CN115197346A - Catalyst for olefin polymerization, preparation method and application thereof - Google Patents
Catalyst for olefin polymerization, preparation method and application thereof Download PDFInfo
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- CN115197346A CN115197346A CN202110379577.8A CN202110379577A CN115197346A CN 115197346 A CN115197346 A CN 115197346A CN 202110379577 A CN202110379577 A CN 202110379577A CN 115197346 A CN115197346 A CN 115197346A
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- catalyst
- magnesium
- titanium
- halide
- magnesium halide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 magnesium halide Chemical class 0.000 claims abstract description 52
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 47
- 239000011777 magnesium Substances 0.000 claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- 239000003607 modifier Substances 0.000 claims abstract description 20
- 239000012442 inert solvent Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 24
- 238000007259 addition reaction Methods 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 14
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 14
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- 229920013716 polyethylene resin Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000000877 morphologic effect Effects 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 239000005968 1-Decanol Substances 0.000 claims description 3
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- MBTRTTIWMFMDQR-UHFFFAOYSA-M magnesium;butan-1-olate;bromide Chemical compound [Br-].CCCCO[Mg+] MBTRTTIWMFMDQR-UHFFFAOYSA-M 0.000 claims description 3
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 claims description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 3
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 3
- SWMSUKCRKOWDGN-UHFFFAOYSA-M magnesium;ethanolate;bromide Chemical compound [Br-].CCO[Mg+] SWMSUKCRKOWDGN-UHFFFAOYSA-M 0.000 claims description 3
- KRTCPMDBLDWJQY-UHFFFAOYSA-M magnesium;ethanolate;chloride Chemical compound [Mg+2].[Cl-].CC[O-] KRTCPMDBLDWJQY-UHFFFAOYSA-M 0.000 claims description 3
- WIMVJXDEZAGHEM-UHFFFAOYSA-M magnesium;methanolate;bromide Chemical compound [Br-].CO[Mg+] WIMVJXDEZAGHEM-UHFFFAOYSA-M 0.000 claims description 3
- ZHLDMBMNKCIBQN-UHFFFAOYSA-M magnesium;methanolate;chloride Chemical compound [Cl-].CO[Mg+] ZHLDMBMNKCIBQN-UHFFFAOYSA-M 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 11
- 239000000835 fiber Substances 0.000 abstract description 10
- 230000000379 polymerizing effect Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—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 provides a catalyst for olefin polymerization, a preparation method and application thereof. The preparation method comprises the following steps: under an inert atmosphere, S1, sequentially adding magnesium halide and alcohol into an inert solvent to obtain a solution of a magnesium halide-alcohol adduct; s2, adding a metal aluminum organic compound into the solution of the magnesium halide-alcohol adduct to form an intermediate product A; s3, mixing the intermediate product A with a morphology modifier to obtain a morphology-modified intermediate product A; and S4, mixing the intermediate product A with the modified form with a titanium halide compound, and drying to obtain the catalyst for olefin polymerization. Based on the synergistic cooperation of the steps in the preparation method, when the prepared catalyst for olefin polymerization is used for synthesizing resin for polymerizing fiber, the catalyst has better catalytic activity, more uniform and concentrated distribution of active centers and more stable release of activity in the application process. Meanwhile, the catalyst has longer service life, is not easy to agglomerate, has higher polymerization stability and is more beneficial to industrialized implementation.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a catalyst for olefin polymerization, and a preparation method and application thereof.
