CN116023536A - Alkoxy magnesium carrier for olefin polymerization, preparation method, catalyst and application - Google Patents
Alkoxy magnesium carrier for olefin polymerization, preparation method, catalyst and application Download PDFInfo
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- CN116023536A CN116023536A CN202111245248.0A CN202111245248A CN116023536A CN 116023536 A CN116023536 A CN 116023536A CN 202111245248 A CN202111245248 A CN 202111245248A CN 116023536 A CN116023536 A CN 116023536A
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- -1 Alkoxy magnesium Chemical compound 0.000 title claims abstract description 70
- 239000011777 magnesium Substances 0.000 title claims abstract description 66
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 85
- 239000002105 nanoparticle Substances 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000010936 titanium Substances 0.000 claims abstract description 46
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000002140 halogenating effect Effects 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000460 chlorine Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 12
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012442 inert solvent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 7
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 238000007385 chemical modification Methods 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 5
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000003900 succinic acid esters Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 claims description 2
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims description 2
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 235000019441 ethanol Nutrition 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000010992 reflux Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses an alkoxy magnesium carrier for olefin polymerization, a preparation method, a catalyst and application thereof. The carrier is prepared from the following raw materials: magnesium powder, mixed alcohol, halogenating agent and nano particles with surfaces chemically modified; the shape of the nanoparticle is spheroid or spherical; the average grain diameter of the nano-particles is 10-1000 nm; preferably 50 to 600nm; the nano particles are at least one of inorganic nano particles or organic nano particles, preferably at least one of inorganic silicon nano particles, magnesium nano particles, aluminum nano particles, titanium nano particles, zirconium nano particles, calcium nano particles, iron nano particles, arsenic nano particles and selenium nano particles. The magnesium alkoxide carrier has the advantages of excellent particle shape, controllable particle size, uniform particle shape and narrow particle size distribution; the catalyst prepared by the carrier has high activity, excellent hydrogen regulation performance, narrow particle distribution, controllable size, excellent particle shape and high polymer bulk density.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an alkoxy magnesium carrier for olefin polymerization, a preparation method, a catalyst and application.
Background
The essential core of polyolefin catalyst research is to regulate and control the polymerization activity of the catalyst, the particle morphology and particle size distribution of the polymer generated by the catalyst, the hydrogen regulation sensitivity of the catalyst, the copolymerization performance of the catalyst and the like on the basis of matching different production process conditions. In many polyolefin production processes, taking polyethylene production process as an example, the slurry polymerization process and the gas phase polymerization process have certain requirements on the catalyst, such as particle size, particle size distribution and the like, in addition to activity and hydrogen regulation performance, in order to match the device conditions. Thus, research on catalysts with excellent particle shapes and adjustable particle sizes has been a core and key technology for polyolefin catalyst development.
The catalyst for olefin polymerization is generally prepared by a plurality of modes such as a dissolution and precipitation method, a loading method, a spraying method and the like, wherein the catalyst taking the alkoxy magnesium as a loading source occupies important positions in the field of polyolefin catalysis by virtue of excellent hydrogen regulation performance and particle morphology. It is known that in the preparation of polyolefin catalysts, the particle morphology of the catalyst can be well reproduced to the particle morphology of the support, and thus, it can be said that a catalyst excellent in performance can be realized by controlling the support from which the catalyst is prepared.
In the prior art, various methods for preparing magnesium alkoxides have been disclosed. Chinese patent CN 101906017a describes a method for preparing alkoxymagnesium from magnesium powder, mixed alcohol and halogen; chinese patent CN104356257A, CN103044585 et al describes a method for preparing a polyolefin catalyst carrier by using silica as a dispersion medium, on the basis of which the fluidity of the polyethylene powder prepared is significantly improved, but the content of polymerized fine powder is high and the bulk density is low.
