CN116023539A - Supported metallocene catalyst suitable for solution polymerization and preparation method and application thereof - Google Patents
Supported metallocene catalyst suitable for solution polymerization and preparation method and application thereof Download PDFInfo
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- CN116023539A CN116023539A CN202111250054.XA CN202111250054A CN116023539A CN 116023539 A CN116023539 A CN 116023539A CN 202111250054 A CN202111250054 A CN 202111250054A CN 116023539 A CN116023539 A CN 116023539A
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- metallocene catalyst
- supported metallocene
- solution polymerization
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 90
- 238000010528 free radical solution polymerization reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000012190 activator Substances 0.000 claims abstract description 13
- 241000282326 Felis catus Species 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 37
- 239000005977 Ethylene Substances 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004711 α-olefin Substances 0.000 claims description 13
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- -1 silane compound Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims 1
- OTUXRAAQAFDEQT-UHFFFAOYSA-N magnesium oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Mg+2].[Si+2]=O.[O-2] OTUXRAAQAFDEQT-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000029087 digestion Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- 229910007926 ZrCl Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a supported metallocene catalyst suitable for solution polymerization, a preparation method and application thereof. The supported metallocene catalyst suitable for solution polymerization has high metallocene content, realizes the loading of more metallocene compounds through the surface modification of the carrier, and is beneficial to playing better catalytic effect in a solution system; the amount of the activator is small, the active center of the catalyst is effectively dispersed through the modified carrier, the activation effect of the aluminum alkyl can be effectively exerted, and the amount of the activator and the cost of the catalyst are reduced; the catalyst system has high catalytic activity, and can realize high catalytic activity of 10-50kg/g cat when being applied to a solution polymerization process; the supported metallocene catalyst has good temperature resistance, is different from the defect of poor heat resistance of the common metallocene catalyst, can resist the high-temperature polymerization condition of 180 ℃ and has no influence on the catalytic activity.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization catalysis, and particularly relates to a supported metallocene catalyst suitable for solution polymerization, and a preparation method and application thereof.
Background
The solution polymerization process has the characteristics of good heat transfer effect, easy control of polymerization temperature, low concentration of system polymer, easy regulation and control of molecular weight distribution and the like, and is often used for producing ethylene homo-or copolymer. In general, the catalysts used in solution polymerization processes tend to be homogeneous catalysts. In recent years, as commercial application of metallocene catalysts has been successful, more and more metallocene catalysts have been developed and successfully used for olefin polymerization. For example, WO2000024792 describes a catalyst system comprising a hafnocene catalyst complex; the Dow chemistry in EP 041685A 2 discloses single metallocene structured bridged catalysts (CGCs); exxon Mobil in US9266977 discloses bridged cyclopentadienyl-indenyl (Cp-Ind) metallocene complexes; triplex-well chemistry in EP2511305 discloses bridged cyclopentadienyl-fluorenyl (Cp-Flu) metallocene complexes. Based on the characteristics of high catalytic activity, wide applicable monomer variety, precise regulation of polymer structure and the like of the metallocene catalyst, the homogeneous metallocene catalyst for the solution polymerization process has become the first choice for producing high-performance olefin polymers.
The supported catalyst is commonly used in gas phase, slurry and bulk polymerization processes, and can adjust the morphology of polymer particles and reasonably disperse catalytic active centers. There are generally two general methods for loading metallocene compounds: one is described in US5087788, US554801, US5719241, etc., inorganic carrier, alkyl aluminoxane, metallocene compound are mixed in toluene for reaction, then filtered, washed with n-hexane, and dried to obtain powdery supported metallocene catalyst; the other is that the alkyl aluminoxane is mixed with the inorganic carrier, then the metallocene compound is added for reaction, and then the powder-shaped supported metallocene catalyst is obtained after filtration, washing and pumping. Of course, there are also reports of optimizing the loading method, modifying the inorganic carrier, developing a novel carrier, and the like by a large number of patents. However, the conventional supported metallocene catalysts have low metal content (generally below 1 wt%) and require high amounts of activator to be used, resulting in high costs and poor temperature resistance, and their catalytic activity is greatly reduced when used in solution polymerization processes (particularly high temperature solution polymerization). Supported metallocene catalysts suitable for solution polymerization processes have been rarely reported.