Background
The special resin for fiber requires high viscosity average molecular weight, narrow molecular weight distribution and uniform particle size distribution of the resin. CN1033703C provides a method for preparing ultra-high molecular weight polyethylene with adjustable molecular weight. This patent employs MgCl 2 And ZnCl 2 The composite carrier carries titanium catalyst, and the molecular weight of the composite carrier is adjustable between 60 and 610 ten thousand and the particle size distribution is good at 65 to 85 DEG CThe invention regulates and controls the molecular weight of the product by adjusting the Zn/Ti molar ratio. However, the catalyst used in this patent is a composite supported catalyst and the resin obtained by polymerization is not directed to fiber applications. CN1149060A discloses a metallocene catalyst for synthesizing high molecular weight polyethylene and a preparation method thereof, wherein a main catalyst is prepared by reacting a compound which is generated by transition metal halide in tetrahydrofuran and has two molecular tetrahydrofuran with dilithium salt of 1, 3-bis (1-indenyl) disiloxyl. The catalyst has high activity in ethylene polymerization or ethylene-alpha-olefin (alpha-olefin containing 3-12 carbon atoms) copolymerization, and the polymer is low-density polyethylene with ultrahigh molecular weight and high melting point of 120-140 ℃. However, the catalyst used in this patent is a metallocene catalyst and the development of fiber specific resins is not described.
In summary, the catalysts used for polymerizing ultra-high molecular weight polyethylene in the prior art have the disadvantages of short service life, easy agglomeration and poor polymerization stability when used for polymerizing fiber-use resins, and are not beneficial to industrial implementation. Therefore, there is a need for a catalyst for olefin polymerization, which has excellent properties of long life, less caking, and high polymerization stability while satisfying high catalytic activity when applied to a resin for fiber polymerization.
Disclosure of Invention
The invention mainly aims to provide a catalyst for olefin polymerization, a preparation method and application thereof, and aims to solve the problems that the catalyst for polymerizing ultrahigh molecular weight polyethylene in the prior art is short in service life, easy to agglomerate, poor in polymerization stability and not beneficial to industrial implementation when used for polymerizing fiber-purpose resin.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a catalyst for olefin polymerization. The preparation method comprises the following steps: under an inert atmosphere, S1, sequentially adding magnesium halide and alcohol into an inert solvent to carry out a first addition reaction to obtain a solution of a magnesium halide-alcohol adduct; s2, adding a metal aluminum organic compound into the solution of the magnesium halide-alcohol adduct to perform a second addition reaction to form an intermediate product A; s3, mixing the intermediate product A with a morphology modifier to perform morphology modification treatment to obtain a morphology-modified intermediate product A; s4, mixing the intermediate product A with the modified form with a titanium halide compound to carry out titanium carrying, and drying to obtain the catalyst for olefin polymerization; wherein the form modifier is one or more of methyl ether, methyl ethyl ether, ethyl propyl ether, n-propyl ether, isopropyl ether, n-butyl ether, ethylene oxide or tetrahydrofuran.
Further, the molar ratio of the morphology modifier to the magnesium halide is (0.1-1): 1.
Further, in the morphological modification treatment process, the treatment temperature is 20-90 ℃, and preferably 20-50 ℃; the treatment time is 1 to 10 hours, preferably 1 to 5 hours.
Further, in the first addition reaction, the reaction temperature is 5-130 ℃, preferably 30-100 ℃; the reaction time is 0.5 to 8 hours, preferably 1 to 5 hours.
Further, in the second addition reaction, the reaction temperature is 0-80 ℃, preferably 0-60 ℃; the reaction time is 0.5 to 5 hours, preferably 1 to 3 hours.
Further, in the titanium-carrying, the reaction temperature is 0-60 ℃, preferably 0-30 ℃; the reaction time is 1 to 10 hours, preferably 1 to 5 hours.
Further, the inert atmosphere is nitrogen, argon or helium, preferably nitrogen; more preferably, the flow rate of the inert gas atmosphere is 100 to 1000mL/min.
Further, the magnesium halide is one or more of magnesium dihalide, C1-C6 alkoxy magnesium halide or C1-C6 alkyl magnesium halide; preferably, the magnesium halide is one or more of magnesium dichloride, magnesium dibromide, methyl magnesium chloride, methyl magnesium bromide, methoxy magnesium chloride, methoxy magnesium bromide, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium chloride or butoxy magnesium bromide.
