CN116063591B - Metal organic compound catalyst for olefin polymerization and preparation method and application thereof - Google Patents
Metal organic compound catalyst for olefin polymerization and preparation method and application thereof Download PDFInfo
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- CN116063591B CN116063591B CN202111269446.0A CN202111269446A CN116063591B CN 116063591 B CN116063591 B CN 116063591B CN 202111269446 A CN202111269446 A CN 202111269446A CN 116063591 B CN116063591 B CN 116063591B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 16
- -1 aluminum compound Chemical class 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 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
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 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
- 150000001242 acetic acid derivatives Chemical class 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
- 238000001035 drying Methods 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- 229910052740 iodine Chemical group 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
- 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
- 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
- 238000005507 spraying 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
- 150000002484 inorganic compounds Chemical class 0.000 claims 6
- 229910010272 inorganic material Inorganic materials 0.000 claims 6
- KJDHHSOIQUFLQD-UHFFFAOYSA-N [(silylamino)silylamino]silylmethane Chemical compound C[SiH2]N[SiH2]N[SiH3] KJDHHSOIQUFLQD-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
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 16
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- PEGHITPVRNZWSI-UHFFFAOYSA-N [[bis(trimethylsilyl)amino]-dimethylsilyl]methane Chemical compound C[Si](C)(C)N([Si](C)(C)C)[Si](C)(C)C PEGHITPVRNZWSI-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012632 extractable Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- 230000004913 activation Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler 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
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 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
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000000047 product Substances 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
- 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
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000009718 spray deposition Methods 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 olefin polymerization catalysts, and particularly relates to a metal organic compound catalyst for olefin polymerization, which comprises an organic aluminum compound, an inorganic oxide carrier and a metal silazane compound, wherein the metal silazane compound is obtained by reacting magnesium halide, alkyl trisilazane compounds, titanium halide and an oxygen-containing electron donor. The polymer prepared by the metal-organic compound catalyst has higher melt index and low oligomer content.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a metal organic compound catalyst for olefin polymerization, a preparation method and application thereof.
Background
In the homopolymerization of ethylene or the copolymerization of ethylene with alpha-olefins, the performance of the catalyst affects the performance of the polymer. Among the gas phase polyethylene catalysts which are now more representative and in widespread use are the titanium based polyethylene high efficiency catalyst from BP company and the J-type slurry fed polyethylene high efficiency catalyst from Univation company. The AvantZ type of catalyst from barsel company is only used in its SPHERILENE process. Slurry catalyst J-type catalyst (UCAT-J) is developed in the generation of Univation to replace the original M-1 type polyethylene catalyst, and has been popularized and applied at home and abroad, and it is expected that J-type catalyst will replace M-1 type catalyst in the next few years, and becomes a new development direction of UNIPOL technology. The J-type catalyst is developed to overcome the defects of the M-1 type catalyst, and the main components of the J-type catalyst are basically the same as those of the M-1 type catalyst, but have obvious differences in preparation process.
CN106543303a relates to a catalyst component for olefin polymerization, catalyst and preparation method thereof. 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.
Chinese patent CN100368440a discloses a spray-dried polymerization catalyst and a polymerization process employing the same, the catalyst comprising a spray-dried composition of an inert porous filler and the reaction product of: the inert porous filler is substantially spherical and has an average particle size of 1 to 12 μm, and the magnesium halide, the solvent, the oxygen-containing electron donor, the mixture of transition metal compounds, or the reaction product. The catalyst is not high enough in activity and contains many oligomers in the polymer.
Chinese patent CN1493599a discloses an improved catalyst for ethylene polymerization, which is improved in catalyst activity by adding alkyl silicate in the mother liquor preparation of the catalyst active component, and reduces oligomer content in the polymer, but the catalyst activity is not high enough.
Therefore, there is a need to develop a catalyst for olefin polymerization having higher activity and melt index and low oligomer content in the polymer.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a metal-organic composite catalyst for olefin polymerization, comprising an organoaluminum compound, an inorganic oxide carrier, a metal silazane composite, and the catalyst is used for olefin polymerization. The catalyst provided by the invention has high activity, the polymer obtained by polymerization reaction has higher melt index, and the content of the oligomer in the obtained polymer is low.
It is an object of the present invention to provide a metal organic composite catalyst for olefin polymerization, comprising an organoaluminum compound, a metal organic/inorganic composite, wherein the metal organic/inorganic composite comprises an inorganic oxide support and a metal silazane composite.