Disclosure of Invention
The invention aims to solve the technical problems of high cost, poor temperature resistance, low high-temperature activity and the like caused by the fact that the metal content of a supported metallocene catalyst is low in the prior art. The invention provides a supported metallocene catalyst suitable for solution polymerization, a preparation method and application thereof, and the supported metallocene catalyst provided by the invention has the advantages of high metal content, high catalytic activity, good temperature resistance, less activator consumption in the preparation process and good commercial prospect.
To achieve the object of the present invention, in a first aspect, the present invention provides a supported metallocene catalyst suitable for solution polymerization, the supported metallocene catalyst comprising a support and a metallocene catalyst supported on the support, wherein the metallocene catalyst has the structure of formula i:
wherein R, R' are each independently selected from alkyl, aryl, or a hydrogen atom; m is a group IVB transition metal element, preferably titanium or zirconium; x is a halogen atom, preferably a chlorine atom.
The present invention is not particularly limited, and silica, silica-alumina, silica-magnesia, magnesium chloride, etc., which are commonly used in the art, may be employed. Meanwhile, the carrier can be unmodified or modified, for example, the carrier is modified conventionally, and the carrier is within the protection scope of the invention.
The alkyl group in the present invention may include methyl, ethyl, n-propyl, isopropyl, etc., and the present invention is not particularly limited thereto.
The aryl group in the present invention may include phenyl, o-tolyl, 1-naphthyl (or α -naphthyl), 2-naphthyl, and the like, which are not particularly limited in the present invention.
As a specific embodiment of the present invention, the mass content of the metallocene in the supported metallocene catalyst is in the range of 1wt% to 10wt%, for example, 1wt%,3wt%,5wt%,7wt%,10wt% and any combination thereof.
The supported metallocene catalyst suitable for solution polymerization has high metallocene content, realizes the loading of more metallocene compounds through the surface modification of the carrier, and is beneficial to playing better catalytic effect in a solution system; the amount of the activator is small, the active center of the catalyst is effectively dispersed through the modified carrier, the activation effect of the aluminum alkyl can be effectively exerted, and the amount of the activator and the cost of the catalyst are reduced; the catalyst system has high catalytic activity, and can realize high catalytic activity of 10-50kg/g cat when being applied to a solution polymerization process; the supported metallocene catalyst has good temperature resistance, is different from the defect of poor heat resistance of the common metallocene catalyst, can resist high-temperature polymerization conditions of 200 ℃ and has no influence on the catalytic activity.
In a second aspect, the present invention provides a method for preparing the supported metallocene catalyst suitable for solution polymerization, comprising the steps of:
s102: mixing a carrier, an activating agent and a solvent, stirring for a first preset time at the temperature of 25-100 ℃, adding a metallocene catalyst with a structure shown in formula I, stirring for reacting for a second preset time, and washing and drying to obtain a supported metallocene catalyst; wherein the weight ratio of the carrier to the activator is 1: (1-5), wherein the weight ratio of the carrier to the solvent is 1: (1-10); preferably, the first preset time is 2-4 hours; the second preset time is 22-26 h.
Preferably, before the step S102, the method further includes a step S101: roasting the unmodified carrier at 540-560 ℃, reducing the temperature to room temperature, adding a surface modifier to modify the unmodified carrier, washing, and filtering to obtain a modified carrier; wherein the weight ratio of the unmodified carrier to the surface modifier is 1: (1-4).
More preferably, the calcination time is 5 to 7 hours.
According to the preparation method of the supported metallocene catalyst suitable for solution polymerization, more metallocene compound is supported by modifying the surface of the carrier, so that better catalytic effect can be exerted in a solution system; the active center of the catalyst is effectively dispersed through the modified carrier, so that the activation effect of the aluminum alkyl can be effectively exerted, and the dosage of the activator and the cost of the catalyst are reduced. In addition, the supported metallocene catalyst prepared by the method has high catalytic activity and good temperature resistance.
As a specific embodiment of the present invention, in the step S102, the solvent is a conventional organic solvent, including but not limited to toluene, xylene, mesitylene, n-hexane, n-heptane, n-octane, isopentane, cyclohexane, carbon tetrachloride.