Further, the inert solvent is C5-C12 aliphatic hydrocarbon solvent or aromatic hydrocarbon solvent.
Preferably, the inert solvent is two or more of n-pentane, n-hexane, n-heptane, n-octane, and n-decane.
Preferably, the inert solvent is used in an amount of 1 to 20L/mol, preferably 1 to 10L/mol, per mole of magnesium halide.
Further, the alcohol is an alcohol having 2 to 20 carbon atoms, preferably an alcohol having 2 to 10 carbon atoms, more preferably one or more of ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 1-octanol, isooctanol, 1-decanol, cyclohexanol, or 2-methyl-1-propanol.
Preferably, the molar ratio of alcohol to magnesium halide per mole is (1-10): 1, preferably (1-5): 1.
Further, the general formula of the metal aluminum organic compound is R n AlX 3-n Wherein R is alkyl with 1-10 carbon atoms, X is halogenated group, and n is more than or equal to 1 and less than or equal to 3.
Preferably, the metalaluminium organic compound is trimethylaluminium, triethylaluminium, diethylaluminium monochloride or ethylaluminium dichloride, more preferably triethylaluminium.
Preferably, the molar ratio of the metal aluminum organic compound to the magnesium halide is (0.5-5): 1.
Further, the titanium halide compound has the general formula of TiX 4 Wherein X is halogen.
Preferably, the titanium halide compound is titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, or titanium tetraiodide, more preferably titanium tetrachloride.
Preferably, the molar ratio of the titanium compound to the magnesium halide is (1-10): 1.
According to another aspect of the present invention, there is provided a catalyst for olefin polymerization, which is produced according to the above-mentioned production method.
According to another aspect of the invention, the catalyst for olefin polymerization is applied to the process of preparing the polyethylene resin by the Hoechst slurry polymerization process.
Further, the polyethylene resin has a viscosity average molecular weight of 3000000 to 8000000, a molecular weight distribution index of 5.0 to 10.0, and a bulk density of 0.35 to 0.45g/cm 3 The median diameter D50 is 120 to 260 mu m.
Based on the synergistic cooperation of the steps in the preparation method, when the catalyst for olefin polymerization prepared by the invention is used for polymerizing fiber resin, the catalyst has better catalytic activity, more uniform and concentrated distribution of active centers and more stable release of activity in the application process. Meanwhile, the catalyst has longer service life, is not easy to agglomerate, has higher polymerization stability and is more beneficial to industrialized implementation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a morphological analysis of a catalyst for olefin polymerization according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background of the invention, the catalysts used for polymerizing ultra-high molecular weight polyethylene in the prior art have the disadvantages of short service life, easy agglomeration and poor polymerization stability when used for polymerizing resin for fiber application, and are not beneficial to industrial implementation. In order to solve the problem, the invention provides a preparation method of a catalyst for olefin polymerization, which comprises the following steps: under an inert atmosphere, S1, sequentially adding magnesium halide and alcohol into an inert solvent to carry out a first addition reaction to obtain a solution of a magnesium halide-alcohol adduct; s2, adding a metal aluminum organic compound into the solution of the magnesium halide-alcohol adduct to perform a second addition reaction to form an intermediate product A; s3, mixing the intermediate product A with a morphology modifier to perform morphology modification treatment to obtain a morphology-modified intermediate product A; s4, mixing the intermediate product A with the modified form with a titanium halide compound to carry out titanium carrying, and drying to obtain the catalyst for olefin polymerization; wherein the form modifier is one or more of methyl ether, methyl ethyl ether, ethyl propyl ether, n-propyl ether, isopropyl ether, n-butyl ether, ethylene oxide or tetrahydrofuran.
