CN117924545A - Supported catalyst and preparation method and application thereof - Google Patents
Supported catalyst and preparation method and application thereof Download PDFInfo
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- CN117924545A CN117924545A CN202211266104.8A CN202211266104A CN117924545A CN 117924545 A CN117924545 A CN 117924545A CN 202211266104 A CN202211266104 A CN 202211266104A CN 117924545 A CN117924545 A CN 117924545A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 62
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 22
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 229910001848 post-transition metal Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 125000003636 chemical group Chemical group 0.000 claims abstract description 7
- 125000004429 atom Chemical group 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 229920000098 polyolefin Polymers 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- -1 C12 aliphatic hydrocarbon Chemical class 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
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- 239000010703 silicon Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
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- 229910052723 transition metal Inorganic materials 0.000 claims description 6
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- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical class C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 4
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052759 nickel Inorganic materials 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
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- 150000003376 silicon Chemical class 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 125000000335 thiazolyl group Chemical group 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 150000001925 cycloalkenes Chemical class 0.000 claims 1
- 150000004696 coordination complex Chemical class 0.000 abstract description 37
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 238000006116 polymerization reaction Methods 0.000 description 29
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 14
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- 239000000243 solution Substances 0.000 description 10
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- PLWSZOQYWKLNIL-UHFFFAOYSA-N 1-butyl-2-chloro-3-methyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1Cl PLWSZOQYWKLNIL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
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- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The present disclosure provides a supported catalyst comprising: an ionic liquid modified carrier, wherein an anion or cation of the ionic liquid reacts with a chemical group on the surface of the carrier to modify the carrier, and the cation of the ionic liquid contains an atom capable of providing an electron; and a complex of a post-transition metal coordinated by a diimine-containing ligand or a phosphine sulfonic acid-containing ligand supported on an ionic liquid modified support, wherein the empty orbitals provided by the heteroatom N or O in the complex ligand interact with electrons provided by carbon atoms in the cation of the ionic liquid, thereby being anchored to the support by the ionic liquid. The method changes the morphological characteristics of the surface of a carrier through ionic liquid to form a medium which is covered on the surface of the carrier and can anchor a metal complex; active centers of metal complexes that facilitate insertion of comonomers into ionic liquid media; thereby improving the activity of the catalyst and the insertion ratio of the polar monomer.
Description
Technical Field
The disclosure relates to the technical field of catalysts, in particular to a supported catalyst, a preparation method and application thereof.
Background
With the widespread use of polyolefins, the design and development of high performance catalysts has received great attention from various communities. Currently, research on polyolefins is mainly focused on two aspects, one of which is based on a homogeneous system, and the polyolefins obtained in this way have a definite molecular structure, which facilitates their modification, making them useful for the mechanism study. The second is based on heterogeneous systems, which are commonly used in the industrial polymerization of polyolefins, which increase the polymerization reactivity, increase the molecular weight of the polymer, and effectively control the morphology of the product to achieve a continuous polymerization process while preventing reactor fouling.
In industrial applications, the polyolefin industry mainly utilizes heterogeneous polymerization systems because they can further increase polymerization reactivity, increase molecular weight of polymers, and can effectively control product morphology to achieve continuous polymerization processes while preventing reactor fouling. Currently, there are three main approaches to heterogeneous olefin polymerization catalysts on solid supports (see figure 1): A. the introduction of a pre-catalyst into a co-catalyst pre-treated support to form ion pairs to produce a supported catalyst is simple and widely used, but generally suffers from low activity and low comonomer insertion due to the large steric hindrance around the active sites caused by the co-catalyst pre-treated solid support. B. Directly supporting the (co-catalyst) -activated metal catalyst on a carrier to prepare a supported catalyst, which is disadvantageous for polymerization systems with sensitive active substances, and the catalyst is easy to deactivate; C. the metal complex may be reacted with the aluminum co-catalyst pretreated support to produce a supported catalyst by a specially designed reaction site (e.g., hydroxyl or amino on the ligand) which differs from method a in that the metal complex is covalently attached to the supported co-catalyst, but this method requires the design of a complex ligand structure.
