAOYSA-N 0.000 description 2
- JQYUQKRFSSSGJM-UHFFFAOYSA-N methyl 2-hydroxy-5-methylbenzoate Chemical compound COC(=O)C1=CC(C)=CC=C1O JQYUQKRFSSSGJM-UHFFFAOYSA-N 0.000 description 2
- ZFUVIMZJBWFGIS-UHFFFAOYSA-N methyl 3-ethyl-2-hydroxybenzoate Chemical compound CCC1=CC=CC(C(=O)OC)=C1O ZFUVIMZJBWFGIS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- WDMROVYOGGIIAR-UHFFFAOYSA-N propan-2-yl 2-hydroxy-3-methylbenzoate Chemical compound CC(C)OC(=O)C1=CC=CC(C)=C1O WDMROVYOGGIIAR-UHFFFAOYSA-N 0.000 description 2
- LNMQKYAMYFOJLB-UHFFFAOYSA-N propan-2-yl 2-hydroxy-4-methylbenzoate Chemical compound CC(C)OC(=O)C1=CC=C(C)C=C1O LNMQKYAMYFOJLB-UHFFFAOYSA-N 0.000 description 2
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- TVZRJUQBNBLAPV-UHFFFAOYSA-N propyl 2-hydroxy-3-methylbenzoate Chemical compound CCCOC(=O)C1=CC=CC(C)=C1O TVZRJUQBNBLAPV-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- 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
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Abstract
The invention provides a spherical magnesium halide adduct, a preparation method and application thereof. The spherical magnesium halide adduct disclosed by the invention is MgXY-mR (OH) r ‑nE‑q((OH) r‑1 RO) 4 Si. The spherical magnesium halide adductsThe particles have good shape, no abnormal material and no adhesion between particles. The olefin polymerization catalyst prepared by taking the spherical magnesium halide adduct as a carrier shows more excellent hydrogen regulation sensitivity and stronger ethylene-propylene copolymerization capability when being used for olefin (especially ethylene and propylene) polymerization.
Description
Technical Field
The invention relates to a spherical magnesium halide adduct, a preparation method and application thereof.
Technical Field
Polyolefins are a class of polymers polymerized from simple olefins, typically using Ziegler-Natta catalysts. Different catalyst compositions and catalyst preparation methods often result in catalysts having different polymerization properties, e.g., some have high polymerization activity and others have low polymerization activity; some have high orientation capability, others have low orientation capability, etc.
Ziegler-Natta catalysts are generally prepared starting from magnesium compounds such as magnesium halides, metal magnesium, alkyl magnesium or alkoxy magnesium. Catalysts using metallic magnesium, alkyl magnesium or alkoxy magnesium as starting materials often use halogen or halogen-containing compounds such as silicon tetrachloride, titanium tetrachloride, halogenated alkanes, etc. as halogenating agents to convert the starting magnesium compounds to magnesium halides, which are further reacted with titanium compounds, electron donors, such as US7704910B2, US7387979B2, US7220694B2, CN95107310.9, US8293672B2, etc. The magnesium compound prepared by reacting metal magnesium, halogen and absolute ethyl alcohol in US7220694B2 is treated by silicon halide, and the further prepared catalyst component has narrow particle size distribution and can effectively improve the bulk density of the polymer, but the catalyst activity and the polymerization isotactic index are not improved. The catalyst component prepared by using the silica gel loaded magnesium compound or the alkoxy magnesium compound prepared by the reaction of silica gel, alkyl magnesium and hydrogen halide in the US8293672B2 and further treating the silica gel loaded magnesium compound or the alkoxy magnesium compound by using silicon halide has high polymerization activity and orientation capability, less polymer fine powder and high bulk density.
The catalyst prepared by further loading the titanium compound and the electron donor compound is generally spherical by adopting an adduct of magnesium halide and alcohol as a carrier. Spherical magnesium halide adducts and their use as supports in the preparation of olefin polymerization catalysts are well known in the art. The spherical magnesium halide adduct carrier catalyst has high polymerization activity and stereotactic capability when being used for olefin (especially propylene) polymerization, and the obtained polymer also has good particle morphology and high apparent density. The magnesium halide-alcohol adducts disclosed are mostly alcohol complexes of magnesium chloride, typically comprising magnesium chloride and an alcohol binary component. Some of the disclosed adducts of magnesium chloride with alcohols also contain a small amount of water. In order to further improve the hydrogen regulating ability, stereotacticity, ethylene-propylene or propylene-butylene copolymerization ability, polymer fines content in production, etc. of the spherical magnesium halide adduct supported catalyst when used for olefin polymerization, researchers have begun to attempt to introduce other electron donor compounds than alcohol and water into the process of preparing adducts of magnesium halide and alcohol. Such as CN1169840C, CN1286863C, CN103073661A, CN101486722B and CN102796131 a. However, the hydrogen sensitivity and the olefin copolymerization capability of the catalyst remain unsatisfactory.
Disclosure of Invention
The present invention aims to provide a magnesium halide adduct and a preparation method thereof, and a catalyst prepared from the magnesium halide adduct shows good hydrogen regulation sensitivity and olefin copolymerization capability when used for olefin (especially ethylene and propylene) polymerization.
The invention provides a spherical magnesium halide adduct, which is shown as a formula (I),
MgXY-mR(OH) r -nE-q((OH) r-1 RO) 4 Si
(I)
in the formula (I), X is chlorine or bromine, Y is chlorine, bromine and C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 6 -C 14 Aryl, C of (2) 1 -C 14 Straight-chain alkoxy, C 3 -C 14 Branched alkoxy and C 6 -C 14 Is one of the aryloxy groups of (a); r is C 1 -C 20 R is an integer of 1 or more; e is a hydroxybenzoyl compound shown in formula (II),
in the formula (II), R 1 Is hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, halogen, nitro, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); alternatively, R 2 、R 3 、R 4 And R is 5 Two or more of which are bonded to each other to form a ring;
in the formula (I), m is 0.5-5, n is 0.001-0.5, and q is 0.001-0.4.