Although various strategies for preparing magnesium alkoxide particles are disclosed, the commercial production of magnesium alkoxide with excellent particle size is still difficult, and it is often necessary to ensure the quality of the support at the expense of yield, especially the preparation of magnesium alkoxide particles with adjustable particle size is more complicated and difficult. Therefore, the preparation of the alkoxy magnesium with excellent particle shape, adjustable particle size, narrow particle size distribution and high bulk density has very important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an alkoxy magnesium carrier for olefin polymerization, a preparation method, a catalyst and application. The magnesium alkoxide carrier has the advantages of excellent particle shape, controllable particle size, uniform particle shape and narrow particle size distribution; the catalyst prepared by the carrier has high activity, excellent hydrogen regulation performance, narrow particle distribution, controllable size, excellent particle shape and high polymer bulk density.
It is an object of the present invention to provide an alkoxymagnesium carrier for olefin polymerization.
The carrier is prepared from the following raw materials:
magnesium powder, mixed alcohol, halogenating agent and nano particles with surfaces chemically modified;
the shape of the nanoparticle is spheroid or spherical; the average grain diameter of the nano-particles is 10-1000 nm; preferably 50 to 600nm;
the nano particles are at least one of inorganic nano particles or organic nano particles, preferably at least one of inorganic silicon nano particles, magnesium nano particles, aluminum nano particles, titanium nano particles, zirconium nano particles, calcium nano particles, iron nano particles, arsenic nano particles and selenium nano particles.
In a preferred embodiment of the present invention,
the magnesium alkoxide carrier is granular, and the average grain diameter is 1-100 mu m, preferably 10-70 mu m;
the particle size distribution is 0.5 to 1.5, preferably 0.6 to 1.1,
the bulk density of the alkoxy magnesium carrier particles is 0.2-0.7 g/cm 3 Preferably 0.2 to 0.6g/cm 3 。
In a preferred embodiment of the present invention,
the nanoparticle is at least one selected from silicon dioxide, titanium dioxide, aluminum oxide, zirconium dioxide, magnesium oxide and calcium oxide, preferably silicon dioxide.
In a preferred embodiment of the present invention,
the nano particles with the surfaces subjected to chemical modification are formed by attaching a layer of inorganic matters and organic siloxane on the surfaces of the nano particles, or the surfaces of the nano particles contain at least one of amino groups, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, mercapto groups, nitro groups, halogen atoms, ester groups, amide groups, urea groups, guanidine groups, aldehyde groups, sulfonic groups and amine groups. Preferably, the surface of the nanoparticle contains at least one of hydroxyl group, amino group, and phenolic hydroxyl group.
In a preferred embodiment of the present invention,
the mixed alcohol is a linear or branched monohydric or polyhydric alcohol, preferably a mixture of alcohols from C1 to C10; more preferably a mixture of ethanol and isooctanol, and/or a mixture of ethanol and butanol; more preferably: the mol content of isooctyl alcohol or butanol in the mixed alcohol is 1% -20%.
In a preferred embodiment of the present invention,
the halogenating agent is at least one of halogen simple substance or inorganic halide, preferably at least one of chlorine, bromine, iodine, magnesium chloride, manganese chloride, mercury chloride, calcium chloride, magnesium bromide, manganese bromide, mercury bromide, calcium bromide, magnesium iodide, manganese iodide, mercury iodide and calcium iodide, more preferably at least one of iodine, magnesium iodide, magnesium chloride and manganese chloride; and/or the number of the groups of groups,
the average grain diameter of the magnesium powder is 50-300 mu m.
In a preferred embodiment of the present invention,
among the raw materials, the raw materials are mixed,
the molar ratio of the halogenating agent to the magnesium powder is (0.0001-0.5): 1, preferably (0.002-0.05): 1;
the mol ratio of the mixed alcohol to the magnesium powder is (1-20): 1, preferably (2-15): 1;
the weight ratio of the nano particles with the surfaces chemically modified to the magnesium powder is (0.0001-2) 1, preferably (0.0001-1) 1.
The second object of the invention is to provide a preparation method of the alkoxy magnesium carrier.
