CN111040054A - Catalyst component for olefin polymerization, preparation method, catalyst and application thereof - Google Patents
Catalyst component for olefin polymerization, preparation method, catalyst and application thereof Download PDFInfo
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- CN111040054A CN111040054A CN201811194087.5A CN201811194087A CN111040054A CN 111040054 A CN111040054 A CN 111040054A CN 201811194087 A CN201811194087 A CN 201811194087A CN 111040054 A CN111040054 A CN 111040054A
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- catalyst
- catalyst component
- titanium
- polymerization
- magnesium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- -1 magnesium halide Chemical class 0.000 claims description 41
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 235000011147 magnesium chloride Nutrition 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical group Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000010413 mother solution Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 claims description 2
- DKLYDESVXZKCFI-UHFFFAOYSA-N n,n-diphenylacetamide Chemical compound C=1C=CC=CC=1N(C(=O)C)C1=CC=CC=C1 DKLYDESVXZKCFI-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- MTAYDNKNMILFOK-UHFFFAOYSA-K titanium(3+);tribromide Chemical compound Br[Ti](Br)Br MTAYDNKNMILFOK-UHFFFAOYSA-K 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 14
- 239000005977 Ethylene Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KFNNIILCVOLYIR-UHFFFAOYSA-N Propyl formate Chemical compound CCCOC=O KFNNIILCVOLYIR-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012632 extractable Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a catalyst component for olefin polymerization, a preparation method thereof, a catalyst and application thereof. The catalyst component comprises: 0.1-5% of titanium, 0.2-10.2% of magnesium, 15-40% of solvent, 0.01-15% of internal electron donor compound and 1-70% of inorganic oxide carrier filler. The catalyst is prepared by a spray drying method, the content of the solvent in the obtained catalyst component particles is low, the catalyst is used for catalyzing ethylene polymerization, the catalyst is high in activity and good in hydrogen regulation performance, and the obtained polymer powder is high in bulk density and low in polymer powder fine powder content.
Description
Technical Field
The invention relates to the field of ethylene and alpha olefin polymerization catalysts, and more particularly relates to a catalyst component for olefin polymerization, a preparation method thereof, a catalyst and an application thereof.
Background
It is well known that high efficiency Ziegler-Natta catalysts for olefin polymerization consist of two parts, a procatalyst and a cocatalyst. The main catalyst is composed of transition metal compounds located in the fourth to eighth main groups of the periodic table, and the cocatalyst is an organic metal compound located in the first to third main groups of the periodic table. In general, the procatalyst can in turn be divided into two fractions: inert carrier and active components loaded on the carrier. The preparation of the main catalyst is generally prepared by adopting the reaction and molding of a titanium halide and a magnesium halide with lattice defects or loading reactants on an inert carrier. The magnesium compound is preferably a magnesium halide having lattice defects, and the magnesium halide having lattice defects may be generated from the magnesium compound, or may be obtained by reacting an electron donor such as alcohol, ether, or ester with a magnesium halide and then removing a part of the electron donor such as alcohol, ether, or ester.
The high level of electron donor or solvent is desirable, and the use of higher levels of promoter aluminum alkyl during polymerization increases both the cost and the residual aluminum content of the resin, leading to increased resin ash and increased haze during film production.
With the continuous development of the technology, the activity, hydrogen regulation sensitivity, copolymerization performance and the bulk density of the polymerization powder, melt index, molecular weight distribution, fine powder content, copolymerization unit distribution and other performance parameters of the Ziegler-Natta type olefin polymerization catalyst are all obviously optimized. However, in order to better meet the requirements of industrial production and obtain polyolefin products with better performance, the above performance parameters of the catalyst and the polymerization powder thereof need to be further improved.