As a specific embodiment of the present invention, the surface modifier is a silane compound.
Preferably, the surface modifier is at least one selected from trimethoxysilane, vinyltrimethoxysilane and n-propyltrimethoxysilane.
As a specific embodiment of the present invention, the activator is at least selected from the group consisting of alkylaluminum and/or alkylaluminoxane, such as methylaluminoxane, methylaluminum, ethylaluminoxane, ethylaluminum, and the like.
As a specific embodiment of the present invention, the carrier is at least one selected from the group consisting of silica, silica-alumina, silica-magnesia and magnesium chloride.
As a specific embodiment of the present invention, the mass content of the metallocene in the supported metallocene catalyst is in the range of 1wt% to 10wt%, for example, 1wt%,3wt%,5wt%,7wt%,10wt% and any combination thereof.
In a third aspect, the present invention provides a supported metallocene catalyst system suitable for solution polymerization, said catalyst system comprising a procatalyst comprising said supported metallocene catalyst and a cocatalyst comprising: alkyl aluminum and/or alkyl aluminoxane.
Preferably, the molar ratio of Al in the cocatalyst to the group IVB transition metal element in the supported metallocene catalyst is 400-600: 1, a step of; for example 400:1,500: 1,600: 1 and any combination thereof.
More preferably, the molar ratio of Al in the cocatalyst to Zr in the supported metallocene catalyst is 400-600: 1, a step of; for example 400:1,500: 1,600: 1 and any combination thereof.
As a specific embodiment of the present invention, the catalyst system has a catalytic activity in the range of from 10kg/g cat to 50kg/g cat, for example 10kg/g cat,20kg/g cat,30kg/g cat,40kg/g cat,50kg/g cat and any combination thereof.
In a fourth aspect, the present invention provides a process for the preparation of a polymer by solution polymerization of ethylene with an α -olefin, comprising the steps of:
carrying out solution polymerization reaction on ethylene and alpha-olefin under the catalysis of the supported metallocene catalyst system, wherein the volume ratio of the ethylene to the alpha-olefin is (1-5): 20, the volume ratio of the mass of the supported metallocene catalyst system to the ethylene is (1-4) g:25mL.
According to the method for preparing the polymer by polymerizing the ethylene and the alpha-olefin in the solution, the high catalytic activity of 10-50kg/g cat is realized due to the addition of the supported metallocene catalyst; and the catalyst has good temperature resistance, can resist the high-temperature polymerization condition of 180 ℃ and ensures that the catalytic activity is not affected.
As a specific embodiment of the invention, the polymerization temperature of the method for preparing the polymer by solution polymerization of ethylene and alpha-olefin is 50-200 ℃, preferably 120-150 ℃.
As a specific embodiment of the present invention, the polymerization pressure is in the range of 1.0MPa to 3.0MPa, for example, 1.0MPa,2.0MPa,3.0MPa, and any combination thereof.
As a specific embodiment of the present invention, the polymerization time is in the range of 0.5h to 2h, for example, 0.5h,1h,1.5h,2h, and any combination thereof.
As a specific embodiment of the present invention, the α -olefin is at least one selected from propylene, 1-butene, 1-hexene, 1-octene and norbornene.
As a specific embodiment of the present invention, the solvent for the solution polymerization is at least one selected from toluene, xylene, mesitylene, 1,2, 4-trichlorobenzene, n-hexane, n-heptane, n-octane, isopentane, cyclohexane, methylcyclohexane, tetrahydrofuran, methylene chloride, 1, 2-dichloroethane and carbon tetrachloride.
In a fifth aspect, the present invention provides a polymer prepared by the method having a weight average molecular weight in the range of 40,000g/mol to 100,000g/mol, such as 40,000g/mol,50,000g/mol,60,000g/mol,70,000g/mol,80,000g/mol,90,000g/mol,100,000g/mol, and any combination thereof.
As a specific embodiment of the present invention, the molecular weight distribution Mw/Mn of the polymer is in the range of 2.0 to 3.5, such as 2.0,2.5,3.0,3.5, and any combination thereof.