The method comprises the following steps:
1) Adding a halogenating agent, mixed alcohol and nano particles with surfaces chemically modified into an inert solvent, stirring for 10-120 min, and then cooling to-15-10 ℃;
2) Adding magnesium powder, heating to 60-90 ℃ for reaction;
3) Filtering, washing and drying to obtain the alkoxy magnesium carrier.
In a preferred embodiment of the present invention,
in the step 1), the inert solvent is selected from at least one of benzene, toluene, xylene, hexane, heptane, octane, decane, white oil and paraffin, preferably at least one of toluene, hexane, decane, heptane and white oil;
the volume ratio of the inert solvent to the mixed alcohol is (0.02-1): 1, preferably (0.05-0.3): 1.
The inert atmosphere is a protective gas which does not participate in the reaction, preferably an inert gas or nitrogen, more preferably from argon, nitrogen.
In a preferred embodiment of the present invention,
the reaction time of the step 2) is 1 to 12 hours.
It is a further object of the present invention to provide a Ziegler-Natta catalyst for olefins.
A reaction product comprising the following components:
a) An alkoxymagnesium carrier according to one of the objects of the present invention;
b) A titanium-containing compound; wherein the titanium-containing compound has the general formula of Ti (OR) n X 4-n Wherein R is C 1 ～C 8 The alkyl X is halogen atom, n is more than or equal to 0 and less than or equal to 4
C) An internal electron donor compound.
Wherein,,
the titanium-containing compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl and Ti (OC) 2 H 5 ) 3 At least one of I; and/or the number of the groups of groups,
the internal electron donor compound is at least one of esters, ethers, phenols, ketones, carboxylic acids and organic siloxane compounds; preferably at least one of esters, ethers and organosiloxanes; more preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, succinic acid ester, diethyl ether, butyl ether, tetrahydrofuran, tetramethoxysilane, tetraethoxysilane.
The preparation method of the Ziegler-Natta catalyst for olefin adopts the conventional preparation method of the Ziegler-Natta catalyst in the prior art.
In the present invention, it can be preferably prepared by the following steps:
the magnesium alkoxide particles are dispersed in a solvent of hexane and toluene, and contacted with a titanium compound containing titanium and an internal electron donor, respectively, to obtain the Ziegler-Natta catalyst for olefin.
The fourth object of the present invention is to provide a catalyst for olefin polymerization.
The catalyst comprises:
1) A catalyst according to the third object of the present invention;
2) An organoaluminum compound;
the general formula of the organic aluminum compound is AlR m X 3-m Wherein R is hydrogen or C 1 ～C 20 And the alkyl group X is halogen atom, and m is more than 0 and less than or equal to 3.
The invention adopts the following technical scheme:
the preparation method of the alkoxy magnesium carrier comprises the following steps:
1) Adding a halogenating agent, mixed alcohol and nano particles with surfaces chemically modified into an inert solvent under an inert atmosphere, and then cooling to-15-10 ℃;
2) Heating to 60-90 ℃, and adding magnesium powder for reaction for one time or multiple times during the period;
3) The reaction is kept for 1 to 12 hours, filtered and washed for 2 to 6 times, and the obtained solid is dried to obtain the alkoxy magnesium carrier.
Wherein the nanoparticles are preferably selected from inorganic nanoparticles, more preferably at least one of silica, titania, alumina, zirconia, magnesia, and calcia; particularly preferably from silica; the morphology of the nanoparticles is preferably selected from spheroids or spheres; the average particle diameter of the nanoparticles is preferably 10 to 1000nm, more preferably 50 to 600nm.
The surface of the nanoparticle in the present invention is subjected to chemical modification. The surface of the nano particle subjected to chemical modification is provided with one or more functional groups, which is beneficial to the good dispersion of the nano particle in a solvent, and meanwhile, the nano particle with the surface subjected to chemical modification can serve as an effective nucleating agent in the growth process of the alkoxy magnesium, is beneficial to the generation of the narrow-distribution alkoxy magnesium carrier particles, and is beneficial to the regulation and control of the particle size of the alkoxy magnesium carrier particles.