Firstly, the invention reacts magnesium halide and alcohol in inert solvent to form magnesium halide-alcohol adduct solution, wherein the inert solvent can dilute the reaction system, which is beneficial to promoting the reaction to proceed forward and does not participate in the reaction, and does not have adverse effect on the dissolution of the magnesium halide. Secondly, the method adds a metal aluminum organic compound into a solution of a magnesium halide-alcohol adduct to carry out a second addition reaction to form an intermediate product A, and then mixes the intermediate product A and a morphology modifier to carry out a morphology modification treatment to obtain a morphology-modified intermediate product A. Therefore, the prepared catalyst has the advantages that the active centers are uniformly distributed, the activity release of the catalyst is more stable in the using process, the service life of the catalyst is longer, and the industrial production is facilitated. Finally, the intermediate product A after the shape modification is mixed with a titanium halide compound to carry titanium, and the mixture is dried to obtain the catalyst for olefin polymerization. It should be emphasized that, in the two addition reactions and the morphology modification treatment, due to the addition of the solvent compound, the raw materials inevitably carry trace impurities, such as water, benzene, sulfur, etc., which affect the forward progress of the subsequent titanium-carrying catalyst, thereby reducing the activity of the catalyst and being not beneficial to the completeness of the catalyst morphology. The invention improves the reaction steps, firstly carries out the addition reaction of the alkyl of the organic aluminum, and then carries out the titanium loading, thus a small part of the alkyl of the organic aluminum can react with impurities in the reaction system, such as water, and a large part of the alkyl of the organic aluminum can also play a role of a catalyst active center protector. Thus, the titanium carrying after the impurity is removed in advance can effectively avoid the negative influence on the activity and the shape of the catalyst, and promote the catalyst to have better catalytic activity, better shape and sphere-like shape (as shown in figure 1). The catalyst is subsequently applied to the process of preparing the polyethylene resin by the Hoechst slurry polymerization process, and the prepared polyethylene resin has better shape, higher bulk density and more uniform and concentrated particle size distribution. In addition, the steps of the preparation method are all carried out in inert atmosphere, so that the system is in an anhydrous and anaerobic state in the whole catalyst preparation process, and the activity and stability of the catalyst are protected as much as possible.
In conclusion, based on the synergistic cooperation of the steps, when the catalyst for olefin polymerization prepared by the invention is used for polymerizing fiber resin, the catalyst has better catalytic activity, more uniform and concentrated distribution of active centers and more stable release of activity in the application process. Meanwhile, the catalyst has longer service life, is not easy to agglomerate, has higher polymerization stability and is more beneficial to industrial implementation.
In a preferred embodiment, the above steps of the preparation process of the present invention are all carried out under mechanical stirring at a speed of 100 to 1000r/min, preferably 100 to 500r/min. Thus, the reaction in each step in the preparation process can be further promoted to be complete.
Preferably, the molar ratio of the morphology modifier to the magnesium halide is (0.1-1): 1. Therefore, the prepared catalyst can be further promoted to be more uniformly distributed, the activity release is more stable in the subsequent application process, the service life is longer, and the industrial production is more facilitated.
In order to further improve the distribution uniformity of the active centers of the catalyst and further avoid the agglomeration phenomenon of the catalyst in the subsequent polymerization reaction, the treatment temperature is 20-90 ℃, preferably 20-50 ℃ in the form modification treatment process; the treatment time is 1 to 10 hours, preferably 1 to 5 hours.
In a preferred embodiment, the first addition reaction is carried out at a temperature of from 5 to 130 ℃ and preferably from 30 to 100 ℃; the reaction time is 0.5 to 8 hours, preferably 1 to 5 hours. Within the range, the prepared catalyst has better shape and lower energy consumption, and is more beneficial to industrial implementation.
Preferably, in the second addition reaction, the reaction temperature is 0-80 ℃, and preferably 0-60 ℃; the reaction time is 0.5 to 5 hours, preferably 1 to 3 hours. Therefore, impurities in the reaction system can be further removed, so that the prepared catalyst has better form, and the polyethylene resin prepared by the catalyst has better form, higher bulk density and more uniform and concentrated particle size distribution when being applied to polymerization reaction subsequently.
