CN116063593B - Catalyst component for olefin polymerization, catalyst containing catalyst component, preparation method and application of catalyst component - Google Patents
Catalyst component for olefin polymerization, catalyst containing catalyst component, preparation method and application of catalyst component Download PDFInfo
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- CN116063593B CN116063593B CN202111277834.3A CN202111277834A CN116063593B CN 116063593 B CN116063593 B CN 116063593B CN 202111277834 A CN202111277834 A CN 202111277834A CN 116063593 B CN116063593 B CN 116063593B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 47
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- -1 magnesium halide Chemical class 0.000 claims abstract description 41
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000010413 mother solution Substances 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 claims description 2
- KFNNIILCVOLYIR-UHFFFAOYSA-N Propyl formate Chemical compound CCCOC=O KFNNIILCVOLYIR-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 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
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 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
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 33
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000012632 extractable Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 1
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- 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
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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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- 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 belongs to the field of catalysts, and provides a catalyst component for olefin polymerization and a catalyst containing the same. The catalyst component comprises: inorganic oxide, alkyl cyclosilazane compound, said alkyl cyclosilazane compound is magnesium halide, titanium halide, alkyl cyclosilazane compound and reaction product of electron donor compound, and use this catalyst component to prepare catalyst product for olefin polymerization. The polymer prepared by the catalyst product has higher melt index, low hexane extractables content and low oligomer content.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst containing the component, a preparation method of the catalyst, and application of the catalyst in olefin polymerization.
Background
The efficient Ziegler-Natta catalyst for olefin polymerization consists of two parts, main catalyst and cocatalyst. The main catalyst is composed of transition metal compounds in the fourth to eighth main groups of the periodic table, and the cocatalyst is an organic metal compound in the first to third main groups of the periodic table. Typically, the procatalyst can in turn be divided into two parts: inert carrier and active component loaded by the same. The preparation of the procatalyst is generally prepared by either reacting a titanium halide with a lattice defective magnesium halide to form or supporting the reactants on an inert support. The magnesium compound is preferably magnesium halide with lattice defect, and magnesium halide with lattice defect can be formed from magnesium compound, or can be obtained by reacting electron donor such as alcohol, ether, ester, etc. with magnesium halide, and then removing part of electron donor such as alcohol, ether, ester, etc.
CN102432713a provides a titanium-containing solid catalyst component for ethylene polymerization and a preparation method, which are obtained through the following three consecutive synthesis steps: 1) Preparing a magnesium-containing solid by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing compound; 2) Treating the magnesium-containing solid with an organometallic compound or a mixture of an organometallic compound and an electron donor compound to obtain a magnesium-containing catalyst support; 3) The catalyst component is obtained by treating the magnesium-containing catalyst support with a transition metal titanium compound in the presence of an inert organic solvent and then with an alkoxy silicon compound. Has the characteristics of simple process, convenient operation, low investment on industrial equipment, easy control of product quality and the like. High catalytic activity, strong copolymerization capability, high polymer bulk density, less subdivision and the like, and is suitable for slurry polymerization or gas phase polymerization of ethylene. However, the catalyst generates more fine powder in industrial application, which is unfavorable for the operation of the device.
CN106543303a adopts another scheme, which relates to a catalyst component, a catalyst and a preparation method thereof for olefin polymerization reaction. The catalyst component comprises: 1) An ultrafine inorganic oxide support, and 2) a reaction product of a magnesium halide, a halogenated hydrocarbon, a titanium halide, and an electron donor compound. The catalyst comprises the reaction product of: (A) the catalyst component of the present invention; and (B) an organoaluminum compound of the formula AlR nX3-n, wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X is halogen, preferably chlorine, bromine or iodine, and 0 < n.ltoreq.3. The catalyst of the invention has high activity, and the obtained polymer has higher bulk density and higher melt index.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention provides a catalyst component for olefin polymerization and a preparation method thereof, and provides a catalyst prepared by using the catalyst component, wherein the catalyst is used in olefin polymerization reaction, and the obtained polymer has a higher melt index and a low oligomer content.
It is an object of the present invention to provide a catalyst component for olefin polymerization comprising an inorganic oxide, an alkyl cyclosilazane complex which is a reaction product of magnesium halide, titanium halide, an alkyl cyclosilazane compound and an electron donor compound.