The invention also provides a preparation method of the spherical magnesium halide adduct, which comprises the following steps:
(1) Mixing MgXY with alcohol and a compound E and heating to obtain a liquid magnesium-containing compound;
(2) Emulsifying the liquid magnesium-containing compound in the presence of an inert liquid medium, and quenching and forming the emulsified product to obtain spherical solid particles;
(3) Contacting the spherical solid particles with a silicon halide in an inert dispersion medium;
in MgXY, X is chlorine or bromine, Y is chlorine, bromine, C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 6 -C 14 Aryl, C of (2) 1 -C 14 Straight-chain alkoxy, C 3 -C 14 Branched alkoxy and C 6 -C 14 Is one of the aryloxy groups of (a);
the alcohol is of the formula R (OH) r The compound is shown as the specification, wherein R in the general formula is C 1 -C 20 R is an integer of 1 or more;
the compound E is a hydroxybenzoyl compound shown in the formula (II),
in the formula (II), R 1 Is hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, halogen, nitro, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); alternatively, R 2 、R 3 、R 4 And R is 5 Two or more of which are bonded to each other to form a ring,
the invention further provides the use of the spherical magnesium halide adducts according to the present invention and prepared by the methods of the present invention for the preparation of olefin polymerization catalysts.
The present inventors have unexpectedly found in a large number of experiments that when a further prepared catalyst is used for polymerization of olefins (particularly ethylene and propylene) using as a carrier a magnesium halide adduct obtained by treating a reaction product of magnesium halide and an alcohol with a silicon halide, the further prepared catalyst shows more excellent hydrogen regulation sensitivity and a stronger ethylene-propylene copolymerization capability. Thus, the catalyst prepared from the magnesium halide adducts of the present invention as a support is very advantageous for the industrial production of high-flow impact polypropylene resins directly from polymerization vessels.
The magnesium halide adducts according to the present invention have good particle morphology, no morphology of the particles (e.g., spheroid, bar, etc.), and no blocking phenomenon between the particles, and thus the polymers obtained by polymerization in the presence of the catalyst system formed from the spherical magnesium halide adducts of the present invention also have good morphology.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.
FIG. 1 is an optical micrograph of a spherical magnesium halide adduct prepared according to example 1 of the present invention.
Detailed Description
The invention provides a spherical magnesium halide adduct, wherein the magnesium halide adduct is shown as a formula (I),
MgXY-mR(OH) r -nE-q((OH) r-1 RO) 4 Si
(I)
in the formula (I), X is chlorine or bromine, Y is chlorine, bromine and C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 6 -C 14 Aryl, C of (2) 1 -C 14 Straight-chain alkoxy, C 3 -C 14 Branched alkoxy and C 6 -C 14 Is one of the aryloxy groups of (a); r is C 1 -C 20 R is an integer of 1 or more; e is a hydroxybenzoyl compound shown in formula (II),
in the formula (II), R 1 Is hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, halogen, nitro, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); alternatively, R 2 、R 3 、R 4 And R is 5 Two or more of which are bonded to each other to form a ring;
m is 0.5-5, n is 0.001-0.5, q is 0.001-0.4.
According to the invention, Y in the MgXY of formula (I) is preferably chlorine, bromine, C 1 -C 5 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 10 Aryl, C of (2) 1 -C 5 Straight-chain alkoxy, C 3 -C 5 Branched alkoxy and C 6 -C 10 Is one of the aryloxy groups of (a). The MgXY in formula (I) may be one magnesium halide compound or a mixture of a plurality of magnesium halide compounds. More preferably, mgXY is two One or more of magnesium chloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxy magnesium chloride, and n-butoxymagnesium chloride. From the viewpoint of availability of raw materials, mgXY is more preferably magnesium dichloride.
According to the invention, R (OH) in formula (I) r In which R is preferably C 1 -C 10 Alkyl or C of (2) 1 -C 10 And r is 1 or 2. R (OH) in formula (I) r May be one alcohol compound or a mixture of a plurality of alcohol compounds. More preferably, R (OH) r Is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, 2-ethylhexanol, ethylene glycol and 1, 3-propanediol.
In the hydroxybenzoyl-type compound represented by the formula (II) according to the present invention, preferably R 1 Is hydrogen, C 1 -C 6 Straight chain alkyl, C 3 -C 6 Branched alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 10 Aryl and C of (2) 7 -C 10 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 10 Aryl and C of (2) 7 -C 10 Is one of aralkyl groups of (a). More preferably, R 1 One selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, benzyl and phenethyl; r is R 2 、R 3 、R 4 And R is 5 Each independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl, and tolyl.
In the formula (I) according to the invention, the E is preferably one of 4-hydroxybenzoic acid compound, 4-hydroxybenzoic acid ester compound, 2-hydroxybenzoic acid compound and 2-hydroxybenzoic acid ester compound; more preferably, it is one of 2-hydroxybenzoic acid-based compound and 2-hydroxybenzoic acid-based compound.