In addition to the above disadvantages, these conventional preparation routes of supported catalysts also face the problem that the metal center of the catalyst is more likely to be detached from the carrier in the presence of polar comonomers, and the problem that polar monomers are limited by steric hindrance of the carrier and are difficult to insert. Therefore, it is important to develop a supported late transition metal catalyst with the capability of efficiently catalyzing the copolymerization of ethylene and polar monomers, which is one of the important scientific problems in the field of transition metal polyolefin catalysts, and is also one of the important ways of realizing the industrial application of functionalized polyolefin.
Disclosure of Invention
To at least partially solve at least one of the above-mentioned technical drawbacks, embodiments of the present disclosure generally provide a supported catalyst, a preparation method thereof, and an application thereof, in which an ionic liquid is introduced into a support, the ionic liquid changes morphology characteristics of the surface of the support, and a medium anchoring a metal complex catalyst is formed on the surface of the support, so that direct interaction between the surface of the support and the metal complex catalyst can be prevented, steric hindrance and poisoning of active centers of the metal complex by the support are reduced, and insertion of a comonomer into the active centers of the metal complex in the ionic liquid medium is facilitated, thereby improving activity of the catalyst and insertion ratio of polar monomers.
To achieve the above object, as an embodiment of one aspect of the present disclosure, there is provided a supported catalyst comprising: an ionic liquid-modified carrier, wherein an anion or cation of the ionic liquid reacts with a chemical group on the surface of the carrier to modify the carrier, and the cation of the ionic liquid contains an atom capable of providing an electron; and a complex of a post-transition metal coordinated by a diimine-containing ligand or a phosphine sulfonic acid-containing ligand supported on the ionic liquid-modified support, wherein an empty orbital provided by a heteroatom N or O in the complex ligand interacts with an electron provided by a carbon atom in a cation of the ionic liquid, thereby being anchored to the support by the ionic liquid.
As an embodiment of another aspect of the present disclosure, there is provided a method for preparing the above supported catalyst, including: under the anhydrous and anaerobic condition, the ionic liquid modified carrier is separated into an organic solvent to obtain an organic dispersion liquid; under the anhydrous and anaerobic condition, dissolving a ligand containing diimine or a complex containing phosphine sulfonic acid and coordinated post-transition metal into an organic solvent to obtain an organic solution; and (3) under the anhydrous and anaerobic condition, adding the organic solution into the organic dispersion liquid to react for 1-120 min, thus obtaining the supported catalyst.
As an embodiment of a further aspect of the present disclosure, there is provided a use of the above supported catalyst for preparing polyolefin, wherein the olefin is polymerized under the action of the above supported catalyst to prepare polyolefin.
The supported catalyst provided by the embodiment of the disclosure introduces the ionic liquid into the carrier in a way that the anions or cations of the ionic liquid react with chemical groups on the surface of the carrier, changes the morphological characteristics of the surface of the carrier, and forms a medium which is covered on the surface of the carrier and can anchor the metal complex; and further, the direct interaction between the surface of the carrier and the metal complex can be prevented, the steric hindrance and poisoning effect of the carrier on the active center of the metal complex are reduced, and the insertion of the comonomer into the active center of the metal complex in the ionic liquid medium is facilitated, so that the activity of the catalyst and the insertion ratio of the polar monomer are improved.