Specifically, the general formula of the organic aluminum compound is A1R nX3-n, wherein R is hydrogen or C1-C20 alkyl, preferably C1-C8 alkyl; x is halogen, preferably chlorine, bromine, iodine; n is more than 0 and less than or equal to 3;
The inorganic oxide carrier can be selected from inorganic oxide carrier components commonly used in the field, preferably at least one selected from oxides of silicon and aluminum, more preferably at least one selected from aluminum oxide and silicon dioxide, and most preferably silicon dioxide; the particle size of the inorganic oxide support is 0.01 to 10. Mu.m, preferably 0.01 to 5. Mu.m, more preferably 0.01 to 1. Mu.m.
In the metal organic compound catalyst for olefin polymerization, the metal silazane compound is obtained by reacting metal halide, alkyl trisilazane compound and oxygen-containing electron donor, wherein the metal halide comprises magnesium halide and titanium halide.
Wherein 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;
The oxygen-containing electron donor is at least one selected from esters, ethers and ketones, preferably at least one selected from alkyl esters of C1-C6 saturated aliphatic carboxylic acids, alkyl esters of C7-C12 aromatic carboxylic acids, C2-C8 aliphatic ethers, C3-C6 cyclic ethers and C3-C8 saturated aliphatic ketones, more preferably at least one selected from formate compounds, acetate compounds, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; specific examples of the oxygen-containing electron donor 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 general formula of the alkyl trisilazanes is N(SiR1R2R3)(SiR4R5R6)(SiR7R8R9),, wherein R 1、R2、R3、R4、R5、R6、R7、R8、R9 is independently selected from H, C-C5 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C8 cycloalkyl or C6-C10 aryl, preferably selected from C1-C5 alkyl; preferably, the alkyl trisilazane compound is at least one selected from the group consisting of nonamethyl trisilazane and nonaethyl trisilazane.
In the above metal organic composite catalyst for olefin polymerization:
the molar ratio of aluminum in the organoaluminum compound to titanium in the metal silazane compound is 5: 1-500: 1, preferably 10:1 to 200:1, a step of;
The titanium content of the metal organic/inorganic composite is 0.1-5%, preferably 0.5-3% by mass;
The dosage ratio of the inorganic oxide carrier to the metal silazane compound is 1: (1 to 20), preferably 1: (2 to 10), more preferably 1: (3-8);
The magnesium halide is used in an amount of 0.1 to 10mol, preferably 1 to 10mol, more preferably 2 to 7mol, per mol of titanium halide; the amount of the alkyl trisilazane compound is 0.01 to 10mol, preferably 0.1 to 10mol, more preferably 0.1 to 3mol; the amount of the oxygen-containing electron donor is 1 to 600mol, preferably 20 to 200mol, more preferably 100 to 200mol.
The second object of the present invention is to provide a method for preparing the metal-organic composite catalyst, which comprises mixing the components including the inorganic oxide carrier, the metal silazane composite and the organic aluminum compound to obtain the metal-organic composite catalyst. The preparation method specifically comprises the following steps:
Stirring components containing magnesium halide, titanium halide, alkyl trisilazane compounds and oxygen-containing electron donors for reaction to obtain mother liquor;
step (2) adding the mother liquor obtained in the step (1) into the inorganic oxide carrier, and mixing to obtain slurry;
Step (3), spraying and drying the slurry obtained in the step (2) to obtain a compound;
and (4) adding the compound obtained in the step (3) into an organic aluminum compound to obtain the metal organic compound catalyst.
The preparation method comprises the following steps:
The reaction temperature in the step (1) is 50-80 ℃ and the reaction time is 2-5 h;
The spray drying conditions in step (3) include: the inlet temperature is 80-240 ℃, preferably 120-200 ℃; the outlet temperature is 60 to 130 ℃, preferably 90 to 110 ℃.
According to the invention, the inorganic oxide carrier is added, so that the metal silazane compound can be uniformly loaded on the carrier, the activity of catalytic metal is fully exerted, the added inorganic oxide carrier is dry in use, namely, no adsorbed water is generated, a sufficient amount of inorganic oxide carrier is mixed with the mother liquor to form slurry suitable for spray drying, the spray dried compound and the organic aluminum compound are matched for use, and the inorganic oxide carrier can be applied to olefin polymerization reaction including olefin homo-polymerization reaction or copolymerization reaction, preferably, the inorganic oxide carrier content in the slurry is 5-50 wt%, and preferably 10-30 wt%.
The third object of the present invention is to provide an application of the metal-organic composite catalyst or the metal-organic composite catalyst obtained by the preparation method, wherein the metal-organic composite catalyst is used for olefin polymerization. After activating the components comprising the metal organic composite catalyst, olefin polymerization is initiated. The solvent used for the activation is selected from hydrocarbon organic solvents, preferably at least one selected from isopentane, hexane, heptane, toluene, xylene, naphtha, and mineral oil.