In the prior art, for example, CN1958620A, CN102295717A, and CN103772536A adopt a method of precipitation and sedimentation in a solution, and a siloxane electron donor, an ortho alkoxy substituted benzoate/carboxylate (or diether) compound electron donor, and a benzoate electron donor are respectively introduced to improve the hydrogen sensitivity of the catalyst. For example, CN1726230A, CN1798774A and CN101050248A adopt a dipping and loading method, and introduce electron donors such as alcohol, ketone, amine, amide, nitrile, alkoxysilane, aliphatic ether and aliphatic carboxylic ester into a magnesium chloride-alcohol adduct spherical carrier formed by high-speed stirring and low-temperature condensation, so as to improve the copolymerization performance of the catalyst. For example, CN102807638A adopts a dipping and loading method, and introduces a compound long-carbon-chain monoester/short-carbon-chain monoester electron donor into a magnesium chloride-alcohol adduct spherical carrier formed by high-speed stirring and low-temperature condensation to improve the activity of the catalyst. For example, CN1103406A adopts an external electron donor method to introduce diether, especially 1, 3-diether electron donor, into the polymerization kettle simultaneously with the catalyst, so as to obtain polyethylene product with narrow molecular weight distribution. For example, EP0219998B1 adopts a method of precipitation and sedimentation in solution, and after obtaining a suspension of particles, an appropriate amount of water, an electron donor, is introduced to improve the particle size and distribution of the obtained polyethylene powder and reduce the content of fine powder.
Spray drying is an efficient method for preparing high efficiency Ziegler-Natta catalysts for olefin polymerization. The method is that dissolved liquid or suspension liquid is sprayed into a hot inert gas drying chamber by gas through a specially designed nozzle for drying, and dispersed atomized micro-droplets are dried into powder or granular products. Once the mist droplets are contacted with the dry carrier gas, evaporation takes place on a saturated vapor film on the surface of the rapidly building droplets. During evaporation, the size distribution of the droplets changes and different products show different characteristics. During evaporation, the droplets tend to swell, collapse, break up or disintegrate, resulting in a porous, irregular shape, which is related to the characteristics of the droplets formed in the spray process. The structural modification of the particles can be influenced by the change of the composition, volume and size of the droplets. Adjusting the conditions of the spray drying process, large, small or aggregated particles can be obtained.
CN1085915A discloses a method for preparing a Ziegler-Natta catalyst system. Reduction of titanium tetrachloride in tetrahydrofuran with magnesium metal to produce TiCl3The catalyst has high titanium content and high activity, and can reduce hexane extractables by times when catalyzing the polymerization of ethylene and α -olefin10Smaller, maintaining a larger D10The total yield of the catalyst needs to be reduced, so that more catalyst particles are generated, the production cost is increased, and more waste residues are generated.
CN104761665A discloses a spray-dried ziegler-natta catalyst composition, which comprises inorganic oxide particles, magnesium halide, an electron donor compound, a silane coupling agent and titanium halide, wherein the silane coupling agent improves the surface performance of a silica carrier, and the catalyst has the characteristics of high activity, good hydrogen regulation sensitivity, low fine powder content and the like.
CN100368440C discloses a spray-dried polymerization catalyst and a polymerization process using the same, the catalyst comprising a spray-dried composition of an inert porous filler and the reaction product of: magnesium halide, solvent, electron donor compound, transition metal compound mixture or reaction product. The catalyst contains an alcohol compound as an electron donor, and uses an inert porous filler with a spherical average particle size of 1-12 mu m to reduce small catalyst particles in the catalyst, so as to reduce the content of particles in a polymer.
CN1993391A discloses a strong spray-dried Ziegler-Natta catalyst composition, which comprises inert porous filler, magnesium halide, solvent or diluent, Lewis base electron donor compound, and mixture or reaction product of transition metal compound, wherein the magnesium halide compound exists in the solvent or diluent in an amount of at least 90% of saturation concentration, and the catalyst particles obtained by spray-drying have an average diameter (D) of 10-70 μm50) Wherein at least 5% of the particles have an internal void volume substantially or completely surrounded by a single surface layer (shell), said layer being characterized in that the particles having a particle diameter of more than 30 μm have an average shell thickness/particle diameter (thickness ratio) determined by SEM techniques of more than 0.2. The catalyst reduces polymer fines by reducing catalyst breakage or catalyst fragments remaining larger after breakage.
Some of the above catalysts can only improve the performance of the olefin polymerization catalyst in one aspect, and some of the catalysts can improve several performances, but the catalysts are still not ideal. Therefore, there is a need to develop a catalyst that can improve the performance parameters of the catalyst and its polymerization powder more completely.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a catalyst component for olefin polymerization, a preparation method thereof, a catalyst and application thereof. The catalyst is used for olefin polymerization, particularly for the polymerization of ethylene and alpha-olefin, and has the characteristics of high activity, good hydrogen regulation performance, low catalyst particle content and solvent content, high bulk density of the obtained polymer powder and low fine powder content of the polymer powder.