In the present invention, in the formula (I), specific examples of the E may be, but are not limited to: 2-hydroxybenzoic acid methyl ester, 2-hydroxybenzoic acid ethyl ester, 2-hydroxybenzoic acid n-propyl ester, 2-hydroxybenzoic acid isopropyl ester, 2-hydroxybenzoic acid n-butyl ester, 2-hydroxybenzoic acid isobutyl ester, 2-hydroxybenzoic acid n-pentyl ester, 2-hydroxybenzoic acid n-hexyl ester, 2-hydroxybenzoic acid benzyl ester, 2-hydroxybenzoic acid phenethyl ester, 2-hydroxy-3-methylbenzoic acid methyl ester, 2-hydroxy-4-methylbenzoic acid methyl ester, 2-hydroxy-5-methylbenzoic acid methyl ester, 2-hydroxy-3-ethylbenzoic acid methyl ester, 2-hydroxy-4-ethylbenzoic acid methyl ester methyl 2-hydroxy-5-ethylbenzoate, ethyl 2-hydroxy-3-methylbenzoate, ethyl 2-hydroxy-4-methylbenzoate, ethyl 2-hydroxy-5-methylbenzoate, ethyl 2-hydroxy-3-ethylbenzoate, ethyl 2-hydroxy-4-ethylbenzoate, ethyl 2-hydroxy-5-ethylbenzoate, n-propyl 2-hydroxy-3-methylbenzoate, n-propyl 2-hydroxy-4-methylbenzoate, n-propyl 2-hydroxy-5-methylbenzoate, n-propyl 2-hydroxy-3-ethylbenzoate, n-propyl 2-hydroxy-4-ethylbenzoate, n-propyl 2-hydroxy-5-ethylbenzoate, isopropyl 2-hydroxy-3-methylbenzoate, isopropyl 2-hydroxy-4-methylbenzoate, isopropyl 2-hydroxy-5-methylbenzoate, isopropyl 2-hydroxy-3-ethylbenzoate, isopropyl 2-hydroxy-4-ethylbenzoate, isopropyl 2-hydroxy-5-ethylbenzoate, isobutyl 2-hydroxy-3-methylbenzoate, isobutyl 2-hydroxy-4-methylbenzoate, isobutyl 2-hydroxy-5-methylbenzoate, isobutyl 2-hydroxy-3-ethylbenzoate, isobutyl 2-hydroxy-4-ethylbenzoate, isobutyl 2-hydroxy-5-ethylbenzoate, ethyl 2-hydroxy-3-n-propylbenzoate, ethyl 2-hydroxy-4-n-propylbenzoate, ethyl 2-hydroxy-5-n-propylbenzoate, ethyl 2-hydroxy-4-isopropylbenzoate, ethyl 2-hydroxy-4-isobutylbenzoate, ethyl 2-hydroxy-4-tert-butylbenzoate, ethyl 2-hydroxy-4-n-pentylbenzoate, ethyl 2-hydroxy-4-pentylbenzoate and ethyl 2-pentylbenzoate.
According to the invention, in formula (I), said ((OH) r-1 RO) 4 In Si, R and R (OH) r Wherein R is as defined above, preferably R is C 1 -C 10 Alkyl or C of (2) 1 -C 10 Alkylene groups of (a). The formula (I) is described ((OH) r-1 RO) 4 Si may be one alkoxy silicon compound or a mixture of alkoxy silicon compounds. More preferably, ((OH) r-1 RO) 4 Si is one or more of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-n-pentyloxysilane, tetra-isopentyloxy silane, diethoxydimethoxy silane, tetra (2-hydroxyethoxy) silane and tetra (3-hydroxypropoxy) silane.
According to the invention, in formula (I), m is preferably from 1.0 to 3.5, n is preferably from 0.003 to 0.2, q is preferably from 0.001 to 0.2; more preferably, m is 1.0 to 2.7, n is 0.005 to 0.12, and q is 0.002 to 0.17; further preferably, n is 0.005-0.08.
According to a more preferred embodiment of the spherical magnesium halide adduct according to the present invention, said MgXY-mR (OH) r -nE-q((OH) r-1 RO) 4 In Si, X and Y are both chlorine; r is C 1 -C 10 Alkyl or C of (2) 1 -C 10 Is an alkylene group, r is 1 or 2; e is a 2-hydroxybenzoate compound shown in formula (III),
in the formula (III), R 1 One selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, benzyl and phenethyl; r is R 2 、R 3 、R 4 And R is 5 Each independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl, and tolyl; m is 1.0-2.7, n is 0.005-0.12, q is 0.002-0.17.
The spherical magnesium halide adducts according to the present invention may further contain water derived from the synthesis feedstock and the trace amounts of water carried by the reaction medium.
The invention also provides a preparation method of the spherical magnesium halide adduct, which comprises the following steps:
(1) Mixing MgXY with alcohol and a compound E and heating to obtain a liquid magnesium-containing compound;
(2) Emulsifying the liquid magnesium-containing compound in the presence of an inert liquid medium, and quenching and forming the emulsified product to obtain spherical solid particles;
(3) Contacting the spherical solid particles with a silicon halide in an inert dispersion medium;
in MgXY, X is chlorine or bromine, Y is chlorine, bromine, C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 6 -C 14 Aryl, C of (2) 1 -C 14 Straight-chain alkoxy, or branched alkoxy and C 6 -C 14 Is one of the aryloxy groups of (a);
the alcohol is of the formula R (OH) r The compound is shown as the specification, wherein R in the general formula is C 1 -C 20 R is an integer of 1 or more;
The compound E is a hydroxybenzoyl compound shown in the formula (II),
in the formula (II), R 1 Is hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, halogen, nitro, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); alternatively, R 2 、R 3 、R 4 And R is 5 Two or more of which are bonded to each other to form a ring.
The silicon halide is one or two of silicon tetrachloride and silicon tetrabromide.