According to an embodiment of the invention, the mixed alcohol is one of a linear or linear monohydric or polyhydric alcohol, preferably a mixture of alcohols from C1 to C10, more preferably a mixture of ethanol and isooctanol, or a mixture of ethanol and butanol. Wherein, the mol content of isooctyl alcohol or butanol in the mixed alcohol is 1-20%.
According to an embodiment of the present invention, the weight ratio of the nanoparticle to magnesium powder is preferably from (0.0001-1): 1; the molar ratio of the halogenating agent to the magnesium powder is preferably from (0.002-0.05): 1; the molar ratio of the mixed alcohol to the magnesium powder is preferably (2-15): 1; the halogenating agent is preferably at least one of iodine simple substance, magnesium iodide, magnesium chloride and manganese chloride.
According to an embodiment of the present invention, the inert solvent is preferably at least one selected from benzene, toluene, xylene, hexane, heptane, octane, decane, white oil, paraffin, more preferably at least one selected from toluene, hexane, decane, heptane, white oil. The inert solvent can not only act as a solvent to prevent aggregation of particles, but also influence the generation mechanism of the alkoxy magnesium to regulate the growth of the alkoxy magnesium.
In the preparation of the alkoxy magnesium carrier, the average particle size of magnesium powder is 50-300 mu m; the shape of the magnesium powder is not particularly limited in the case of good reaction, and preferably spherical particles.
In the preparation of the alkoxy magnesium carrier provided by the invention, magnesium powder can be added at one time or can be added in multiple times according to the particle size requirement of the alkoxy magnesium particles.
In the preparation of the alkoxy magnesium carrier provided by the invention, the halogenating agent and the magnesium powder can be added into the reaction system independently or can be added into the reaction system in the form of solution or slurry.
In the preparation of the alkoxy magnesium carrier, the addition sequence and the reaction temperature of the reaction substances can be adjusted according to the product requirement; the reaction degree is judged according to the discharge amount of hydrogen.
In the preparation of the alkoxy magnesium carrier provided by the invention, the form, the type and the stirring rate of the stirring paddle are not limited, and the stirring paddle is adjusted according to the requirements of products.
In the preparation of the alkoxy magnesium carrier provided by the invention, the reaction product can be washed by adopting ethanol, mixed alcohol and any organic solvent, and the washing mode is not limited.
The product of the alkoxy magnesium carrier provided by the invention can be stored in a dry powder form or a suspension slurry form after being dried.
A Ziegler-Natta catalyst for the polymerization of olefins comprising the reaction product of:
a) The alkoxy magnesium carrier particles;
b) A titanium-containing compound; wherein the titanium-containing compound has the general formula of Ti (OR) n X 4-n Wherein R is C 1 ～C 8 The alkyl, X is halogen atom, n is more than or equal to 0 and less than or equal to 4; the titanium compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl and Ti (OC) 2 H 5 ) 3 At least one of I, preferably TiCl 4
C) An internal electron donor compound.
According to an embodiment of the present invention, the internal electron donor compound is at least one selected from esters, ethers, phenols, ketones, carboxylic acids, and organosiloxanes; preferably at least one of esters, ethers and organosiloxanes; more preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, succinic acid ester, diethyl ether, butyl ether, tetrahydrofuran, tetramethoxysilane, tetraethoxysilane.
A catalyst for olefin polymerization, comprising:
1) Ziegler-Natta catalysts as described above;
2) An organoaluminum compound;
the general formula of the organic aluminum compound is AlR m X 3-m Wherein R is hydrogen or C 1 ～C 20 The hydrocarbon group X is halogen atom, 0 < m.ltoreq.3, and the organoaluminum compound may be selected from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、AlH(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 、AlCl(CH 2 CH 3 ) 2 And AlCl 2 (CH 2 CH 3 ) At least one of them.