For the purpose of further balancing the activity and stability of the catalyst, the reaction temperature in the titanium carrier is 0-60 ℃, preferably 0-30 ℃; the reaction time is 1 to 10 hours, preferably 1 to 5 hours.
For the purpose of further improving the activity and stability of the catalyst, the inert atmosphere is nitrogen, argon or helium, preferably nitrogen; the flow rate of the inert gas atmosphere is preferably 100 to 1000mL/min, and more preferably 600 to 800mL/min.
For the purpose of further improving the stability of the catalyst, further prolonging the service life of the catalyst when the catalyst is applied to the subsequent polymerization reaction and improving the polymerization stability, the magnesium halide is preferably one or more of magnesium dihalide, C1-C6 alkoxy magnesium halide or C1-C6 alkyl magnesium halide; preferably, the magnesium halide is one or more of magnesium dichloride, magnesium dibromide, methyl magnesium chloride, methyl magnesium bromide, methoxy magnesium chloride, methoxy magnesium bromide, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium chloride or butoxy magnesium bromide. Preferably, the alcohol is an alcohol having 2 to 20 carbon atoms, preferably an alcohol having 2 to 10 carbon atoms, more preferably one or more of ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 1-octanol, isooctanol, 1-decanol, cyclohexanol or 2-methyl-1-propanol; preferably, the molar ratio of alcohol to magnesium halide is (1-10): 1, preferably (1-5): 1, per mole.
Preferably, the inert solvent is a C5-C12 aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent; preferably, the inert solvent is two or more of n-pentane, n-hexane, n-heptane, n-octane and n-decane; preferably, the inert solvent is used in an amount of 1 to 20L/mol, preferably 1 to 10L/mol, per mole of magnesium halide. Therefore, the forward progress of the reaction can be further promoted to be better, no interference is generated on the reaction system, and the subsequent drying treatment process is easier to remove.
For the purpose of further improving the activity of the catalyst, it is preferred that the metalloalumino-organic compound has the formula R n AlX 3-n Wherein R is alkyl with 1-10 carbon atoms, X is halogenated group, n is more than or equal to 1 and less than or equal to 3; preferably, the metalaluminium organic compound is trimethylaluminium, triethylaluminium, diethylaluminium monochloride or ethylaluminium dichloride, more preferably triethylaluminium; preferably, the molar ratio of the metal aluminum organic compound to the magnesium halide is (0.5-5): 1. Preferably, titanium halide compoundsThe general formula is TiX 4 Wherein, X is halogen; preferably, the titanium halide compound is titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, or titanium tetraiodide, more preferably titanium tetrachloride; preferably, the molar ratio of the titanium compound to the magnesium halide is (1-10): 1.
The invention also provides a catalyst for olefin polymerization, which is characterized in that the catalyst for olefin polymerization is prepared by the preparation method.
Based on the reasons, the catalyst for olefin polymerization prepared by the invention has longer service life, is not easy to agglomerate and has higher polymerization stability when being used for polymerizing resin for fiber application, thereby being more beneficial to industrialized implementation. The prepared catalyst has the advantages of uniform distribution of active centers, stable activity release of the catalyst in the use process, long service life of the catalyst and contribution to industrial production.
The invention also provides a process for preparing the polyethylene resin by applying the catalyst for olefin polymerization to a polymerization process of a Hoechst slurry method.
Based on the reasons, the catalyst for olefin polymerization prepared by the invention can be used in the process of preparing polyethylene resin by a Hoechst slurry polymerization process, and has the advantages of stable activity release, longer service life, difficult agglomeration, higher polymerization stability and more contribution to industrial implementation. Preferably, the polyethylene resin has a viscosity average molecular weight of 3000000 to 8000000, a molecular weight distribution index of 5.0 to 10.0, and a bulk density of 0.35 to 0.45g/cm 3 The median diameter D50 is 120 to 260 mu m. Based on this, the polyethylene resin is more beneficial to the spinning processing test in the later period.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the present application as claimed.