As a specific embodiment of the present invention, the polymer has a melt index at 190℃and 2.16kg load in the range of 1.0g/10min to 12g/10min, such as 1.0g/10min,3.0g/10min,5.0g/10min,7.0g/10min,9.0g/10min,12.0g/10min and any combination thereof.
The supported metallocene catalyst suitable for solution polymerization has high metallocene content, realizes the loading of more metallocene compounds through the surface modification of the carrier, and is beneficial to playing better catalytic effect in a solution system; the amount of the activator is small, the active center of the catalyst is effectively dispersed through the modified carrier, the activation effect of the aluminum alkyl can be effectively exerted, and the amount of the activator and the cost of the catalyst are reduced; the catalyst system has high catalytic activity, and can realize high catalytic activity of 10-50kg/g cat when being applied to a solution polymerization process; the supported metallocene catalyst has good temperature resistance, is different from the defect of poor heat resistance of the common metallocene catalyst, can resist the high-temperature polymerization condition of 180 ℃ and has no influence on the catalytic activity.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting the invention in any way.
The test methods in the following examples and comparative examples are as follows:
ICP test:
the test is carried out by adopting an ICP-OES analysis spectrometer, and a standard curve is prepared by adopting 5% nitric acid and a gravimetric method: xg (elemental mother liquor) +xg (5% nitric acid), wherein: zr standard solution, 0.1ppm, 0.5ppm, 1ppm, 5ppm, 10ppm, working curve total 5 points (accurate to + -0.0001 g).
Weighing 90-200mg of a sample, accurately adding 0.1mg of the sample into a digestion tank, adding 6mL of a digestion agent nitric acid and 0.5mL of hydrofluoric acid, shaking uniformly, sleeving a nuclear magnetic sleeve and an explosion-proof bracket, digesting (rt-120 ℃ for 15min,120-150 ℃ for 10 min) by using a microwave digestion instrument, cooling to 50 ℃ (2 h) after digestion, taking out the sample in the digestion tank, fixing the volume into a plastic sample bottle, fixing the volume to 50g, taking out 1g of the sample from the fixed volume of the 50g of the sample, and fixing the volume to 50g of the sample in a new plastic sample bottle for later use. The above steps were weighed 2 times in parallel.
Blank: and (3) not weighing the sample, adding 6mL of a digestion agent nitric acid and 0.5mL of hydrofluoric acid, shaking uniformly, sleeving a nuclear magnetic sleeve and an explosion-proof bracket, digesting by using a microwave digestion instrument (rt-120 ℃ for 15min,120-150 ℃ for 10 min), cooling to 50 ℃ (2 h) after digestion is finished, taking out the sample in the digestion tank, fixing the volume into a plastic sample bottle, fixing the volume to 50g, taking out 1g of the sample from the 50g of the fixed volume, and fixing the volume to 50g of the sample in a new plastic sample bottle for later use.
And (5) respectively feeding the prepared sample to be tested and the blank into an instrument for detection. Wherein the Zr element measuring wavelength is selected from 339.1nm and 343.8nm, and the corresponding metal content in the sample is calculated according to a standard curve
Melt index determination
The mass of the sample at 190℃under a standard weight of 2.16kg for 10min through a standard die was determined using a melt index apparatus according to GB-3682.1-2018 determination of melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of plastics thermoplastics.
Molecular weight and molecular weight distribution determination
The test was performed using a gel permeation chromatograph according to ASTM D6474-1999, standard Test Method for Determining Molecular Weight Distribution and Molecular Weight Averages of Polyolefins by High Temperature Gel Permeation Chromatography. 3.2mg of the sample was weighed, 8mL of 1,2, 4-trichlorobenzene was added to dissolve it completely into a homogeneous transparent solution of 0.4mg/mL, and the test was performed at 150 ℃.