In order to achieve the above object, one object of the present invention is to provide a catalyst component for olefin polymerization, comprising:
based on the total weight of the catalyst as 100 percent,
according to the invention, preferably, the molar ratio between magnesium and titanium is greater than 3: 1, preferably greater than 5: 1; the molar ratio of the internal electron donor compound to magnesium is (0.01-0.6): 1, preferably (0.08-0.4): 1; the molar ratio of the solvent to magnesium is less than 3: 1, preferably less than 2: 1.
according to the invention, the internal electron donor compound is a compound of the general formula (I), wherein R is1，R2，R3The alkyl groups are the same or different from each other and are independently selected from hydrogen, straight-chain alkyl or branched-chain alkyl of 1-18 carbons, cycloalkyl, aryl, alkaryl or aralkyl.
Specifically, the internal electron donor compound is at least one selected from the group consisting of N-methylformamide, 2-phenylacetamide, N-dimethylformamide, N-dimethylacetamide, N-dimethylformamide, N-diphenylacetamide, N-diethyldodecanamide, N-dimethylpropionamide, N-dimethylp-methylbenzamide, N-diphenylacetamide, and the like.
The added internal electron donor compound can inhibit the expansion, collapse, breakage or splitting of fog drops in the evaporation process of spray drying, thereby reducing the generation of porous and irregularly-shaped catalyst component particles, further reducing the content of polymer fine powder caused by excessive polymer particles in the polymerization process, and simultaneously being beneficial to reducing the content of a solvent in the catalyst component particles.
According to the invention, preferably, the solvent is at least one of an ester, an ether or a ketone, preferably selected from C1～C4Alkyl esters of saturated fatty carboxylic acids, C7～C8Alkyl esters of aromatic carboxylic acids, C2～C6Fatty ethers, C3～C4Cyclic ethers and C3～C6At least one of saturated aliphatic ketones; preferably, the donor solvent is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone; further preferably at least one of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; tetrahydrofuran is most preferred. These solvents may be used alone or in combination.
According to the invention, the inorganic oxide carrier filler is preferably an oxide of silicon and/or an oxide of aluminum, and the particle size is 0.01-10 micrometers, preferably 0.01-5 micrometers, and more preferably 0.1-1 micrometer; preferably, the inorganic oxide carrier filler is silica with a particle size of 0.1 to 10 microns, preferably 0.1 to 1 micron.
The silicon oxide or the aluminum oxide is an inert carrier, the inert carrier is used in spray drying to help control the shape and the composition of the catalyst particles, and the generated catalyst particles have good shape and high strength and are not easy to crush.
Preferably, whichever inorganic oxide support filler (filler) is selected, it should be dry, i.e., free of absorbed moisture. Drying the filler by heating for a period of time at a temperature below the sintering or melting point of the filler material (however, some fillers such as fumed silica naturally have a low residual moisture content due to their particular method of manufacture); typically, drying is carried out using a temperature of at least 100 ℃, lower temperatures being possible when an extended drying time is acceptable or when the filler has a low melting or sintering temperature; the inorganic filler material is usually dried at the temperature of 200-800 ℃; also, the filler material may be treated with one or more Lewis acids (e.g., trialkylaluminum compounds or organosilanes), optionally in an amount of 1 to 10 wt%, to remove polar impurities including water or hydroxyl groups.
The second object of the present invention is to provide a method for preparing the catalyst component for olefin polymerization, which comprises the following steps:
step S1, mother liquor preparation: contacting a solvent, magnesium halide, a titanium-containing compound and an internal electron donor compound, and reacting to prepare a mother solution;
step S2, carrier blending: adding an inorganic oxide support filler during or after step S1 to blend to obtain a slurry suspension;
step S3, spray forming: spray-drying the slurry suspension obtained in step S2 to obtain the catalyst component.
Wherein, the total amount of the raw materials is 100 percent:
according to the catalyst component, the reaction product of the magnesium halide, the titanium-containing compound, the solvent and the internal electron donor compound is loaded on the inorganic oxide carrier filler.