Example 1
The preparation process of the catalyst for olefin polymerization is as follows:
under nitrogen (flow rate 600 mL/min):
1. adding 0.05mol of anhydrous magnesium chloride into a 500ml three-neck flask, adding 100ml of inert solvent toluene, and uniformly stirring at the stirring speed of 500r/min;
2. then adding 0.1mol of 1-propanol to carry out a first addition reaction, and reacting for 2 hours at 60 ℃ to obtain a solution of a magnesium chloride-alcohol adduct; wherein the molar ratio of the 1-propanol to the anhydrous magnesium chloride is 2;
3. keeping the reaction temperature at 60 ℃, adding 0.025mol of triethyl aluminum for a second addition reaction, and reacting for 2 hours to form an intermediate product A; wherein the molar ratio of triethyl aluminum to anhydrous magnesium chloride is 0.5;
4. cooling to 30 ℃, adding 0.02mmol of each of a morphology modifier methyl ethyl ether and tetrahydrofuran to perform morphology modification treatment for 1h to obtain a morphology-modified intermediate product A; wherein the molar ratio of the morphological modifier to the anhydrous magnesium chloride is 0.8;
5. keeping the temperature at 30 ℃ unchanged, slowly adding 0.2mol of titanium tetrachloride, and carrying out titanium carrying for 2h; wherein the molar ratio of titanium tetrachloride to anhydrous magnesium chloride is 4;
6. the stirring was stopped, and after standing for 30 minutes, the supernatant liquid was taken out, and the solid particles were dried to obtain an olefin polymerization catalyst.
Example 2
The only difference from example 1 is that: the consumption of the anhydrous magnesium chloride is 0.04mol; the dosage of the 1-propanol is 0.08mol; the dosage of triethyl aluminum is 0.03mol; the amount of titanium tetrachloride used was 0.4mol. Wherein the molar ratio of triethyl aluminum to anhydrous magnesium chloride is 0.75; the molar ratio of the morphology modifier to the anhydrous magnesium chloride is 1; the molar ratio of titanium tetrachloride to anhydrous magnesium chloride is 10.
Example 3
The only difference from example 1 is that:
in the step 1, the consumption of anhydrous magnesium chloride is 0.01mol, and the consumption of an inert solvent toluene is 300ml;
in the step 2, the using amount of the 1-propanol is 0.05mol, the reaction temperature is 100 ℃, and the reaction time is 5 hours;
in the step 3, the reaction temperature is 0 ℃, the using amount of triethyl aluminum is 0.01mol, and the reaction time is 3h;
in the step 4, the treatment temperature is 20 ℃, and the treatment time is 2 hours;
in the step 5, the reaction temperature is 20 ℃, the usage amount of titanium tetrachloride is 0.1mol, and the reaction time is 5 hours;
wherein the molar ratio of 1-propanol to anhydrous magnesium chloride is 5; the molar ratio of titanium tetrachloride to anhydrous magnesium chloride is 10.
Example 4
The only difference from example 1 is that:
in the step 1, the consumption of anhydrous magnesium chloride is 0.02mol, the consumption of an inert solvent toluene is 200ml, and the stirring speed is 200r/min;
in the step 2, the dosage of the 1-propanol is 0.02mol, the reaction temperature is 30 ℃, and the reaction time is 1h;
in the step 3, the dosage of the triethyl aluminum is 0.01mol;
in the step 4, 0.01mmol of each of the morphology modifier methyl ethyl ether and tetrahydrofuran is adopted, the treatment temperature is 40 ℃, and the treatment time is 2 hours;
in the step 5, the reaction time is 1h;
wherein the molar ratio of 1-propanol to anhydrous magnesium chloride is 1; the molar ratio of the morphology modifier to the anhydrous magnesium chloride is 1; the molar ratio of titanium tetrachloride to anhydrous magnesium chloride was 10.