Preferably, the organoaluminum compound is selected from Al (CH) 2 CH 3 ) 3 And/or Al (i-Bu) 3 。
The invention has the following beneficial technical effects:
1. the particle shape and the particle size distribution of the alkoxy magnesium carrier particles are improved by introducing the surface-modified functional nano particles; obtaining alkoxyl magnesium carrier particles with controllable particle size, uniform particle shape and narrow particle size distribution;
2. the magnesium alkoxide carrier particles are used for preparing the catalyst for olefin polymerization, and the obtained catalyst has high activity, narrow particle distribution, controllable size, excellent particle shape and high polymer bulk density;
3. the catalyst for olefin polymerization with different sizes prepared by using the alkoxy magnesium carrier is suitable for different polymerization processes.
Drawings
FIG. 1 is a scanning electron microscope image of inorganic nanoparticles;
FIG. 2 is a scanning electron microscope image of the alkyl magnesium support particles of example 1;
FIG. 3 is a scanning electron microscope image of the catalyst for olefin polymerization of example 1:
FIG. 4 is a scanning electron microscope image of the polyethylene powder of example 6.
FIG. 5 is a scanning electron microscope image of the alkyl magnesium support particles of comparative example 1.
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
In the following examples and comparative examples:
1. content (%) = (W1-W0)/w1×100% of organic matter in the surface chemically modified nanoparticle, wherein W1 is W0g of silica modified weight.
2. Particle size and particle size distribution of the magnesium alkoxide support and catalyst: a MalvernMastersizer TM 2000 laser particle sizer was used. Wherein span= (D90-D10)/D50.
3. Particle form of inorganic nanoparticles, magnesium alkoxide support and catalyst: an electron scanning microscope model S4800 of Hitachi was used.
4. Bulk density of magnesium alkoxide particles and polymer: measured by the weight of loose solids per unit volume.
5. The preparation method of the surface-modified nano silicon dioxide comprises the following steps: 100mL of dopamine Tris-HCl solution (10 mM, pH 8.5) with the concentration of 2mg/mL is prepared, after stirring for 1min, 1g (with the particle size of about 250 nm) of silicon dioxide microspheres are added into the solution, the reaction lasts for 3h, clear liquid is filtered and filtered, deionized water and ethanol are used for washing for multiple times, and brown solid particle powder is obtained after drying, wherein the modification amount of the polymer is about 5.6%.
The starting materials used in the remaining examples were all commercially available products.
The invention will be further illustrated with reference to specific examples.
Example 1
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, 0.3g of iodine, 120mL of mixed alcohol (ethanol and isooctanol, the molar ratio of ethanol to isooctanol is 2:0.05) and 60mg of modified nano SiO are added into 30mL of toluene 2 Stirring for 30min, and then cooling to 0 ℃;
(2) Adding 6.3g of magnesium powder, heating to 75 ℃ for reaction, and maintaining the reflux temperature for reaction for 4 hours;
(3) Standing for sedimentation, press-filtering clear liquid, washing with absolute ethyl alcohol and hexane four times, separating, and drying to obtain white solid powder (alkoxy magnesium carrier) with good fluidity.
The particle size and distribution of the product were measured by a particle size distribution instrument, and the results are shown in Table 1.
Examples 2 to 3
The same procedure as in example 1 was followed, except that: nano SiO added into the reaction system 2 The amounts of (2) were adjusted to 6mg and 600mg, respectively.
The particle size and distribution of the product were measured by a particle size distribution instrument, and the results are shown in Table 1.
Examples 4 to 5
The same procedure as in example 1 was followed, except that: the inorganic nano particles are made of nano SiO 2 Respectively adjusting to titanium dioxide and calcium oxide.
The particle size and distribution of the product were measured by a particle size distribution instrument, and the results are shown in Table 1.