Wherein the titanium-containing compound is titanium halide and/or a product of reducing titanium halide by aluminum and magnesium, and the general formula of the product of reducing titanium halide by aluminum is TiXm·nAlXpWherein n is more than 0 and less than or equal to 1, m is more than 0 and less than or equal to 3, p is more than 0 and less than or equal to 3, and X is halogen; the general formula of the product of magnesium reduction titanium halide is TiXmqMgXr, where q is greater than 0 and less than or equal to 1, m is greater than 0 and less than or equal to 3, r is greater than 0 and less than or equal to 3, X is halogen;
according to the present invention, preferably, the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide or magnesium diiodide, further preferably magnesium dichloride; the titanium halide is titanium bromide and/or titanium chloride, preferably at least one selected from titanium tribromide, titanium tetrabromide, titanium trichloride or titanium tetrachloride, and more preferably titanium trichloride and/or titanium tetrachloride;the product of the aluminum reduction of the titanium halide is preferably TiCl3·1/3AlCl3The product of magnesium reduction of titanium halide is preferably TiCl3·1/2MgCl2。
According to the present invention, the product of aluminum reduction of titanium halide, the product of reduction of titanium halide can be prepared by a method conventional in the art.
The inorganic oxide support filler may be added at any time during the preparation of the mother liquor, for example, magnesium halide, inorganic oxide support filler, titanium-containing compound and internal electron donor compound are mixed and reacted in a solvent to obtain a slurry liquid, and the obtained slurry liquid is spray-dried to obtain the catalyst component.
Preferably, the carrier is blended as follows: the prepared mother liquor was blended with inorganic oxide support filler to obtain a slurry suspension.
According to the present invention, preferably, in the step S1, the reaction temperature is normal temperature to 85 ℃, and the reaction time is not less than 0.1 hour.
According to the present invention, preferably, the spraying conditions in the step S3 include: the inlet temperature is 100-240 ℃, and preferably 120-160 ℃; the outlet temperature is 60-130 ℃, and preferably 90-115 ℃.
In the above preparation method, a sufficient amount of inorganic oxide support filler should be mixed with the mother liquor to form a slurry suitable for spray drying.
It is a further object of the present invention to provide a catalyst for olefin polymerization prepared from the following components:
(A) the above catalyst component and/or the catalyst component obtained by the above production method;
(B) the general formula is A1RbX’3-bWherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X' is a halogen, preferably chlorine, bromine or iodine, and 0 < b.ltoreq.3.
Preferably, in the formula A1RbX’3-bWherein b is more than 1 and less than or equal to 3.
Preferably, the general formulaIs A1RqX’3-qThe organic aluminum compound is at least one selected from triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum or diethyl aluminum monochloride.
Preferably, in the catalyst, the molar ratio of aluminum contained in component (B) to titanium contained in component (a) is (5:1) to (1000:1), preferably (10:1) to (200: 1).
In order to make the solid catalyst component obtained after spray-drying suitable for the production of ethylene polymers, it is necessary to activate the catalyst component with an activator component, an organoaluminum compound. Preferably, the solid catalyst component obtained by the present invention is reacted with an activator component in a hydrocarbon solvent to obtain a catalyst; or reacting the solid catalyst component obtained in the present invention with an activator component during polymerization to initiate olefin polymerization.
Preferably, the hydrocarbon solvent is at least one of isopentane, hexane, heptane, toluene, xylene, naphtha or mineral oil.
The fourth purpose of the invention is to provide an application of the catalyst in olefin polymerization, especially ethylene homopolymerization or copolymerization.
The catalyst of the present invention is suitable for homopolymerization of various ethylene or copolymerization of ethylene and other α -olefin, wherein α -olefin is one or a mixture of several of propylene, butene, pentene, hexene, octene and 4-methylpentene-1.
Compared with the prior art, the invention has the following advantages:
the catalyst for olefin polymerization or copolymerization is prepared by using inorganic oxide carrier filler as a carrier, dissolving magnesium halide by using a solvent, adding a certain proportion of a titanium-containing compound and an internal electron donor compound, and performing spray drying. The catalyst has low solvent content in component particles, few catalyst particles and high activity, good hydrogen regulation performance, and the obtained polymer powder has high bulk density and low fine powder content.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The invention is further illustrated by the following examples:
the test method comprises the following steps:
1. activity: expressed as the weight of resin obtained per gram of catalyst;
2. polymer Melt Index (MI): determined according to ASTM D1238-99, load 2.16kg, 190 ℃;
3. polymer apparent Bulk Density (BD): the test was performed with reference to ASTM D1895-69 standard.