According to the method of the present invention, in the MgXY, Y is preferably chlorine, bromine or C 1 -C 5 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 10 Aryl, C of (2) 1 -C 5 Straight-chain alkoxy, C 3 -C 5 Branched alkoxy and C 6 -C 10 Is one of the aryloxy groups of (a). The MgXY may be one magnesium halide compound or a mixture of a plurality of magnesium halide compounds. More preferably, mgXY is one or more of magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxymethyl chloride, and n-butoxymagnesium chloride. From the viewpoint of availability of raw materials, mgXY is more preferably magnesium dichloride.
According to the method of the invention, in the presence of said alcohol R (OH) r In the case where R is preferably C 1 -C 10 Alkyl or C of (2) 1 -C 10 And r is 1 or 2. The R (OH) r May be one alcohol compound or a mixture of a plurality of alcohol compounds. More preferably, R (OH) r Is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, 2-ethylhexanol, ethylene glycol and 1, 3-propanediol.
In the hydroxybenzoyl-type compound of the formula (II) according to the process of the present invention, preferably, R 1 Is hydrogen, C 1 -C 6 Straight chain alkyl, C 3 -C 6 Branched alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 10 Aryl and C of (2) 7 -C 10 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 10 Aryl and C of (2) 7 -C 10 Is one of aralkyl groups of (a).
According to the method of the present invention, in the hydroxybenzoyl-type compound represented by the formula (II), R is more preferably 1 One selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, benzyl and phenethyl; r is R 2 、R 3 、R 4 And R is 5 Each independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl, and tolyl.
According to the method of the invention, the compound E is one of 4-hydroxybenzoic acid compound, 2-hydroxybenzoic acid compound and 2-hydroxybenzoic acid compound; preferably, the compound E is one of a 2-hydroxybenzoic acid compound and a 2-hydroxybenzoic acid compound.
Specific examples of compound E according to the method of the present invention may be, but are not limited to: 2-hydroxybenzoic acid methyl ester, 2-hydroxybenzoic acid ethyl ester, 2-hydroxybenzoic acid n-propyl ester, 2-hydroxybenzoic acid isopropyl ester, 2-hydroxybenzoic acid n-butyl ester, 2-hydroxybenzoic acid isobutyl ester, 2-hydroxybenzoic acid n-pentyl ester, 2-hydroxybenzoic acid n-hexyl ester, 2-hydroxybenzoic acid benzyl ester, 2-hydroxybenzoic acid phenethyl ester, 2-hydroxy-3-methylbenzoic acid methyl ester, 2-hydroxy-4-methylbenzoic acid methyl ester, 2-hydroxy-5-methylbenzoic acid methyl ester, 2-hydroxy-3-ethylbenzoic acid methyl ester, 2-hydroxy-4-ethylbenzoic acid methyl ester methyl 2-hydroxy-5-ethylbenzoate, ethyl 2-hydroxy-3-methylbenzoate, ethyl 2-hydroxy-4-methylbenzoate, ethyl 2-hydroxy-5-methylbenzoate, ethyl 2-hydroxy-3-ethylbenzoate, ethyl 2-hydroxy-4-ethylbenzoate, ethyl 2-hydroxy-5-ethylbenzoate, n-propyl 2-hydroxy-3-methylbenzoate, n-propyl 2-hydroxy-4-methylbenzoate, n-propyl 2-hydroxy-5-methylbenzoate, n-propyl 2-hydroxy-3-ethylbenzoate, n-propyl 2-hydroxy-4-ethylbenzoate, n-propyl 2-hydroxy-5-ethylbenzoate, isopropyl 2-hydroxy-3-methylbenzoate, isopropyl 2-hydroxy-4-methylbenzoate, isopropyl 2-hydroxy-5-methylbenzoate, isopropyl 2-hydroxy-3-ethylbenzoate, isopropyl 2-hydroxy-4-ethylbenzoate, isopropyl 2-hydroxy-5-ethylbenzoate, isobutyl 2-hydroxy-3-methylbenzoate, isobutyl 2-hydroxy-4-methylbenzoate, isobutyl 2-hydroxy-5-methylbenzoate, isobutyl 2-hydroxy-3-ethylbenzoate, isobutyl 2-hydroxy-4-ethylbenzoate, isobutyl 2-hydroxy-5-ethylbenzoate, ethyl 2-hydroxy-3-n-propylbenzoate, ethyl 2-hydroxy-4-n-propylbenzoate, ethyl 2-hydroxy-5-n-propylbenzoate, ethyl 2-hydroxy-4-isopropylbenzoate, ethyl 2-hydroxy-4-isobutylbenzoate, ethyl 2-hydroxy-4-tert-butylbenzoate, ethyl 2-hydroxy-4-pentylbenzoate and ethyl 2-pentylbenzoate.
According to the process of the invention, the silicon halide is preferably silicon tetrachloride.
The amounts of MgXY, alcohol, compound E and silicon halide used in the process according to the invention may be suitably selected according to the composition of the intended spherical magnesium halide adduct. Preferably, the alcohol is used in an amount of 1 to 5.5 moles, the compound E is used in an amount of 0.001 to 0.52 mole, and the silicon halide is used in an amount of 0.1 to 10 moles, relative to 1 mole of MgXY in terms of magnesium; more preferably, the amount of the alcohol is 2 to 3.7 moles, the amount of the compound E is 0.003 to 0.22 moles, and the amount of the silicon halide is 0.2 to 8 moles, relative to 1 mole of MgXY in terms of magnesium; it is further preferred that the amount of alcohol is 2.4 to 3.7 moles, the amount of compound E is 0.005 to 0.13 moles, and the amount of silicon halide is 0.4 to 6.5 moles, relative to 1 mole of MgXY in terms of magnesium.
In the process according to the invention, traces of water in MgXY, alcohol and compound E described above may also participate in the adduct-forming reaction.