Example 5
The only difference from example 1 is that the morphology modifier is diethyl ether and ethylene oxide, each 0.02mmol.
Example 6
The difference from the example 1 is only that the morphology modifier is 0.01mmol of each of ethyl ether, n-propyl ether and isopropyl ether, wherein the molar ratio of the morphology modifier to anhydrous magnesium chloride is 0.6.
Example 7
The only difference from example 1 is that the morphology modifier was dimethyl ether and n-butyl ether, each in an amount of 0.02mmol.
Example 8
The only difference from example 1 is the first addition reaction, the reaction temperature is 5 ℃ and the reaction time is 5h.
Example 9
The only difference from example 1 is the first addition reaction, the reaction temperature is 130 ℃ and the reaction time is 3h.
Example 10
The only difference from example 1 is that the reaction temperature is 0 ℃ and the reaction time is 2h.
Example 11
The only difference from example 1 is that the reaction temperature is 60 ℃ and the reaction time is 3h.
Example 12
The only difference from example 1 is the second addition reaction, the reaction temperature is 80 ℃ and the reaction time is 2h.
Example 13
The only difference from example 1 is that the treatment temperature was 90 ℃ and the treatment time was 1 hour during the morphological modification treatment.
Example 14
The only difference from example 1 is that the treatment temperature was 50 ℃ and the treatment time was 3 hours during the morphological modification treatment.
Example 15
The only difference from example 1 is that triethylaluminium is used in an amount of 0.25mol and the molar ratio of triethylaluminium to anhydrous magnesium chloride is 5.
Comparative example 1
Preparation of the catalyst:
in the presence of high purity N 2 In the fully displaced reactor, 0.042mol of anhydrous MgCl is added in sequence 2 0.39mol of n-decane, 0.14mol of 2-ethylhexanol was added under stirring, the temperature was raised to 130 ℃ and maintained for 1.5 hours, the solution was cooled to 60 ℃ and 0.0026mol of benzoyl chloride was added, the solution was cooled to-10 ℃, 0.36mol of titanium tetrachloride was dropped thereinto and maintained for 70 minutes, then the temperature was raised to 110 ℃ and maintained for 1 hour, and after filtration, washing with hexane was carried out 4 times, and vacuum-drying was carried out to obtain a solid catalyst component.
And (3) performance characterization:
(1) Topography analysis
The particle morphology of the catalyst was observed by using a Japanese JSM-6701F electron scanning electron microscope at 300 times magnification, as shown in FIG. 1.
(2) The catalysts in the above examples and comparative examples are applied to a Hoechst slurry polymerization process to prepare the special resin for polyethylene fibers:
n for polymerizers 2 Starting stirring after replacement, adding solvent oil, and sequentially adding alkyl aluminum and a catalyst in the process; circulating in a boiling water bath, heating a polymerization kettle, introducing a polymerization monomer for polymerization reaction, stopping the reaction after 1-5 h, cooling and discharging, separating and drying polymer slurry to obtain polyethylene resin solid powder, wherein the performance test is shown in the following table 1:
TABLE 1
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A method for preparing a catalyst for olefin polymerization, comprising the steps of: under the condition of inert atmosphere,
s1, sequentially adding magnesium halide and alcohol into an inert solvent to perform a first addition reaction to obtain a solution of a magnesium halide-alcohol adduct;
s2, adding a metal aluminum organic compound into the solution of the magnesium halide-alcohol adduct to perform a second addition reaction to form an intermediate product A;
s3, mixing the intermediate product A with a morphology modifier to perform morphology modification treatment to obtain a morphology-modified intermediate product A;
s4, mixing the intermediate product A after the morphological modification with a titanium halide compound to carry out titanium carrying, and drying to obtain the catalyst for olefin polymerization;
wherein the form modifier is one or more of methyl ether, methyl ethyl ether, ethyl propyl ether, n-propyl ether, isopropyl ether, n-butyl ether, ethylene oxide or tetrahydrofuran.