Specifically, among the above catalyst components:
The general formula of the alkyl cyclosilazane compound is (R n1Rn2SiNH)n, wherein n=1-9,R n1、Rn2 is the same or different and is independently selected from at least one of H, C-C5 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C8 cycloalkyl and C6-C10 aryl, preferably at least one of C1-C5 alkyl and C6-C10 aryl;
The electron donor compound is at least one selected from esters, ethers and ketones, preferably at least one selected from alkyl esters of C1-C4 saturated aliphatic carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 aliphatic ethers, C3-C4 cyclic ethers and C3-C6 saturated aliphatic ketones; specific examples of the electron donor compound include, but are not limited to: 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, methyl isobutyl ketone, preferably at least one of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, methyl isobutyl ketone; more preferably tetrahydrofuran;
The inorganic oxide is at least one selected from the group consisting of oxides of silicon and aluminum, preferably at least one selected from the group consisting of aluminum oxide and silicon dioxide, and more preferably silicon dioxide;
the particle size of the inorganic oxide is 0.001 to 10. Mu.m, preferably 0.005 to 5. Mu.m, more preferably 0.01 to 2. Mu.m, most preferably 0.01 to 1. Mu.m;
The magnesium halide is at least one selected from magnesium chloride, magnesium bromide and magnesium iodide;
The titanium halide is at least one selected from titanium trichloride, titanium tetrachloride, titanium tribromide and titanium tetrabromide, preferably at least one selected from titanium trichloride and titanium tetrachloride.
Among the above catalyst components:
The inorganic oxide content in the catalyst component is 5-50%, preferably 10-30%, more preferably 15-25% by mass;
The magnesium halide is used in an amount of 0.1 to 15mol, preferably 1 to 10mol, more preferably 2 to 7mol, per mol of titanium halide; the amount of the alkyl cyclosilazane compound is 0.01 to 10mol, preferably 0.05 to 8mol, more preferably 0.1 to 3mol; the electron donor compound is used in an amount of 1 to 600mol, preferably 10 to 500mol, more preferably 100 to 200mol;
The titanium content of the catalyst component is 0.1 to 5%, preferably 1 to 3%, more preferably 1.5 to 2.5% by mass.
The second object of the present invention is to provide a method for preparing the above catalyst component for olefin polymerization, comprising loading the component containing the alkyl cyclosilazane complex onto the inorganic oxide, thereby obtaining the catalyst component. The preparation method specifically comprises the following steps:
Step 1, mother liquor preparation: mixing the components comprising the magnesium halide, the titanium halide, the alkyl cyclosilazane compound and the electron donor compound, and heating for reaction to obtain an alkyl cyclosilazane compound mother solution;
step 2, carrier doping: uniformly mixing the alkyl cyclosilazane compound mother liquor obtained in the step 1 with inorganic oxide to obtain slurry;
step 3, spray forming: and (3) drying the slurry obtained in the step (2) to obtain the catalyst component.
In the preparation method, the reaction temperature in the step1 is 55-80 ℃ and the reaction time is 2-6 h;
And (2) drying the inorganic oxide added in the step (2) to remove adsorbed water, mixing with the mother solution, and drying by adopting drying equipment and drying conditions commonly used in the field. The amount of the inorganic oxide to be added is not particularly limited as long as it is a slurry capable of spray-drying after mixing the inorganic oxide with the mother liquor, and preferably the inorganic oxide content in the slurry is 2 to 60%, preferably 5 to 35%;
The drying in the step 3 is spray drying, preferably, the conditions of the spray drying include: the inlet temperature is 80-240 ℃, preferably 120-220 ℃; the outlet temperature is 60 to 130 ℃, preferably 90 to 110 ℃.
Another object of the present invention is to provide a catalyst for olefin polymerization, comprising: the above catalyst component or the catalyst component obtained by the above production method, preferably, further comprises an organoaluminum compound.
Wherein the general formula of the organic aluminum compound is AlR nX3-n, wherein R is hydrogen or C1-C20 alkyl, preferably hydrogen or C1-C6 alkyl, X is halogen, and n is more than 0 and less than or equal to 3; preferably, the organic aluminum compound is at least one selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and diethylaluminum chloride;
The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component was 5: 1-500: 1, preferably 10:1 to 200:1.