According to the method of the present invention, the conditions for heating the mixture of MgXY, alcohol and compound E are not particularly limited as long as the heating conditions allow MgXY to react with alcohol and compound E, thereby forming a liquid magnesium-containing compound. Generally, the heating conditions may include: the temperature can be 80-140 ℃ and the time can be 0.5-4 hours.
In the method of the present invention, further comprising emulsifying the magnesium-containing compound in a liquid state in the presence of an inert liquid medium, and quenching the emulsified product to form spherical solid particles.
The inert liquid medium may be any of a variety of liquid media commonly used in the art that do not chemically interact with the magnesium-containing compound. For example: silicone oils and/or inert liquid hydrocarbon solvents. In particular, the inert liquid medium may be one or more of kerosene, paraffinic oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil. The inert liquid medium according to the invention is preferably methyl silicone oil or a mixture of methyl silicone oil and white oil.
According to the method of the present invention, the amount of the inert liquid medium may be selected according to the amount of the specific MgXY. In general, the inert liquid medium is used in an amount of 0.2 to 13L relative to 1 mole of MgXY in terms of magnesium. Preferably, the inert liquid medium is used in an amount of 0.6 to 6.5L with respect to 1 mole of MgXY in terms of magnesium.
According to the method of the present invention, the liquid magnesium-containing compound may be mixed with an inert liquid medium, and then the resulting mixture is emulsified, thereby effecting emulsification of the liquid magnesium-containing compound; the inert liquid medium may also be used as a reaction medium for preparing the liquid magnesium-containing compound (i.e., the inert liquid medium is mixed with MgXY, alcohol, and compound E) to obtain a mixture containing the liquid magnesium-containing compound, and the mixture is emulsified to thereby effect emulsification of the liquid magnesium-containing compound; a part of the inert liquid medium may be used as a reaction medium for preparing the liquid magnesium-containing compound, thereby obtaining a mixture containing the liquid magnesium-containing compound, and then the mixture is mixed with the remaining part of the inert liquid medium and emulsified, thereby realizing the emulsification of the liquid magnesium-containing compound, and the proportion of the inert liquid medium participating in the preparation of the liquid magnesium-containing compound to the total amount of the inert liquid medium is not particularly limited, and may be any proportion.
According to the process of the present invention, surfactants such as fatty acid glycerides, fatty acid sorbitan, polysorbate, polyoxyethylene ethers or polyoxyethylene-polyoxypropylene copolymers may also optionally be added to the inert liquid medium, if desired. The amount of surfactant may be conventional in the art, for example: the surfactant may be used in an amount of 0.001 to 1 mole with respect to 1 mole of MgXY in terms of magnesium.
According to the method of the present invention, the magnesium-containing compound in a liquid state may be emulsified by various methods known to those skilled in the art, for example: the liquid magnesium-containing compound may be emulsified by subjecting the liquid magnesium-containing compound to high-speed shearing in the presence of an inert liquid medium. Such high shear methods are well known to those skilled in the art, for example: CN1151183C (i.e., stirring a liquid magnesium-containing compound in an inert liquid medium at a speed of 2000-5000 rpm), and if necessary, the stirring speed may be as low as 500 rpm; CN1267508C discloses rotating (the speed of rotation may be 100-3000 rpm) a mixture of a liquid magnesium-containing compound and an inert liquid medium in a super gravity bed; CN1463990a discloses that a mixture of a liquid magnesium-containing compound with silicone oil and white oil is output in an emulsifying machine at a speed of 1500-8000 rpm; US6020279 discloses emulsifying a mixture containing a liquid magnesium-containing compound by spraying.
According to the process of the present invention, the emulsified product may be quench formed using methods well known to those skilled in the art to yield spherical solid particles. For example: the emulsified product may be quenched to shape by transferring the emulsified product into a liquid cooling medium.
The liquid cooling medium according to the method of the present invention may be various liquid mediums commonly used in the art that do not chemically interact with the magnesium-containing compound. For example, the liquid cooling medium may be an inert hydrocarbon solvent. Specific examples of the liquid cooling medium may include, but are not limited to: n-pentane, n-hexane, n-heptane, gasoline and petroleum ether.
According to the method of the invention, the temperature of the liquid cooling medium is such that the emulsified product can be cooled and shaped. In general, the temperature of the liquid cooling medium may be from-50℃to 0℃and preferably from-40℃to-20 ℃. The amount of the cooling medium is not particularly limited as long as the amount of the cooling medium is sufficient to cool and shape the emulsified product. Specifically, the volume ratio of the cooling medium to the emulsified product is 1-15:1, preferably 2-9:1.
The method according to the present invention may further comprise washing and drying the spherical solid particles obtained by rapid cooling molding. The washing may be performed by a method known to those skilled in the art, and the obtained spherical solid particles may be washed, for example, with an inert hydrocarbon solvent (for example, n-pentane, n-hexane, n-heptane, petroleum ether, and gasoline). The conditions for the drying are not particularly limited in the present invention, and examples thereof include: the drying temperature may be 20-70 ℃ and the drying time may be 0.5-10 hours. According to the present invention, the drying may be performed under normal pressure or reduced pressure.
According to the method of the present invention, the conditions for the contact reaction of the spherical solid particles and the silicon halide in the step (3) are not particularly limited, and preferably, the solid particles and the silicon halide are pre-contacted for 5 to 60 minutes under the condition of-20 to 10 ℃, and then the temperature is raised to 20 to 80 ℃ for continuing the reaction for 1 to 6 hours; more preferably, the solid particles are pre-contacted with the silicon halide at a temperature of-15 to 5 ℃ for 5 to 30 minutes, and then heated to 30 to 70 ℃ for further reaction for 1 to 5 hours.