4. The values of the sieve analysis were based on: refer to the astm d-1921 standard.
5. The particle size of the catalyst is as follows: measured using a MasterSIZER2000 particle sizer, termed D10、D50、D90Expressed, i.e. a particular percentage of the standard logarithmic particle size distribution, e.g. the catalyst particle size having D50The median particle diameter is 24 μm when the particle diameter is 24 μm; d10By 7 μm is meant that 10% of the particles are less than 7 μm in diameter. D90By 45 μm is meant that 90% of the particles have a particle size of less than 45 μm.
6. Titanium and magnesium contents: measuring by using a Spectrumlab 752s ultraviolet-visible spectrophotometer; the internal electron donor content of the solid catalyst component adopts liquid nuclear magnetism1H-NMR。
7. THF content: the Agilent Technologies 7890A GC System was used for the determination.
The starting materials used in the examples are all commercially available.
Example 1
(1) Preparation of the catalyst component
Introducing nitrogen gas into a reaction vessel equipped with a temperature controller, a stirrer and a reflux condenserInto a 250ml four-necked flask with blow-off and protection, 100ml of Tetrahydrofuran (THF), 3.73 g of magnesium chloride and 0.89ml of TiCl were added successively under stirring40.18 g of N, N-dimethylacetamide, and the mixture is heated to 68 ℃ with stirring, and the mixture is refluxed for 2 hours at the constant temperature to obtain a mother solution. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
To a 250ml four-necked flask equipped with a temperature controller, a stirrer, and a reflux condenser, purged with nitrogen and protected, 6.5 g of silica gel (Cabot Corporation TS-610, particle diameter 0.1 to 1 μm) was added, the above mother liquor was added under stirring, and the stirring was continued at a constant temperature of 68 ℃ under reflux for 2 hours to completely disperse the silica gel in the mother liquor, to obtain a slurry suspension. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
In closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 145 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively about 27mL/min and 350L/h, and the carrier gas (N) is adjusted2) The flow rate was adjusted so that the outlet temperature became 98 ℃ to obtain a solid catalyst component. The resulting catalyst component has a desired particle diameter D50About 20-23 microns. The catalyst component parameters obtained are shown in Table 1.
(2) Ethylene slurry polymerization
Adding 1L hexane into a 2L polymerization kettle which is firstly purged by nitrogen and then purged by hydrogen, simultaneously adding 1 mL of 1mmol triethyl aluminum and 20 mg catalyst components, heating to 70 ℃, adding hydrogen to 0.28Mpa, adding ethylene to 1.03Mpa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging. The polymerization results are shown in Table 2.
Example 2
(1) Preparation of the catalyst component
A temperature controller, a stirrer,In a 250ml four-neck flask of a reflux condenser which is purged with nitrogen and protected, 100ml Tetrahydrofuran (THF) and 0.33 g magnesium powder (average particle diameter 80-100 μm) are added successively under stirring, and then 4ml TiCl is slowly added over 0.5 hour4Heating to 50 deg.C, stirring at constant temperature for 6 hr to obtain solution of titanium trichloride, magnesium chloride and tetrahydrofuran. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
Into a 250ml four-necked flask equipped with a temperature controller, a stirrer, and a reflux condenser, purged with nitrogen and protected, 77ml of Tetrahydrofuran (THF), 3.79 g of magnesium chloride, 33.3ml of a supernatant of the above solution left to stand for 1 hour, and 0.3 g of N, N-dimethylacetamide were added successively under stirring, and the temperature was raised to 68 ℃ under stirring, followed by reflux reaction at a constant temperature for 2 hours at this temperature to obtain a mother liquor. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
To a 250ml four-necked flask equipped with a temperature controller, a stirrer, and a reflux condenser, purged with nitrogen and protected, 6.5 g of silica gel (Cabot Corporation TS-610, particle diameter 0.1 to 1 μm) was added, the above mother liquor was added under stirring, and the stirring was continued at a constant temperature of 68 ℃ under reflux for 2 hours to completely disperse the silica gel in the mother liquor, to obtain a slurry suspension. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
In closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 145 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively about 24mL/min and 330L/h, and the carrier gas (N) is adjusted2) The flow rate was adjusted so that the outlet temperature was 102 ℃ to obtain a solid catalyst component. The resulting catalyst component has a desired particle diameter D50About 20-23 microns. The catalyst component parameters obtained are shown in Table 1.