Example 6
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, 0.13g of iodine is added into 30mL of toluene,200mL of mixed alcohol (ethanol and isooctyl alcohol, the addition amount of isooctyl alcohol is 2 mL), 60mg of modified nano SiO 2 Stirring for 30min, and then cooling to-15 ℃;
(2) Adding 6.3g of magnesium powder (particle size of 70 mu m respectively), heating to 60 ℃ for reaction, and maintaining the reflux temperature for reaction for 4 hours;
(3) Standing for sedimentation, press-filtering clear liquid, washing with absolute ethyl alcohol and hexane four times, separating, and drying to obtain white solid powder (alkoxy magnesium carrier) with good fluidity.
The particle size and distribution of the product were measured by a particle size distribution instrument, and the results are shown in Table 1.
Example 7
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, 0.66g of iodine, 50mL of mixed alcohol (ethanol and isooctanol, the addition amount of isooctanol is 10 mL) and 60mg of modified nano SiO are added into 30mL of toluene 2 Stirring for 90min, and then cooling to 10 ℃;
(2) Adding 6.3g of magnesium powder (particle size of 300 mu m), heating to 90 ℃ for reaction, and maintaining the reflux temperature for reaction for 8 hours;
(3) Standing for sedimentation, press-filtering clear liquid, washing with absolute ethyl alcohol and hexane four times, separating, and drying to obtain white solid powder (alkoxy magnesium carrier) with good fluidity.
The particle size and distribution of the product were measured by a particle size distribution instrument, and the results are shown in Table 1.
Comparative example 1
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, adding 0.3g of iodine, 120mL of mixed alcohol and 30mL of toluene, stirring for 30min, and then cooling to 0 ℃;
(2) Adding 6.3g of magnesium powder, heating to 75 ℃ for reaction, and maintaining the reflux temperature for reaction for 4 hours;
(3) Standing for sedimentation, press-filtering clear liquid, washing with absolute ethyl alcohol and hexane for four times, separating and drying to obtain white solid powder.
The particle size and distribution of the product were measured by the same method as in example, and the results are shown in Table 1.
Comparative example 2
In the reactor with stirrer, a reflux condensing pipe is installed, a conduit is inserted above the reflux condensing pipe, and the other end of the conduit is connected with an oil seal device, so that H can be observed conveniently 2 Is generated. The reactor was fully replaced with high purity nitrogen.
(1) Under the protection of nitrogen, 0.3g of iodine, 120mL of mixed alcohol, 30mL of toluene and 60mg of unmodified nano SiO are added 2 Then cooling to 0 ℃;
(2) Adding 6.3g of magnesium powder, heating to 75 ℃ for reaction, and maintaining the reflux temperature for reaction for 4 hours;
(3) Standing for sedimentation, press-filtering clear liquid, washing with absolute ethyl alcohol and hexane for four times, separating and drying to obtain white solid powder.
The particle size and distribution of the product were measured by the same method as in example, and the results are shown in Table 1.
Example 8
Into a stirred 5-port reaction vessel with 300mL of nitrogen fully replaced, 4g of the diethoxy magnesium carrier prepared in example 1 and 40mL of toluene were added, the temperature was reduced to-15 ℃, and 20mL of TiCl was slowly added dropwise under stirring 4 When in use, the time is 1h; heating to 100deg.C, keeping the temperature for 2h, standing for settling, decanting supernatant, and adding 30mL TiCl again to the obtained solid 4 And 3mL of tetraethoxysilane, keeping the temperature for 1h, standing and settling, press-filtering the clear liquid, washing with 100mL of hexane for multiple times at 60 ℃ and drying to obtain the solid catalyst with good fluidity.
After the stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of triethylaluminum with the concentration of 1M are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, the pressure in the kettle reaches 0.28MPa by introducing hydrogen, the total pressure in the kettle reaches 0.73MPa by introducing ethylene, and the polymerization is carried out for 2 hours at 80 ℃.
The polymer properties were evaluated using a particle size distribution instrument and polymerization characterization, and the results are shown in table 2.
Examples 9 to 10, comparative example 3
The same procedure as in example 6 was followed, except that the magnesium alkoxide used was derived from examples 2 to 3 and comparative example 1, respectively.
The polymer properties were evaluated using a particle size distribution instrument and polymerization characterization, and the results are shown in table 2.