According to the process of the present invention, in step (3), the inert dispersion medium may be any of a variety of liquid media commonly used in the art that do not chemically interact with the magnesium halide adducts. For example, the inert dispersion medium may be an inert hydrocarbon solvent. Specific examples of the inert dispersion medium may include, but are not limited to: n-pentane, n-hexane, n-heptane, gasoline and petroleum ether.
According to the process of the present invention, in order to obtain a spherical magnesium halide adduct, the process may further comprise filtering the product obtained after the contact reaction, washing 1 to 10 times with an inert hydrocarbon solvent, and then drying. The inert hydrocarbon solvent may be the same as or different from the inert hydrocarbon solvents described above. The drying conditions may be the same as or different from the above-described drying conditions.
The process according to the invention enables the preparation of magnesium halide adducts in the form of spheres and during the preparation neither blocking nor forming a shaped mass between the particles occurs.
The present invention also provides a spherical magnesium halide adduct prepared by the process of the present invention.
The spherical magnesium halide adducts according to the present invention and prepared by the process of the present invention are further reacted with titanium halide and an electron donor compound to obtain catalysts suitable for the polymerization and copolymerization of olefins, in particular propylene, ethylene. The present invention thus further provides the spherical magnesium halide adducts of the present invention and the use of the spherical magnesium halide adducts prepared by the methods of the present invention in olefin polymerization catalysts.
The invention is further described below in connection with examples, which are not intended to limit the scope of the invention.
The testing method comprises the following steps:
1. polymer melt index (M.I): measured according to the method specified in ASTM D1238-99.
2. Polymer Isotactic Index (II): the measurement is carried out by adopting an n-heptane extraction method (n-heptane boiling extraction is carried out for 6 hours), and the specific operation is as follows: 2g of a dried polymer sample was weighed, placed in an extractor and extracted with boiling n-heptane for 6 hours, then the residue was dried to constant weight, and the ratio of the weight (g) of the obtained residue to 2 was the isotactic index.
3. Xylene solubles content (X.S): baking the copolymer in a vacuum drying oven at 75 ℃ for 30min, and rapidly cooling to room temperature in a dryer; weighing about 2g of copolymer, putting into a 500ml conical flask, adding 200ml of dimethylbenzene, heating and dissolving, cooling a dissolved sample at room temperature for 12-14 min, putting into a constant-temperature water bath, cooling and crystallizing at 25 ℃ for 60min, filtering crystals, heating, baking, weighing and calculating the content of the soluble matters.
4. Ethylene content: the film formation method is carried out by using a Magna-IR760 type infrared spectrometer of Nicolet company, and the film formation method is carried out under the hot pressing at 170 ℃ and 20MPa.
5. The morphology of the samples was observed by means of an optical microscope commercially available from Nikon company under the model Eclipse E200.
6. The alcohol, compound E and silicon alkoxide content of the magnesium halide adduct was determined by gas chromatography, and the Mg content of the magnesium halide adduct was determined by chemical titration.
Ethyl 2-hydroxybenzoate in the following examples was commercially available from Shanghai double happiness fragrance adjuvants, inc.; magnesium chloride is commercially available from Fu Shun Xin Yi titanium factory; absolute ethanol is commercially available from Beijing chemical plant as analytically pure; methyl silicone oil is commercially available from the company of Dow Corning (Shanghai) with a viscosity of 300 centipoise/20 ℃; silicon tetrachloride was commercially available from ala Ding Shiji, inc.
Example 1
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) Preparation of spherical magnesium halide adducts
In a 500mL reaction vessel, 150mL white oil, 30g magnesium chloride, 50mL absolute ethanol, and 1mL ethyl 2-hydroxybenzoate were added, and the temperature was raised to 120℃with stirring. After reacting at constant temperature for 2 hours, the mixture was pressed into 300mL of methyl silicone oil preheated to 120℃and dispersed for 30 minutes with high-speed stirring (1600 rpm) to perform emulsification. Then, the emulsified product was pressed into 2L of hexane cooled to-30℃in advance with nitrogen gas to be solidified and formed. The liquid was removed by filtration, and the solid was washed 5 times with 300mL of hexane and dried under vacuum to obtain spherical solid particles.
In a 300mL glass reaction flask, 100mL of hexane and 3.4mL of silicon tetrachloride were sequentially added under nitrogen protection, cooled to 0 ℃, 10.0g of the spherical solid particles prepared above were added, and stirring was maintained at 0℃for 10 minutes. After that, the temperature was slowly raised to 40℃and reacted at constant temperature for 4 hours. Filtering out liquid, washing the obtained solid with hexane at 60 ℃ for 5 times (hexane amount is 90 mL/time); and vacuum drying the resulting solid to obtain a spherical magnesium halide adduct. The compositions are shown in Table 1, and the morphology of the particles observed with an optical microscope is shown in FIG. 1.
(2) Preparation of olefin polymerization catalyst component
In a 300mL glass reaction flask, 18mL of hexane and 90mL of titanium tetrachloride were sequentially added under nitrogen protection, cooled to-20℃and 8.0g of the spherical magnesium halide adduct prepared in the above (1) was added and stirred at-20℃for 30 minutes. Thereafter, the temperature was slowly raised to 110℃and 1.5mL of diisobutylphthalate was added during the temperature rise. After reaction at 110℃for 30 minutes, the liquid was filtered off. 80mL of titanium tetrachloride was added, the temperature was raised to 120℃and the liquid was filtered off after 30 minutes at 120 ℃; the above operation was repeated once. Finally, washing the obtained solid with hexane at 60 ℃ for 5 times (the hexane dosage is 80 mL/time); and vacuum-drying the obtained solid to obtain a spherical catalyst component.