It is a fourth object of the present invention to provide the use of the above catalyst in olefin polymerization. The application comprises the following steps: the components including the components in the catalyst and the organic aluminum compound are added into a solvent for reaction, and then olefin polymerization reaction is initiated. Wherein the solvent is selected from hydrocarbon organic solvents, preferably at least one selected from isopentane, hexane, heptane, toluene, xylene, naphtha and mineral oil.
The invention adopts a spray drying process to uniformly load the alkyl cyclosilazane compound on an inorganic oxide carrier to obtain a solid catalyst component, and is suitable for olefin polymerization catalysts. When in use, the titanium metal in the catalyst component is reduced by an activator component (such as an organic aluminum compound) to be in a state capable of initiating olefin polymerization reaction. In general, the catalyst component and the activator component may be reacted in a hydrocarbon organic solvent to obtain a catalyst, or the catalyst component and the activator component may be reacted in the polymerization process to initiate the olefin polymerization reaction.
The catalyst of the invention is suitable for the polymerization reaction of various olefins, including homo-polymerization reaction or copolymerization reaction, especially for the homo-polymerization of various ethylene or the copolymerization of ethylene and alpha-olefin, wherein the alpha-olefin can be selected from one of propylene, butene, pentene, hexene, octene and 4-methylpentene-1. The polymerization process can adopt a gas phase method, a slurry method and a solution method, and is more suitable for gas phase fluidized bed polymerization. The conditions for the polymerization of the olefin may be conventionally selected according to the prior art and will not be described in detail herein.
The alkyl cyclosilazane compound adopted by the invention contains electron donor compound and metal halide, and simultaneously, the alkyl cyclosilazane compound is added, the mixture is loaded on an inorganic oxide carrier after the mixing reaction, and then, an activator component, namely an organic aluminum compound, is added for activation, so that the catalyst with high activity, good dispersibility, high strength and difficult rupture can be obtained, and the catalyst is applied to olefin polymerization reaction, and the obtained polymer has low oligomer content and higher melt index. The nitrogen atoms in the alkyl cyclosilazane compound contain lone pair electrons, and after the compound forms a ring structure, the compound has stronger electron donating capability due to the electron effect among the compound, and can effectively improve the polymerization efficiency of the active center of the catalyst after being coordinated with the active center.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
1. Catalyst activity: expressed as weight of resin obtained per gram of catalyst;
2. Polymer Melt Index (MI): 6932 melt index meter, CEAST company, italy;
3. hexane extractables content in polymer powder (wt%): extracting dry polymer powder by using hexane, specifically leaching the polymer by using hexane for 4 hours, wherein the weight difference between the polymer powder before and after extraction accounts for the weight of the polymer powder before extraction, namely the hexane extractable content in the polymer powder;
4. determination of titanium content in the catalyst component: dissolving a catalyst sample with 1M sulfuric acid, measuring a dissolving solution by using a spectrophotometer, and calculating by using a working curve to obtain titanium content;
5. the superfine inorganic oxide content is obtained by calculating the mass ratio of the fed amount to the produced catalyst.
The raw materials used in the examples were all commercial products.
Example 1
This example is intended to illustrate the catalyst component of the present invention, its preparation method, catalyst and its use.
(1) Preparation of the catalyst component
To a 250mL three-necked flask purged with nitrogen, 3.0gTiCl 4 g anhydrous MgCl 2, 2.8mL hexamethylcyclotrisilamine and 200mL tetrahydrofuran were added successively, and the temperature was raised to 65℃with stirring, and the reaction was carried out at constant temperature for 3 hours, and the temperature was lowered to 35℃to obtain a mother liquor.
To a 250mL three-necked flask purged with nitrogen, 12g of silica gel (Cabot Corporation TS-610, particle size 0.02-0.1 μm) was added, the cooled mother liquor was added, the temperature was kept at 35℃and stirred for 1 hour, and after mixing the silica gel, the mother liquor was spray-dried with a spray dryer under spray conditions: the catalyst component was obtained at an inlet temperature of 195℃and an outlet temperature of 110℃with a titanium content of 2.38% by weight and a silica content of 24% by weight.