1. Preparation of supported metallocene catalysts
Example 1: preparation method of supported metallocene catalyst A
Under the protection of nitrogen, 20g of silica gel is placed in a muffle furnace to be roasted for 6 hours at 550 ℃, the roasted silica gel is transferred into a 250mL three-neck flask, and the nitrogen atmosphere is maintained to be cooled to normal temperature. Then, 40g of n-propyltrimethoxysilane was added and stirred for 3 hours, 150mL of toluene was added and filtered, and 50 mL. Times.2 times of toluene was used for washing, and the modified silica gel was obtained by filtration. Then 20mL of 1M methyl was added100mL of toluene was added to the aluminoxane toluene solution, the mixture was stirred well at 80℃for 3 hours, and finally 0.02mol of ethylene-bridged indene dichloro-zirconocene Et was added 2 (Ind) 2 ZrCl 2 The reaction was stirred for an additional 24 hours. After the completion of the reaction, the mixture was filtered, thoroughly washed with 100mL of n-hexane X3 times, and dried by suction to obtain 22.3g of a powdery supported metallocene catalyst A in total. The metal content was 3.8wt% as determined by ICP, based on the total weight of the supported metallocene catalyst.
Example 2: preparation method of supported metallocene catalyst B
With zirconocene dichloride Cp 2 ZrCl 2 Replacement of ethylene bridged indene zirconocene Et in example 1 2 (Ind) 2 ZrCl 2 Other conditions were the same as in example 1 to obtain 21.5g of a powdery supported metallocene catalyst B in total. The metal content was 3.5wt% as determined by ICP, based on the total weight of the supported metallocene catalyst.
Example 3: preparation method of supported metallocene catalyst C
Under the protection of nitrogen, 20g of aluminum oxide is placed in a muffle furnace to be roasted for 8 hours at 600 ℃, the roasted aluminum oxide is transferred into a 250mL three-neck flask, and the nitrogen atmosphere is maintained to be cooled to normal temperature. Then, 40g of n-propyltrimethoxysilane was added and stirred for 3 hours, 150mL of toluene was added and filtered, and 50 mL. Times.2 times of toluene was used for washing, and the modified alumina was obtained by filtration. Then 20mL of 1M methylaluminoxane toluene solution was added, 100mL of toluene was added, and the mixture was sufficiently stirred at 100℃for 3 hours, finally 0.02mol of ethylene bridged indene dichloro-zirconocene Et was added 2 (Ind) 2 ZrCl 2 The reaction was stirred for an additional 24 hours. After completion of the reaction, the mixture was filtered and washed thoroughly with 100mL of n-hexane X3 times, and then, the mixture was dried by suction to obtain 23.1g of a total of the powdery supported metallocene catalyst C. The metal content was 5.1wt% by ICP measurement, based on the total weight of the supported metallocene catalyst.
Example 4: preparation method of supported metallocene catalyst D
The ethylene bridged indene zirconocene Et2 (Ind) 2ZrCl2 of example 3 was replaced with zirconocene dichloride Cp2ZrCl2, and the other conditions were the same as in example 3 to obtain 21.9g in total of the powdery supported metallocene catalyst D. The metal content was 4.7wt% as determined by ICP, based on the total weight of the supported metallocene catalyst.
Example 5: preparation method of supported metallocene catalyst E
Under the protection of nitrogen, 20g of the silica-magnesia carrier is placed in a muffle furnace to be roasted for 4 hours at 450 ℃, the roasted silica-magnesia carrier is transferred into a 250mL three-neck flask, and the nitrogen atmosphere is maintained to be cooled to normal temperature. Then, 40g of n-propyltrimethoxysilane was added and stirred for 3 hours, 150mL of toluene was added and filtered, and 50 mL. Times.2 times of toluene was used for washing, and the modified silica-magnesia carrier was obtained by filtration. Then 20mL of 1M methylaluminoxane toluene solution was added, 100mL of toluene was added, and the mixture was sufficiently stirred at 80℃for 3 hours, finally 0.02mol of ethylene bridged indene dichloro-zirconocene Et was added 2 (Ind) 2 ZrCl 2 The reaction was stirred for an additional 24 hours. After the completion of the reaction, the reaction mixture was filtered and washed thoroughly with 100mL of n-hexane X3 times, and then dried by suction to obtain 20.6g of a total of the powdery supported metallocene catalyst E. The metal content was 1.3wt% as determined by ICP, based on the total weight of the supported metallocene catalyst.