TABLE 1
| Numbering device | Nanoparticles | Mg/％ | D50/μm | Span | BD/g/cm 3 |
| Example 1 | SiO 2 | 21.34 | 35.88 | 0.70 | 0.37 |
| Example 2 | SiO 2 | 21.14 | 60.32 | 0.82 | 0.32 |
| Example 3 | SiO 2 | 21.32 | 10.23 | 0.69 | 0.56 |
| Example 4 | TiO 2 | 21.16 | 38.78 | 0.88 | 0.36 |
| Example 5 | CaO | 21.33 | 38.93 | 0.98 | 0.35 |
| Example 6 | SiO 2 | 22.03 | 33.71 | 1.10 | 0.31 |
| Example 7 | SiO 2 | 21.26 | 41.20 | 1.07 | 0.29 |
| Comparative example 1 | Without any means for | 21.12 | 45.46 | 1.40 | 0.27 |
| Comparative example 2 | Plain SiO 2 | 21.29 | 43.76 | 1.46 | 0.28 |
TABLE 2
| Numbering device | D50/μm | Span | Ac/KgPE/gCat | BD/g/cm 3 | MI 2.16 /g/10min |
| Example 8 | 35.21 | 0.69 | 33 | 0.33 | 2.01 |
| Example 9 | 59.96 | 0.82 | 31 | 0.29 | 1.92 |
| Example 10 | 10.15 | 0.70 | 36 | 0.38 | 2.15 |
| Comparative example 3 | 44.32 | 1.02 | 28 | 0.24 | 1.89 |
As shown in tables 1-2 and the scanning photo, compared with the comparative example, the introduction of the chemically modified nano particles in the embodiment of the invention can effectively regulate and control the particle size of the alkoxy magnesium particles, the particle size distribution of the particles is narrower, and the bulk density of the alkoxy magnesium particles is slightly higher; the catalyst for olefin polymerization prepared by using the catalyst as a carrier has high activity, narrow particle distribution, controllable size, excellent particle shape and high bulk density of polymer obtained by polymerization. Therefore, the introduction of the modified nano particles is beneficial to improving the comprehensive performance of the alkoxy magnesium particles and the catalyst thereof.
The embodiments of the present invention have been described above, the description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (13)
1. An alkoxymagnesium support for olefin polymerization, characterized in that: the carrier is prepared from the following raw materials:
magnesium powder, mixed alcohol, halogenating agent and nano particles with surfaces chemically modified;
the shape of the nanoparticle is spheroid or spherical; the average grain diameter of the nano-particles is 10-1000 nm; preferably 50 to 600nm;
the nano particles are at least one of inorganic nano particles or organic nano particles, preferably at least one of inorganic silicon nano particles, magnesium nano particles, aluminum nano particles, titanium nano particles, zirconium nano particles, calcium nano particles, iron nano particles, arsenic nano particles and selenium nano particles.
2. The alkoxy magnesium support for olefin polymerization according to claim 1, wherein:
the magnesium alkoxide carrier is granular, and the average grain diameter is 1-100 mu m, preferably 10-70 mu m;
the particle size distribution of the alkoxy magnesium carrier is 0.5-1.5, preferably 0.6-1.1;
the bulk density of the alkoxy magnesium carrier particles is 0.2-0.7 g/cm 3 Preferably 0.2 to 0.6g/cm 3 。
3. The alkoxy magnesium support for olefin polymerization according to claim 1, wherein:
the nanoparticle is at least one selected from silicon dioxide, titanium dioxide, aluminum oxide, zirconium dioxide, magnesium oxide and calcium oxide, preferably silicon dioxide.
4. The alkoxy magnesium support for olefin polymerization according to claim 1, wherein:
the nano particles with the surfaces subjected to chemical modification are formed by attaching a layer of inorganic matters and organic siloxane on the surfaces of the nano particles, or the surfaces of the nano particles contain at least one of amino groups, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, mercapto groups, nitro groups, halogen atoms, ester groups, amide groups, urea groups, guanidine groups, aldehyde groups, sulfonic groups and amine groups; preferably, the surface of the nanoparticle contains at least one of hydroxyl group, amino group, and phenolic hydroxyl group.