(2) Slurry polymerization of ethylene
Adding 1L of hexane into a 2L polymerization kettle blown and discharged by nitrogen, simultaneously adding 4mL of 1M triethylaluminum/hexane and 0.02g of the catalyst component in the step (1), heating to 75 ℃, adding 0.18Mpa of hydrogen, adding 0.75Mpa of ethylene after hydrogenation, heating to 85 ℃, reacting for 2 hours, and cooling and discharging. The polymerization results are shown in Table 1.
Example 2
(1) Preparation of the catalyst component
The difference from example 1 is that: the amount of hexamethylcyclotrisilamine used was 5.6mL, and the titanium content of the resulting catalyst component was 2.41wt% and the silica content was 22wt%.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Example 3
(1) Preparation of the catalyst component
The same as in example 1 except that hexamethylcyclotrisilamine was used in an amount of 1.4mL, the titanium content of the obtained catalyst component was 2.35% by weight, and the silica content was 25% by weight.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Example 4
(1) Preparation of the catalyst component
The same as in example 1 except that hexamethylcyclotrisilamine was changed to hexaphenylcyclotrisilamine in an amount of 3.6g, the titanium content of the obtained catalyst component was 2.39% by weight and the silica content was 21% by weight.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Comparative example 1
(1) Preparation of the catalyst component
To a 250mL three-necked flask purged with nitrogen, 3.0g TiC1 4, 8.0g anhydrous MgCl 2 and 200mL tetrahydrofuran were successively added, and the mixture was stirred and heated to 65℃to perform a constant temperature reaction for 3 hours and then cooled to 35℃to obtain a mother liquor.
To a 250mL three-necked flask purged with nitrogen, 12g of silica gel (Cabot Corporation TS-610, particle size 0.02 to 0.1 μm) was added, the cooled mother liquor was added, the temperature was kept at 35℃and stirred for 1 hour, and after mixing the silica gel, the mother liquor was spray-dried with a spray dryer under spray conditions: the catalyst component was obtained at an inlet temperature of 195℃and an outlet temperature of 110℃with a titanium content of 2.2% by weight and a silica content of 25% by weight.
(2) Slurry polymerization of ethylene
1L of hexane is added into a 2L polymerization kettle blown off by nitrogen, 2mL of 1M triethylaluminum/hexane and 0.01g of catalyst are added, the temperature is raised to 75 ℃, 0.18Mpa of hydrogen is added, 0.75Mpa of ethylene is added after the hydrogenation is finished, the temperature is raised to 85 ℃, and the temperature is reduced and the material is discharged after the reaction is carried out for 2 hours. The polymerization results are shown in Table 1.
TABLE 1 catalyst Performance obtained in examples and comparative examples
As can be seen from the polymerization data in Table 1, the catalyst activity of the present invention was higher under the same polymerization conditions, and the resulting polymer had a higher melt index and a lower hexane extractables content.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.
Claims (17)
1. A catalyst component for olefin polymerization, comprising an inorganic oxide and an alkyl cyclosilazane compound, wherein the alkyl cyclosilazane compound is a reaction product of magnesium halide, titanium halide, alkyl cyclosilazane compound and electron donor compound; the alkyl cyclosilazane compound is at least one of hexamethyl cyclosilazane and hexaphenyl cyclosilazane, the electron donating compound is 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, the inorganic oxide is at least one of silicon oxide and aluminum oxide, and the particle size of the inorganic oxide is 0.001-10 mu m; the inorganic oxide content in the catalyst component is 5-50% by mass; the dosage of the magnesium halide is 0.1-15 mol, the dosage of the alkyl cyclosilazane compound is 0.01-10 mol, and the dosage of the electron donor compound is 1-600 mol; the titanium content of the catalyst component is 0.1-5% by mass.
2. The catalyst component according to claim 1, characterized in that,
The inorganic oxide is at least one of alumina and silica; and/or the number of the groups of groups,
The particle size of the inorganic oxide is 0.005-5 mu m; and/or the number of the groups of groups,
The magnesium halide is at least one selected from magnesium chloride, magnesium bromide and magnesium iodide; and/or the number of the groups of groups,
The titanium halide is at least one selected from titanium trichloride, titanium tetrachloride, titanium tribromide and titanium tetrabromide.