(3) Olefin homo-polymerization
The propylene liquid phase bulk polymerization was carried out in a 5L stainless steel autoclave. 5mL of a hexane solution of triethylaluminum (concentration: 0.5 mmol/mL), 1mL of a hexane solution of cyclohexylmethyldimethoxysilane (concentration: 0.1 mmol/mL) and 9mg of the spherical catalyst component prepared in step (2) were sequentially added to the reaction vessel under nitrogen protection. The autoclave was closed and 6.5L of hydrogen (standard volume) and 2.3L of liquid propylene were added. The temperature was raised to 70℃and the reaction was carried out for 1 hour. Then cooling, releasing pressure, discharging and drying to obtain polypropylene. The polymerization results are shown in Table 2.
(4) Copolymerization of olefins
In a 5L stainless steel autoclave, 5mL of a hexane solution of triethylaluminum (concentration: 0.5 mmol/mL), 1mL of a hexane solution of cyclohexylmethyldimethoxysilane (concentration: 0.1 mmol/mL) and 9mg of the spherical catalyst component prepared in step (2) were sequentially added to the autoclave under nitrogen protection. The autoclave was closed and 6.5L of hydrogen (standard volume) and 2.3L of liquid propylene were added. The temperature was raised to 70℃and the reaction was carried out for 1.5 hours. Then, the remaining propylene in the autoclave was purged, and a hydrogen/ethylene/propylene mixture (hydrogen: ethylene: propylene=1:26.6:34.6 (molar ratio)) prepared in advance was rapidly added, and the temperature was rapidly raised to 75 ℃ to react for 0.5h. The reactor pressure was controlled at 1.3MPa during the gas phase polymerization. And then cooling, releasing pressure, discharging and drying to obtain the polypropylene. The polymerization results are shown in Table 3.
Comparative example 1
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) of example 1, except that the contact reaction was carried out without using silicon tetrachloride. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) of example 1, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (2) of example 1, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 1 (3) except that the catalyst component was the catalyst component prepared in the above step (2). The polymerization results are shown in Table 3.
Example 2
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) of example 1 except that the temperature at which silicon tetrachloride was contacted with spherical solid particles was reacted was 60 ℃. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) of example 1, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 1, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 1 (4) except that the catalyst component was the catalyst component prepared in the above step (2). The polymerization results are shown in Table 3.
Example 3
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) of example 1, except that 34mL of silicon tetrachloride was used. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) of example 1, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 1, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 1 (4) except that the catalyst component was the catalyst component prepared in the above step (2). The polymerization results are shown in Table 3.
Example 4
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) of example 3 except that the temperature at which silicon tetrachloride was contacted with spherical solid particles was reacted was 60 ℃. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) of example 3, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 3, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 3 (4) except that the catalyst component was the catalyst component prepared in the above step (2). The polymerization results are shown in Table 3.
Example 5
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) of example 1 except that the time for the contact reaction of silicon tetrachloride with the spherical solid particles was 2 hours. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) of example 1, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 1, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 1 (4) except that the catalyst component was the catalyst component prepared in the above step (2). The polymerization results are shown in Table 3.
Example 6
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) in example 5, except that 34mL of silicon tetrachloride was used. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) in example 5, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 5, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 5 (4) except that the catalyst component was the catalyst component prepared in the above step (2).
The polymerization results are shown in Table 3.
Example 7
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) of example 5, except that the temperature at which silicon tetrachloride was precontacted with spherical solid particles was-10 ℃. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) in example 5, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 5, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 5 (4) except that the catalyst component was the catalyst component prepared in the above step (2).
The polymerization results are shown in Table 3.
Example 8
This example illustrates a spherical magnesium halide adduct according to the present invention, a process for its preparation and its use.
(1) A spherical magnesium halide adduct was produced in the same manner as in (1) in example 7, except that silicon tetrachloride was used in an amount of 34mL. The compositions are listed in table 1.
(2) A spherical catalyst component was prepared in the same manner as in (2) of example 7, except that the magnesium halide adduct was the magnesium halide adduct prepared in the above-mentioned step (1).
(3) Propylene polymerization was carried out in the same manner as in (3) of example 7, except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 2.
(4) Ethylene propylene impact copolymerization was performed in the same manner as in example 7 (4) except that the catalyst component was the catalyst component prepared in the above-mentioned step (2). The polymerization results are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
The polymerization results of the catalysts formed from the magnesium halide adducts of the present invention when used in propylene homo-and ethylene propylene copolymerization are shown in tables 2 and 3, respectively. As can be seen from a comparison of the data in table 2, the catalyst prepared with the spherical magnesium halide adducts according to the present invention as a carrier shows more excellent hydrogen response when used for propylene polymerization than the catalyst prepared with the adducts of the prior art as a carrier. As can be seen from a comparison of the data in table 3, the catalyst prepared with the spherical magnesium halide adduct according to the present invention as a carrier shows more excellent ethylene propylene copolymerization ability when used for ethylene propylene impact copolymerization polymerization than the catalyst prepared with the adduct of the prior art as a carrier.
In a word, when the catalyst prepared by taking the adduct obtained according to the invention as a carrier is used for propylene homo-polymerization and copolymerization, the catalyst shows better hydrogen regulation sensitivity and stronger ethylene-propylene copolymerization capability, and the comprehensive performance is better.
FIG. 1 is an optical micrograph of the morphology of particles of the magnesium halide adduct prepared in example 1, which demonstrates that the morphology of the particles of the magnesium halide adduct according to the present invention is good, substantially free of foreign materials and free of blocking between the particles.