(2) Ethylene slurry polymerization
Adding 1L hexane into a 2L polymerization kettle which is firstly purged by nitrogen and then purged by hydrogen, simultaneously adding 1 mL of 1mmol triethyl aluminum and 20 mg catalyst components, heating to 70 ℃, adding hydrogen to 0.28Mpa, adding ethylene to 1.03Mpa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging. The polymerization results are shown in Table 2.
Example 3
(1) Preparation of the catalyst component
Into a 250ml four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and a nitrogen purge and guard were charged, while stirring, 100ml of Tetrahydrofuran (THF), 5.3 g of magnesium chloride and 2.1 g of TiCl in succession3·1/3AlCl3(TOSOH FINECHEM Corporation, TiCl3-AA), 0.38 g of N, N-dimethylacetamide, and heated to 68 ℃ with stirring, and refluxed at this temperature for 2 hours to obtain a mother liquor. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
To a 250ml four-necked flask equipped with a temperature controller, a stirrer, and a reflux condenser, purged with nitrogen and protected, 7.2 g of silica gel (Cabot Corporation TS-610, particle diameter of 0.1 to 1 μm) was added, the above mother liquor was added under stirring, and the stirring was continued at a constant temperature of 68 ℃ under reflux for 2 hours to completely disperse the silica gel in the mother liquor, to obtain a slurry suspension. During this process, the atmosphere was kept under nitrogen (< 5 ppmH)2O)；
In closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 145 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively about 23mL/min and 330L/h, and the carrier gas (N) is adjusted2) The flow rate was adjusted so that the outlet temperature became 103 ℃ to obtain a solid catalyst component. The resulting catalyst component has a desired particle diameter D50About 20-23 microns. The obtained catalystThe formulation parameters are shown in Table 1.
(2) Ethylene slurry polymerization
Adding 1L hexane into a 2L polymerization kettle which is firstly purged by nitrogen and then purged by hydrogen, simultaneously adding 1 mL of 1mmol triethyl aluminum and 20 mg catalyst components, heating to 70 ℃, adding hydrogen to 0.28Mpa, adding ethylene to 1.03Mpa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging. The polymerization results are shown in Table 2.
Example 4
The same procedure as in example 2 was repeated, except that the amount of N, N-dimethylacetamide added in the preparation of the catalyst component in step (1) was changed from 0.3 g to 0.5 g.
Example 5
The same as in example 2 except that 0.3 g of N, N-dimethylacetamide was changed to 0.5 g of N, N-dimethylbenzamide in the preparation of the catalyst component in step (1) in comparison with example 2.
Example 6
The same as in example 2 except that 0.3 g of N, N-dimethylacetamide was changed to 0.42 g of N, N-diphenylacetamide in the preparation of the catalyst component in step (1).
Example 7
In comparison with example 3, except that 2.1 g of TiCl were used in the preparation of the catalyst component in step (1)3·1/3AlCl3Changed to 1.1 g TiCl3·1/3AlCl3Otherwise, the same as in example 3.
Example 8
In comparison with example 3, except that 2.1 g of TiCl were used in the preparation of the catalyst component in step (1)3·1/3AlCl3Changed to 3.1 g TiCl3·1/3AlCl3Otherwise, the same as in example 3.
Example 9
The procedure of example 3 was repeated except that 5.3 g of magnesium chloride was changed to 6.3 g of magnesium chloride in the preparation of the catalyst component in step (1).
Example 10
The procedure of example 3 was repeated except that 5.3 g of magnesium chloride was changed to 3.7 g of magnesium chloride in the preparation of the catalyst component in step (1).
Comparative example 1
The same as in example 1 was repeated except that 0.18 g of N, N-dimethylacetamide was not added in the preparation of the catalyst component in step (1) in comparison with example 1.
Comparative example 2
The same as in example 2 except that 0.3 g of N, N-dimethylacetamide was not added in the preparation of the catalyst component in step (1) as compared with example 2.
Comparative example 3
The same as in example 3 except that 0.38 g of N, N-dimethylacetamide was not added in the preparation of the catalyst component in step (1) as compared with example 3.