3. The catalyst component according to claim 2, characterized in that,
The titanium halide is at least one selected from titanium trichloride and titanium tetrachloride.
4. The catalyst component according to claim 2, characterized in that,
The electron donor compound is at least one selected from methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; and/or the number of the groups of groups,
The inorganic oxide is selected from silica; and/or the number of the groups of groups,
The particle size of the inorganic oxide is 0.01-2 mu m.
5. The catalyst component according to claim 4, characterized in that,
The electron donor compound is at least one selected from methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; and/or the number of the groups of groups,
The inorganic oxide is selected from silica; and/or the number of the groups of groups,
The particle size of the inorganic oxide is 0.01-1 mu m.
6. The catalyst component according to claim 5, characterized in that,
The inorganic oxide content in the catalyst component is 10-30% by mass; and/or the number of the groups of groups,
The dosage of the magnesium halide is 1-10 mol, the dosage of the alkyl cyclosilazane compound is 0.05-8 mol, and the dosage of the electron donor compound is 10-500 mol; and/or the number of the groups of groups,
The titanium content of the catalyst component is 1-3% by mass.
7. The catalyst component according to claim 6, characterized in that,
The inorganic oxide content in the catalyst component is 15-25% by mass; and/or the number of the groups of groups,
The dosage of the magnesium halide is 2-7 mol based on each mol of titanium halide; the dosage of the alkyl cyclosilazane compound is 0.1-3 mol; the dosage of the electron donor compound is 100-200 mol; and/or the number of the groups of groups,
The titanium content of the catalyst component is 1.5-2.5% by mass.
8. A method for preparing the catalyst component for olefin polymerization according to any one of claims 1 to 7, comprising loading a component comprising the alkyl cyclosilazane complex onto the inorganic oxide to obtain the catalyst component.
9. The preparation method according to claim 8, characterized in that the preparation method specifically comprises the following steps:
Step 1, mother liquor preparation: mixing the components comprising the magnesium halide, the titanium halide, the alkyl cyclosilazane compound and the electron donor compound, and heating for reaction to obtain an alkyl cyclosilazane compound mother solution;
step 2, carrier doping: uniformly mixing the alkyl cyclosilazane compound mother liquor obtained in the step 1 with inorganic oxide to obtain slurry;
step 3, spray forming: and (3) drying the slurry obtained in the step (2) to obtain the catalyst component.
10. The method according to claim 9, wherein,
The reaction temperature in the step 1 is 55-80 ℃ and the reaction time is 2-6 h; and/or the number of the groups of groups,
The inorganic oxide content in the slurry in the step 2 is 2-60%; and/or the number of the groups of groups,
The drying in the step 3 is spray drying.
11. The method according to claim 10, wherein,
The inorganic oxide content in the slurry in the step 2 is 5-35%; and/or the number of the groups of groups,
The spray drying conditions include: the inlet temperature is 80-240 ℃, and the outlet temperature is 60-130 ℃.
12. The method according to claim 11, wherein,
The spray drying conditions include: the inlet temperature is 120-220 ℃; the outlet temperature is 90-110 ℃.
13. A catalyst for olefin polymerization comprising: the catalyst component according to any one of claims 1 to 7 or the catalyst component obtained by the production method according to any one of claims 8 to 12, wherein the catalyst for olefin polymerization further comprises an organoaluminum compound.
14. The catalyst of claim 13, wherein the catalyst is,
The general formula of the organic aluminum compound is AlR nX3-n, wherein R is hydrogen or C1-C20 alkyl, X is halogen, and n is more than 0 and less than or equal to 3; and/or the number of the groups of groups,
The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component was 5: 1-500: 1.
15. The catalyst of claim 14, wherein the catalyst is,
The general formula of the organic aluminum compound is AlR nX3-n, wherein R is hydrogen or C1-C6 alkyl, X is halogen, and n is more than 0 and less than or equal to 3; and/or the number of the groups of groups,
The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component was 10: 1-200: 1.
16. The catalyst of claim 15, wherein the catalyst is,
The organic aluminum compound is at least one selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and diethylaluminum chloride.
17. Use of the catalyst of any one of claims 13 to 16 in olefin polymerization.
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