Example 6: preparation method of supported metallocene catalyst F
Substitution of ethylene bridged indene zirconocene dichloride Et in example 5 with zirconocene dichloride Cp2ZrCl2 2 (Ind) 2 ZrCl 2 Other conditions were the same as in example 5 to obtain 20.4g of a powdery supported metallocene catalyst F in total. The metal content was 1.6wt% as determined by ICP, based on the total weight of the supported metallocene catalyst.
Example 7: preparation method of supported metallocene catalyst G
50mL of a 1M toluene solution of triisobutylaluminum was used in place of the 1M toluene solution of methylaluminoxane in example 1, and the other conditions were the same as in example 1 to obtain a total of 21.6G of a powdery supported metallocene catalyst G, and the content of the metal measured by ICP was 2.6% by weight based on the total weight of the supported metallocene catalyst.
Example 8: preparation method of supported metallocene catalyst H
50mL of a 1M toluene solution of triethylaluminum was used in place of the 1M toluene solution of methylaluminoxane in example 1 under the same conditions as in example 1 to obtain a total of 20.4g of a powdery supported metallocene catalyst H, and the metal content by ICP measurement was 1.0% by weight based on the total weight of the supported metallocene catalyst.
2. Solution polymerization process
Polymerization reaction of ethylene and alpha-olefin solution
Example 9:
the supported metallocene catalyst A is used for ethylene and hexene copolymerization, and the specific process is as follows: firstly, vacuumizing a 500mL polymerization kettle, heating the polymerization kettle to a temperature of 110 ℃, then, replacing air with high-purity nitrogen, and cooling. 50mL of hexene and 200mL of toluene were added sequentially to the polymerization vessel under nitrogen protection, followed by Triisobutylaluminum (TiBA) in a ratio of promoter to Al/Zr molar ratio=500 in the supported catalyst. Heating the polymerization kettle to the set polymerization temperature of 120 ℃, introducing ethylene into the polymerization kettle, and adjusting the ethylene to the set polymerization pressure of 2.0MPa. Finally, 2.4mg of the supported catalyst A of example 1 was added to start the polymerization; the ethylene is kept continuously to be replenished in the reaction process, and the instantaneous consumption of ethylene monomer is collected on line by using a mass flowmeter and recorded by a computer. After reacting for 1h at 120 ℃, stopping introducing ethylene gas, cooling, slowly releasing the ethylene gas in the polymerization kettle, releasing pressure, and adding 50mL of 5% hydrochloric acid/ethanol mixed solution to terminate the reaction; the polymer was washed, filtered, dried in vacuo and weighed to give 33.6g of polymer, which was characterized for polymer physical properties, catalyst performance and product characterization data as shown in Table 1.
Example 10:
the polymerization temperature was adjusted to 150℃under the same conditions as in example 9 to obtain 34.7g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data were shown in Table 1.
Example 11:
the polymerization temperature was adjusted to 180℃under the same conditions as in example 9 to obtain 35.9g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data were shown in Table 1.
Example 12:
the polymerization temperature was adjusted to 90℃under the same conditions as in example 9 to obtain 30.2g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data are shown in Table 1.
Example 13:
using 2.6mg of the supported metallocene catalyst B, the other conditions were the same as in example 9, to obtain 17.4g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data were shown in Table 1.
TABLE 1 characterization data for copolymerization reaction products of ethylene and hexene
Note that: polymerization activity was calculated from the ratio of the polymer yield (unit: g) to the catalyst addition (unit: mol); the comonomer content is obtained by nuclear magnetic resonance hydrogen spectrum analysis; the molecular weight and molecular weight distribution (polydispersity) were measured by high temperature gas chromatography (calibrated with 1,2, 4-trichlorobenzene as solvent, polystyrene); melt index determination standard gbt3682-2018.
In Table 1, examples 9-12 show that the reaction temperature is kept high in catalytic activity at 90-180 ℃ and excellent high-temperature tolerance is shown, and examples 9 and 13 show that the catalytic performance of the supported metallocene catalyst A is slightly higher than that of the supported metallocene catalyst B.