Claims (10)
1. A spherical magnesium halide adduct represented by the formula (I),
MgXY-mR(OH) r -nE-q((OH) r-1 RO) 4 Si
(I)
in the formula (I), X is chlorine or bromine, Y is chlorine, bromine and C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 6 -C 14 Aryl, C of (2) 1 -C 14 Straight-chain alkoxy, C 3 -C 14 Branched alkoxy and C 6 -C 14 Is one of the aryloxy groups of (a); r is C 1 -C 20 R is an integer of 1 or more; e is a compound represented by formula (II),
in the formula (II), R 1 Is hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, halogen, nitro, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); alternatively, R 2 、R 3 、R 4 And R is 5 Two or more of which are bonded to each other to form a ring;
in the formula (I), m is 0.5-5, n is 0.001-0.5, and q is 0.001-0.4.
2. The spherical magnesium halide adduct according to claim 1, wherein Y in the MgXY of formula (I) is chlorine, bromine, C 1 -C 5 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 10 Aryl, C of (2) 1 -C 5 Straight-chain alkoxy, C 3 -C 5 Branched alkoxy and C 6 -C 10 Is one of the aryloxy groups of (a); preferably, the method comprises the steps of,MgXY is one or more of magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxy magnesium chloride and n-butoxymagnesium chloride.
3. The spherical magnesium halide adduct according to claim 1, wherein said R (OH) in formula (I) r Wherein R is C 1 -C 10 Alkyl or C of (2) 1 -C 10 And r is 1 or 2; preferably, R (OH) r Is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, 2-ethylhexanol, ethylene glycol and 1, 3-propanediol.
4. The spherical magnesium halide adduct according to claim 1, wherein in the compound represented by formula (II), R 1 Is hydrogen, C 1 -C 6 Straight chain alkyl, C 3 -C 6 Branched alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 10 Aryl and C of (2) 7 -C 10 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, C 1 -C 8 Straight chain alkyl, C 3 -C 8 Branched alkyl, C 3 -C 6 Cycloalkyl, C 6 -C 10 Aryl and C of (2) 7 -C 10 One of the aralkyl groups of (a); preferably, in the compound represented by the formula (II), R 1 One selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, benzyl and phenethyl, R 2 、R 3 、R 4 And R is 5 Each independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl, and tolyl.
5. The spherical magnesium halide adduct according to any one of claims 1 to 4, wherein the compound E is one of 4-hydroxybenzoic acid type compound, 2-hydroxybenzoic acid type compound and 2-hydroxybenzoic acid type compound; preferably, the compound E is one of a 2-hydroxybenzoic acid compound and a 2-hydroxybenzoic acid compound.
6. The spherical magnesium halide adduct according to claim 1, wherein ((OH) r-1 RO) 4 In Si, R is C 1 -C 10 Alkyl or C of (2) 1 -C 10 An alkylene group of (a); preferably, ((OH) r-1 RO) 4 Si is one or more of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-n-pentyloxysilane, tetra-isopentyloxy silane, diethoxydimethoxy silane, tetra (2-hydroxyethoxy) silane and tetra (3-hydroxypropoxy) silane.
7. The spherical magnesium halide adduct according to any one of claims 1 to 6, wherein in formula (I), m is 1.0 to 3.5, n is 0.003 to 0.2, and q is 0.001 to 0.2.
8. The spherical magnesium halide adduct according to claim 7, wherein in formula (I), m is 1.0 to 2.7, n is 0.005 to 0.12, q is 0.002 to 0.17; preferably, n is 0.005-0.08.
9. Use of a spherical magnesium halide adduct according to any one of claims 1 to 8 in the preparation of an olefin polymerization catalyst.
10. A process for the preparation of the spherical magnesium halide adduct of any one of claims 1 to 8, which comprises:
(1) Mixing MgXY with alcohol and a compound E and heating to obtain a liquid magnesium-containing compound;
(2) Emulsifying the liquid magnesium-containing compound in the presence of an inert liquid medium, and quenching and forming the emulsified product to obtain spherical solid particles;
(3) Contacting the spherical solid particles with a silicon halide in an inert dispersion medium;
in MgXY, X is chlorine or bromine, Y is chlorine, bromine, C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 6 -C 14 Aryl, C of (2) 1 -C 14 Straight-chain alkoxy, C 3 -C 14 Branched alkoxy and C 6 -C 14 Is one of the aryloxy groups of (a);
the alcohol is of the formula R (OH) r The compound is shown as the specification, wherein R in the general formula is C 1 -C 20 R is an integer of 1 or more;
the compound E is a hydroxybenzoyl compound shown in the formula (II),
In the formula (II), R 1 Is hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); r is R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, halogen, nitro, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 7 -C 20 One of the aralkyl groups of (a); alternatively, R 2 、R 3 、R 4 And R is 5 Two or more of which are bonded to each other to form a ring;
the silicon halide is one or two mixtures of silicon tetrachloride and silicon tetrabromide;
the amount of alcohol is 1 to 5.5 moles, the amount of compound E is 0.001 to 0.52 mole, and the amount of silicon halide is 0.1 to 10 moles, relative to 1 mole of MgXY calculated as magnesium.
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| CN1861645A (en) * | 2005-05-11 | 2006-11-15 | 北京燕化高新催化剂有限公司 | Ball shape catalyst for ethylene polymerization and preparation process thereof |
| CN102796131A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN102796212A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method |
| CN103819585A (en) * | 2012-11-16 | 2014-05-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application |
| CN104140482A (en) * | 2014-08-06 | 2014-11-12 | 淄博新塑化工有限公司 | Catalyst additive and catalyst for olefin polymerization |
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| CN1861645A (en) * | 2005-05-11 | 2006-11-15 | 北京燕化高新催化剂有限公司 | Ball shape catalyst for ethylene polymerization and preparation process thereof |
| CN102796131A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN102796212A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method |
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