2. The method according to claim 1, wherein the molar ratio of the morphology modifier to the magnesium halide is (0.1 to 1): 1.
3. The method according to claim 1 or 2, wherein the morphology modification treatment is carried out at a temperature of 20 to 90 ℃, preferably 20 to 50 ℃; the treatment time is 1 to 10 hours, preferably 1 to 5 hours.
4. The method according to claim 1, wherein the first addition reaction is carried out at a reaction temperature of 5 to 130 ℃, preferably 30 to 100 ℃; the reaction time is 0.5 to 8 hours, preferably 1 to 5 hours.
5. The method according to claim 1, wherein the second addition reaction is carried out at a reaction temperature of 0 to 80 ℃, preferably 0 to 60 ℃; the reaction time is 0.5 to 5 hours, preferably 1 to 3 hours.
6. The method according to any one of claims 1 to 5, wherein the reaction temperature during the titanium loading is 0 to 60 ℃, preferably 0 to 30 ℃; the reaction time is 1 to 10 hours, preferably 1 to 5 hours.
7. The method according to any one of claims 1 to 6, wherein the inert atmosphere is nitrogen, argon or helium, preferably nitrogen; preferably, the flow rate of the inert atmosphere is 100 to 1000mL/min.
8. The preparation method according to any one of claims 1 to 6, wherein the magnesium halide is one or more of magnesium dihalide, C1-C6 alkoxy magnesium halide or C1-C6 alkyl magnesium halide; preferably, the magnesium halide is one or more of magnesium dichloride, magnesium dibromide, methyl magnesium chloride, methyl magnesium bromide, methoxy magnesium chloride, methoxy magnesium bromide, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium chloride or butoxy magnesium bromide.
9. The production method according to any one of claims 1 to 6, wherein the inert solvent is a C5-C12 aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent;
preferably, the inert solvent is two or more of n-pentane, n-hexane, n-heptane, n-octane and n-decane;
preferably, the inert solvent is used in an amount of 1 to 20L/mol, preferably 1 to 10L/mol, per mole of the magnesium halide.
10. The production method according to any one of claims 1 to 6, characterized in that the alcohol is an alcohol having 2 to 20 carbon atoms, preferably an alcohol having 2 to 10 carbon atoms, more preferably one or more of ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 1-octanol, isooctanol, 1-decanol, cyclohexanol or 2-methyl-1-propanol;
preferably, the molar ratio of the alcohol to the magnesium halide is (1-10): 1, preferably (1-5): 1.
11. The process according to any one of claims 1 to 6, wherein the organometallic compound has the general formula R n AlX 3-n Wherein R is alkyl with 1-10 carbon atoms, X is halogenated group, n is more than or equal to 1 and less than or equal to 3;
preferably, the metalaluminum organic compound is trimethylaluminum, triethylaluminum, diethylaluminum monochloride or ethylaluminum dichloride, more preferably triethylaluminum;
preferably, the molar ratio of the metal aluminum organic compound to the magnesium halide is (0.5-5): 1.
12. The process according to any one of claims 1 to 6, wherein the titanium halide compound has the general formula TiX 4 Wherein, X is halogen;
preferably, the titanium halide compound is titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, or titanium tetraiodide, more preferably titanium tetrachloride;
preferably, the molar ratio of the titanium compound to the magnesium halide is (1-10): 1.
13. A catalyst for olefin polymerization, characterized in that it is produced by the production method according to any one of claims 1 to 12.
14. The catalyst for olefin polymerization according to claim 13, which is used in a process for preparing a polyethylene resin by a Hoechst slurry polymerization process.
15. The use according to claim 14, wherein the polyethylene resin has a viscosity average molecular weight of 3000000 to 8000000, a molecular weight distribution index of 5.0 to 10.0, and a bulk density of 0.35 to 0.45g/cm 3 The median diameter D50 is 120 to 260 mu m.
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