In order to make the solid catalyst component obtained after spray-drying suitable for use in producing olefin polymers, an activator component (e.g., an organoaluminum compound) is used to reduce the titanium atom in the catalyst component to a state that allows ethylene to be efficiently polymerized. Generally, the catalyst component described above is reacted with an activator component in a hydrocarbon solvent to obtain a catalyst; the polymerization of olefins may also be initiated after the reaction of the above-described catalyst component with the activator component in a solvent during the polymerization process. The catalyst of the invention is suitable for homo-polymerization of various kinds of ethylene or 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 invention provides a metal organic compound catalyst for olefin polymerization, which takes inorganic oxide with a specific particle size range as a carrier, adopts an oxygen-containing electron donor to dissolve metal halide, adds alkyl trisilazane compounds to react to prepare mother liquor, finally adopts a spray forming mode to prepare catalyst components, and then obtains a high-activity catalyst through activation. The nitrogen atom in the alkyl trisilazane compound contains lone pair electrons, has a strong electron donating effect, 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, 2.0gTiCl 4 g anhydrous MgCl 2, 1.8g nonamethyltrisilazane, 10mL mineral oil and 130mL tetrahydrofuran were successively added, and the mixture was heated to 65℃with stirring, allowed to react at constant temperature for 3 hours, and cooled to 35℃to give a mother liquor.
Adding 8 g of silica gel (CabotCorporation TS-610 with the particle size of 0.02-0.1 um) into a 250mL three-necked flask blown out by nitrogen, adding the cooled mother solution, maintaining the temperature at 35 ℃, stirring for 1 hour, and then spray-drying the mother solution obtained by mixing the silica gel by a spray dryer under the 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
1L of hexane is added into a 2L polymerization kettle blown and discharged by nitrogen, 4mL 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.
Example 2
(1) Preparation of the catalyst component
The difference from example 1 is that: the amount of nonamethyltrisilazane used was 3.7g, and the titanium content of the resulting catalyst component was 2.42% by weight, and the silica content was 23% by weight.
(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 the amount of nonamethyltrisilazane used was 0.9g, the titanium content of the resulting catalyst component was 2.31% 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 nonamethyltrisilazane was changed to nonaethyltrisilazane in an amount of 1.5g, the titanium content of the obtained catalyst component was 2.37% 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, 2.0g TiC1 4, 5.3g anhydrous MgCl 2, 10mL mineral oil and 130mL tetrahydrofuran were successively added, and the mixture was stirred and heated to 65℃to perform a constant temperature reaction for 3 hours, and the temperature was lowered to 35℃to obtain a mother liquor.
Adding 8g of silica gel (CabotCorporation TS-610 with the particle size of 0.02-0.1 micron) into a 250mL three-necked flask blown out by nitrogen, adding the cooled mother solution, maintaining the temperature at 35 ℃, stirring for 1 hour, and then spray-drying the mother solution obtained by mixing the silica gel by a spray dryer under the 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 (14)
1. A metal organic compound catalyst for olefin polymerization, comprising an organic aluminum compound and a metal organic/inorganic compound, wherein the metal organic/inorganic compound comprises an inorganic oxide carrier and a metal silazane compound, the metal silazane compound is obtained by reacting a metal halide, an alkyl trisilazane compound and an oxygen-containing electron donor, and the metal halide comprises magnesium halide and titanium halide; the general formula of the organic aluminum compound is A1R 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; the inorganic oxide carrier is at least one selected from silicon oxide and aluminum oxide, and the particle size of the inorganic oxide carrier is 0.01-10 mu m; the oxygen-containing electron donor is at least one selected from formate compounds, acetate compounds, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; the alkyl trisilazane compound is at least one selected from the group consisting of nine methyl trisilazane and nine ethyl trisilazane.
2. The catalyst of claim 1, wherein the catalyst is,
The organic aluminum compound has a general formula of A1R nX3-n, wherein R is C1-C8 alkyl; x is chlorine, bromine or iodine; n is more than 0 and less than or equal to 3; and/or the number of the groups of groups,
The inorganic oxide carrier is at least one selected from alumina and silica; and/or the number of the groups of groups,
The particle size of the inorganic oxide carrier is 0.01-5 mu m.
3. A catalyst according to claim 2, wherein,
The inorganic oxide carrier is selected from silicon dioxide; and/or the number of the groups of groups,
The particle size of the inorganic oxide carrier is 0.01-1 mu m.