TABLE 1 catalyst component parameters
As can be seen from Table 1, the addition of the internal electron donor of the present invention can effectively reduce the tetrahydrofuran content in the catalyst component particles and the D content of the catalyst component particles10Larger, smaller particles.
TABLE 2 Polymer Properties
As shown in Table 2, the catalyst of the present invention has high activity in catalyzing ethylene polymerization, and the obtained polyethylene powder has low fine powder content, high bulk density and good hydrogen response.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. 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 (10)
1. A catalyst component for the polymerization of olefins, characterized in that it comprises:
based on the total weight of the catalyst as 100 percent,
wherein the internal electron donor compound is a compound of a general formula (I), R in the formula (I)1，R2，R3The alkyl groups are the same or different from each other and are independently selected from hydrogen, straight-chain alkyl or branched-chain alkyl of 1-18 carbons, cycloalkyl, aryl, alkaryl or aralkyl.
2. The catalyst component for the polymerization of olefins according to claim 1 characterized in that it comprises:
based on the total weight of the catalyst as 100 percent,
3. the catalyst component for the polymerization of olefins according to claim 1 or 2, characterized in that:
the internal electron donor compound is at least one selected from N-methylformamide, 2-phenylacetamide, N-dimethylformamide, N-dimethylacetamide, N-dimethylbenzamide, N-diphenylacetamide, N-diethyldodecanamide, N-dimethylpropionamide, N-dimethyl-p-methylbenzamide and N, N-diphenylacetamide.
4. The catalyst component for the polymerization of olefins according to claim 1 or 2, characterized in that:
the inorganic oxide carrier filler is silicon oxide and/or aluminum oxide, and the particle size is 0.01-10 micrometers, preferably 0.01-5 micrometers;
the inorganic oxide carrier filler is preferably silicon dioxide with the particle size of 0.1-10 micrometers.
5. A process for the preparation of a catalyst component for the polymerization of olefins according to any of the claims from 1 to 4, characterized in that it comprises the following steps:
step S1, mother liquor preparation: contacting a solvent, magnesium halide, a titanium-containing compound and an internal electron donor compound, and reacting to prepare a mother solution;
step S2, carrier blending: adding an inorganic oxide support filler during or after step S1 to blend to obtain a slurry suspension;
step S3, spray forming: spray-drying the slurry suspension obtained in step S2 to obtain the catalyst component;
wherein, the total amount of the raw materials is 100 percent:
6. the process for preparing a catalyst component for the polymerization of olefins according to claim 5, characterized in that:
the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide or magnesium diiodide;
the titanium-containing compound is titanium halide and/or a product of reducing titanium halide by aluminum and magnesium, and the general formula of the product of reducing titanium halide by aluminum is TiXm·nAlXpWherein n is more than 0 and less than or equal to 1, m is more than 0 and less than or equal to 3, p is more than 0 and less than or equal to 3, and X is halogen; the general formula of the product of magnesium reduction titanium halide is TiXmqMgXr, where q is greater than 0 and less than or equal to 1, m is greater than 0 and less than or equal to 3, r is greater than 0 and less than or equal to 3, and X is halogen.
7. The process for preparing a catalyst component for the polymerization of olefins according to claim 6, characterized in that:
the titanium halide is titanium bromide or titanium chloride, preferably at least one of titanium tribromide, titanium tetrabromide, titanium trichloride or titanium tetrachloride;
the product of the aluminum reduction of the titanium halide is TiCl3·1/3AlCl3The product of magnesium reduction of titanium halide is TiCl3·1/2MgCl2。
8. The process for preparing a catalyst component for the polymerization of olefins according to claim 5, characterized in that:
in step S3, the spraying conditions include: the inlet temperature is 100-240 ℃, and preferably 120-160 ℃; the outlet temperature is 60-130 ℃, and preferably 90-115 ℃.
9. A catalyst for the polymerization of olefins, characterized in that it is prepared from the following components:
(A) the catalyst component according to any one of claims 1 to 4 or obtained by the production method according to claim 5;
(B) the general formula is A1RbX’3-bWherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, b is more than 0 and less than or equal to 3, and X' is a halogen.
10. Use of the catalyst of claim 9 in the polymerization of olefins.
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| CN113563497B (en) * | 2020-04-28 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method, catalyst and application thereof |
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