Example 14:
the supported metallocene catalyst A is used for the copolymerization of ethylene and octene, and the specific process is as follows: firstly, vacuumizing a 500mL polymerization kettle, heating the polymerization kettle to a temperature of 110 ℃, then, replacing air with high-purity nitrogen, and cooling. 30mL of octene and 200mL of toluene were added sequentially to the polymerization vessel under nitrogen protection, followed by Triisobutylaluminum (TiBA) in a ratio of cocatalyst to Al/Zr molar ratio=500 in the supported catalyst. Heating the polymerization kettle to the set polymerization temperature of 90 ℃, introducing ethylene into the polymerization kettle, and adjusting the ethylene to the set polymerization pressure of 2.0MPa. Finally, 2.4mg of the supported catalyst of example 1 was added to start the polymerization; the ethylene is kept continuously to be replenished in the reaction process, and the instantaneous consumption of ethylene monomer is collected on line by using a mass flowmeter and recorded by a computer. After reacting for 0.5h at 90 ℃, stopping introducing ethylene gas, cooling, slowly releasing the ethylene gas in the polymerization kettle, releasing pressure, and adding 50mL of 5% hydrochloric acid/ethanol mixed solution to terminate the reaction; the polymer was washed, filtered, dried in vacuo and weighed to give 61.4g of polymer, which was characterized for polymer physical properties, catalyst performance and product characterization data as shown in Table 2.
Example 15:
the polymerization temperature was adjusted to 120℃under the same conditions as in example 14 to obtain 75.4g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data are shown in Table 2.
Example 16:
the polymerization temperature was adjusted to 150℃under the same conditions as in example 14 to obtain 69.5g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data were shown in Table 2.
Example 17:
the polymerization temperature was adjusted to 180℃under the same conditions as in example 14 to obtain 85.7g of a polymer, and the polymerization physical properties were characterized, and the catalyst properties and the product characterization data are shown in Table 2.
Example 18:
the polymerization temperature was adjusted to 120℃and the octene feed was adjusted to 60mL, and the other conditions were the same as in example 14, giving 103.2g of polymer, characterizing the physical properties of the polymerization, and the catalyst performance and product characterization data are shown in Table 2.
Example 19:
the polymerization temperature was adjusted to 120℃and the octene feed was adjusted to 90mL, and the other conditions were the same as in example 14, giving 118.8g of polymer, characterizing the physical properties of the polymerization, and the catalyst performance and product characterization data are shown in Table 2.
Example 20:
the polymerization temperature was set to 120℃and the reaction pressure was set to 1.5MPa, and the conditions were the same as in example 14, except that 57.4g of a polymer was obtained, and polymerization physical properties were characterized, and the catalyst properties and product characterization data were shown in Table 2.
Example 21:
the polymerization temperature was set to 120℃and the reaction pressure was set to 1.0MPa, and the conditions were the same as in example 14, except that 49.8g of a polymer was obtained, and polymerization physical properties were characterized, and the catalyst properties and the reaction product characterization data were shown in Table 2.
TABLE 2 characterization data for copolymerization reaction products of ethylene and octene
As can be seen from Table 2, the supported catalyst has high catalytic activity in catalyzing the copolymerization of ethylene and octene, the polymerization temperature still maintains high polymerization activity at 180 ℃, the advantages of high temperature resistance of the supported catalyst are reflected, and the comparison of examples 14 and 18-20, through the adjustment of ethylene pressure and octene input amount, the product melt index has wider adjustability (1.3-11.5 g/10min@190 ℃).
Any numerical value recited in this disclosure includes all values incremented by one unit from the lowest value to the highest value if there is only a two unit interval between any lowest value and any highest value. For example, if the amount of one component, or the value of a process variable such as temperature, pressure, time, etc., is stated to be 50-90, it is meant in this specification that values such as 51-89, 52-88 … …, and 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 units may be considered as appropriate. This is only a few examples of the specific designations. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A supported metallocene catalyst suitable for solution polymerization, characterized in that the supported metallocene catalyst comprises a support and a metallocene catalyst supported on the support, wherein the metallocene catalyst has the structure of formula i:
wherein R, R' are each independently selected from alkyl, aryl, or a hydrogen atom; m is a group IVB transition metal element, preferably titanium or zirconium; x is a halogen atom, preferably a chlorine atom.
2. The supported metallocene catalyst according to claim 1, which is suitable for solution polymerization, wherein the mass content of metallocene in the supported metallocene catalyst is 1wt% to 10wt%.