5. The alkoxy magnesium support for olefin polymerization according to claim 1, wherein:
the mixed alcohol is a linear or branched monohydric or polyhydric alcohol, preferably a mixture of alcohols from C1 to C10; more preferably a mixture of ethanol and isooctanol, and/or a mixture of ethanol and butanol.
6. The alkoxy magnesium support for olefin polymerization according to claim 1, wherein:
the halogenating agent is at least one of halogen simple substance or inorganic halide, preferably at least one of chlorine, bromine, iodine, magnesium chloride, manganese chloride, mercury chloride, calcium chloride, magnesium bromide, manganese bromide, mercury bromide, calcium bromide, magnesium iodide, manganese iodide, mercury iodide and calcium iodide, more preferably at least one of iodine, magnesium iodide, magnesium chloride and manganese chloride; and/or the number of the groups of groups,
the average grain diameter of the magnesium powder is 50-300 mu m.
7. The alkoxy magnesium support for olefin polymerization according to claim 1, wherein:
among the raw materials, the raw materials are mixed,
the molar ratio of the halogenating agent to the magnesium powder is (0.0001-0.5): 1, preferably (0.002-0.05): 1;
the mol ratio of the mixed alcohol to the magnesium powder is (1-20): 1, preferably (2-15): 1;
the weight ratio of the nano particles with the surfaces chemically modified to the magnesium powder is (0.0001-2) 1, preferably (0.0001-1) 1.
8. A process for the preparation of a magnesium alkoxide support according to any one of claims 1 to 7, characterized in that it comprises:
1) Adding a halogenating agent, mixed alcohol and nano particles with surfaces chemically modified into an inert solvent under the protection of inert atmosphere, stirring for 10-120 min, and then cooling to-15-10 ℃;
2) Adding magnesium powder, heating to 60-90 ℃ for reaction;
3) Filtering, washing and drying to obtain the alkoxy magnesium carrier.
9. The method of preparing as claimed in claim 8, wherein:
in the step 1), the inert solvent is selected from at least one of benzene, toluene, xylene, hexane, heptane, octane, decane, white oil and paraffin, preferably at least one of toluene, hexane, decane, heptane and white oil;
the volume ratio of the inert solvent to the mixed alcohol is (0.02-1): 1, preferably (0.05-0.3): 1.
10. The method of preparing as claimed in claim 8, wherein:
the reaction time of the step 2) is 1 to 12 hours.
11. A Ziegler-Natta catalyst for the polymerization of olefins, characterized in that: a reaction product comprising the following components:
a) The magnesium alkoxide carrier according to any one of claims 1 to 7;
b) A titanium-containing compound; wherein the titanium-containing compound has the general formula of Ti (OR) n X 4-n Wherein R is C 1 ～C 8 The alkyl, X is halogen atom, n is more than or equal to 0 and less than or equal to 4;
c) An internal electron donor compound.
12. The Ziegler-Natta catalyst according to claim 11, characterized in that:
the saidThe titanium-containing compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl and Ti (OC) 2 H 5 ) 3 At least one of I; and/or the number of the groups of groups,
the internal electron donor compound is at least one of esters, ethers, phenols, ketones, carboxylic acids and organic siloxane compounds; preferably at least one of esters, ethers and organosiloxanes; more preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, succinic acid ester, diethyl ether, butyl ether, tetrahydrofuran, tetramethoxysilane, tetraethoxysilane.
13. A catalyst for olefin polymerization, characterized in that the catalyst comprises:
1) The catalyst of claim 11 or 12;
2) An organoaluminum compound;
the general formula of the organic aluminum compound is AlR m X 3-m Wherein R is hydrogen or C 1 ～C 20 And the alkyl group X is halogen atom, and m is more than 0 and less than or equal to 3.
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