4. The catalyst of claim 1, wherein the catalyst is,
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.
5. The catalyst according to claim 4, wherein,
The titanium halide is at least one selected from titanium trichloride and titanium tetrachloride.
6. The catalyst of claim 1, wherein the catalyst is,
The oxygen-containing electron donor is at least one selected from 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.
7. The catalyst of claim 1, wherein the catalyst is,
The molar ratio of aluminum in the organoaluminum compound to titanium in the metal silazane compound is 5: 1-500: 1, a step of; and/or the number of the groups of groups,
The titanium content of the metal organic/inorganic compound is 0.1-5% by mass percent; and/or the number of the groups of groups,
The dosage ratio of the inorganic oxide carrier to the metal silazane compound is 1: (1-20); and/or the number of the groups of groups,
The magnesium halide is used in an amount of 0.1 to 10mol per mol of titanium halide; the dosage of the alkyl trisilazane compound is 0.01-10 mol; the dosage of the oxygen-containing electron donor is 1-600 mol.
8. The catalyst of claim 7, wherein the catalyst is,
The molar ratio of aluminum in the organoaluminum compound to titanium in the metal silazane compound is 10:1 to 200:1, a step of; and/or the number of the groups of groups,
The titanium content of the metal organic/inorganic compound is 0.5-3% by mass percent; and/or the number of the groups of groups,
The dosage ratio of the inorganic oxide carrier to the metal silazane compound is 1: (2-10); and/or the number of the groups of groups,
The magnesium halide is used in an amount of 1 to 10mol per mol of titanium halide; the dosage of the alkyl trisilazane compound is 0.1-10 mol; the dosage of the oxygen-containing electron donor is 20-200 mol.
9. The catalyst of claim 8, wherein the catalyst is,
The dosage ratio of the inorganic oxide carrier to the metal silazane compound is 1: (3-8); and/or the number of the groups of groups,
The magnesium halide is used in an amount of 2 to 7mol per mol of titanium halide; the dosage of the alkyl trisilazane compound is 0.1-3 mol; the dosage of the oxygen-containing electron donor is 100-200 mol.
10. A method for preparing a metal-organic composite catalyst according to any one of claims 1 to 9, comprising mixing components comprising the inorganic oxide carrier, the metal silazane composite and the organic aluminum compound to obtain the metal-organic composite catalyst.
11. The preparation method according to claim 10, characterized in that it comprises in particular the following steps:
Stirring components containing magnesium halide, titanium halide, alkyl trisilazane compounds and oxygen-containing electron donors for reaction to obtain mother liquor;
Step (2), adding the mother liquor obtained in the step (1) into an inorganic oxide carrier, and mixing to obtain slurry;
step (3), spraying and drying the slurry obtained in the step (2) to obtain a metal organic/inorganic compound;
And (4) adding the metal organic/inorganic compound obtained in the step (3) into an organic aluminum compound to obtain the metal organic compound catalyst.
12. The method according to claim 11, wherein,
The reaction temperature in the step (1) is 50-80 ℃ and the reaction time is 2-5 h; and/or the number of the groups of groups,
The spray drying conditions in step (3) include: the inlet temperature is 80-240 ℃; the outlet temperature is 60-130 ℃.
13. The method according to claim 12, wherein,
The spray drying conditions in step (3) include: the inlet temperature is 120-200 ℃; the outlet temperature is 90-110 ℃.
14. A metal-organic composite catalyst according to any one of claims 1 to 9 or a metal-organic composite catalyst obtained by the production process according to any one of claims 10 to 13 for olefin polymerization.
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| CN1321111A (en) * | 1999-09-16 | 2001-11-07 | 出光石油化学株式会社 | Transition metal catalysts and processes for producing alpha-olefin and vinyl compound polymer |
| CN104245132A (en) * | 2012-04-17 | 2014-12-24 | 莫门蒂夫性能材料股份有限公司 | High activity catalyst for hydrosilylation reactions and methods of making the same |
| CN106543316A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | For the catalytic component of olefinic polymerization, catalyst and preparation method thereof |
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| CN1321111A (en) * | 1999-09-16 | 2001-11-07 | 出光石油化学株式会社 | Transition metal catalysts and processes for producing alpha-olefin and vinyl compound polymer |
| CN104245132A (en) * | 2012-04-17 | 2014-12-24 | 莫门蒂夫性能材料股份有限公司 | High activity catalyst for hydrosilylation reactions and methods of making the same |
| CN106543316A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | For the catalytic component of olefinic polymerization, catalyst and preparation method thereof |
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