3. The method for preparing a supported metallocene catalyst suitable for solution polymerization according to claim 1 or 2, comprising the steps of:
s102: mixing a carrier, an activating agent and a solvent, stirring for a first preset time at the temperature of 25-100 ℃, adding a metallocene catalyst with a structure shown in formula I, stirring for reacting for a second preset time, and washing and drying to obtain a supported metallocene catalyst; wherein the weight ratio of the carrier to the activator is 1: (1-5), wherein the weight ratio of the carrier to the solvent is 1: (1-10); preferably, the first preset time is 2-4 hours; the second preset time is 22-26 hours;
preferably, before the step S102, the method further includes a step S101: roasting the unmodified carrier at 540-560 ℃, reducing the temperature to room temperature, adding a surface modifier to modify the unmodified carrier, washing, and filtering to obtain a modified carrier; wherein the weight ratio of the unmodified carrier to the surface modifier is 1: (1-4); more preferably, the calcination time is 5 to 7 hours.
4. The method for preparing a supported metallocene catalyst suitable for solution polymerization according to claim 3, wherein the surface modifier is a silane compound, preferably, the surface modifier is at least one selected from trimethoxysilane, vinyltrimethoxysilane and n-propyltrimethoxysilane; and/or the number of the groups of groups,
the activator is at least selected from alkyl aluminum and/or alkyl aluminoxane; and/or the number of the groups of groups,
the unmodified carrier is at least one selected from silicon oxide, silicon oxide-aluminum oxide, silicon oxide-magnesium oxide and magnesium chloride; and/or the number of the groups of groups,
the mass content of the metallocene in the supported metallocene catalyst is 1-10wt%.
5. A supported metallocene catalyst system suitable for solution polymerization, characterized in that the catalyst system comprises a procatalyst comprising the supported metallocene catalyst of claim 1 or 2 and a cocatalyst comprising: alkyl aluminum and/or alkyl aluminoxane;
preferably, the molar ratio of Al in the cocatalyst to the group IVB transition metal element in the supported metallocene catalyst is 400-600: 1, a step of;
more preferably, the molar ratio of Al in the cocatalyst to Zr in the supported metallocene catalyst is 400-600: 1.
6. the supported metallocene catalyst system suitable for solution polymerization according to claim 5, characterized in that the catalytic activity of the catalyst system is from 10kg/g cat to 50kg/g cat.
7. A process for the preparation of a polymer by solution polymerization of ethylene with an α -olefin, comprising the steps of:
carrying out solution polymerization reaction on ethylene and alpha-olefin under the catalysis of the supported metallocene catalyst system as claimed in claim 5 or 6, wherein the volume ratio of the ethylene to the alpha-olefin is (1-5): 20, the volume ratio of the mass of the supported metallocene catalyst system to the ethylene is (1-4) g:25mL.
8. The process for the preparation of a polymer by solution polymerization of ethylene and α -olefins according to claim 7, characterized in that the polymerization temperature is 50 ℃ to 200 ℃, preferably 120 ℃ to 150 ℃; and/or the number of the groups of groups,
the polymerization pressure is 1.0MPa to 3.0MPa; and/or the number of the groups of groups,
the polymerization reaction time is 0.5 h-2 h.
9. The method for preparing a polymer by solution polymerization of ethylene and alpha-olefin according to claim 7 or 8, wherein the alpha-olefin is at least one selected from propylene, 1-butene, 1-hexene, 1-octene and norbornene; and/or the number of the groups of groups,
the solvent for the solution polymerization reaction is at least one selected from toluene, xylene, mesitylene, 1,2, 4-trichlorobenzene, n-hexane, n-heptane, n-octane, isopentane, cyclohexane, methylcyclohexane, tetrahydrofuran, dichloromethane, 1, 2-dichloroethane and carbon tetrachloride.
10. The polymer prepared by the process of any one of claims 7-9, wherein the polymer has a weight average molecular weight of 40,000g/mol to 100,000g/mol; and/or the molecular weight distribution Mw/Mn of the polymer is 2.0-3.5; and/or the melt index of the polymer at 190 ℃ under 2.16kg load is 1.0g/10 min-12 g/10min.
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