Drawings
FIG. 1 is a schematic diagram of three main pathways for heterogeneous olefin polymerization catalysts;
FIG. 2 is a scanning electron microscope image of SiO 2 untreated with an ionic liquid in a comparative example prepared according to an exemplary embodiment of the present disclosure;
FIG. 3 is a scanning electron microscope image of an ionic liquid carrier (IL Support 1) prepared according to one exemplary embodiment of the present disclosure;
FIG. 4 is a FT-IR diagram of an ionic liquid carrier (IL Support 1) prepared according to one example embodiment of the present disclosure;
FIG. 5 is a scanning electron microscope (SEM-EDS) spectrum of a supported catalyst of formula (I 1) prepared according to an exemplary embodiment of the present disclosure; and
FIG. 6 is a graph showing comparison of polymer morphology prepared by using a homogeneous diimine type metal complex A and an ionic liquid modified carrier-supported diimine type metal complex A as a catalyst in the polymerization reaction of catalyzing ethylene under certain conditions.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same.
Because the structure and the type of the carrier are important to improve the performance of the supported catalyst; therefore, by modifying the carrier structure and introducing the carrier with a novel structure, the modified carrier can form high-efficiency anchoring with various types of post-transition metal catalysts, has the characteristics of high loading rate, high universality and the like, so that a series of novel high-performance loaded post-transition metal catalysts with high catalytic activity can be prepared more simply, and the loaded post-transition metal catalysts are used for preparing functionalized polyolefin materials with high molecular weight.
According to an aspect of the present disclosure, there is provided a supported catalyst comprising: an ionic liquid modified carrier, wherein an anion or cation of the ionic liquid reacts with a chemical group on the surface of the carrier to modify the carrier, and the cation of the ionic liquid contains an atom capable of providing an electron; and a complex of a post-transition metal coordinated by a diimine-containing ligand or a phosphine sulfonic acid-containing ligand supported on an ionic liquid modified support, wherein the empty orbitals provided by the heteroatom N or O in the complex ligand interact with electrons provided by carbon atoms in the cation of the ionic liquid, thereby being anchored to the support by the ionic liquid.
The supported catalyst provided by the embodiment of the disclosure introduces the ionic liquid into a carrier in a way that anions or cations of the ionic liquid react with chemical groups on the surface of the carrier, changes the morphological characteristics of the surface of the carrier, and forms a medium which is covered on the surface of the carrier and can anchor the metal complex; and further, the direct interaction between the surface of the carrier and the metal complex can be prevented, the steric hindrance and poisoning effect of the carrier on the active center of the metal complex are reduced, and the insertion of the comonomer into the active center of the metal complex in the ionic liquid medium is facilitated, so that the activity of the catalyst and the insertion ratio of the polar monomer are improved.
In some embodiments of the present disclosure, the ionic liquid modified support comprisesOr (b)Any one of them; wherein R 'in-OR' comprises any of hydrogen, a substituted OR unsubstituted aliphatic hydrocarbon group of C 1～C6, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group, substituted OR unsubstituted phenyl, a is an integer from 1 to 20, e.g., a is 2,6, 10, 12, 16, 19; r in- (AlCl nR3-n) m comprises a hydrocarbon group of C 1～C12, n is an integer from 0 to 3, e.g., n is 1,2, m is an integer from 1 to 20, e.g., m is 3, 8, 12, 16, 19; y comprises any one of substituted pyrrolidinium and substituted imidazolium, wherein the substituent of the substituted pyrrolidinium and the substituted imidazolium comprises any one of hydrogen, substituted or unsubstituted aliphatic hydrocarbon group of C 1～C6, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group and substituted or unsubstituted phenyl; the carrier comprises any one of silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate and carbon black; the post-transition metal comprises any one of nickel and palladium; the ionic liquid comprises
Any one of the following.
In some embodiments of the present disclosure, the diimine-containing ligands include Any one of them; the phosphine sulfonic acid-containing ligands includeAr comprises any one of substituted phenyl and substituted naphthyl, wherein the substituents in the substituted phenyl and substituted naphthyl comprise hydrogen, substituted or unsubstituted C 1～C12 aliphatic hydrocarbon, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon, and substituted or unsubstituted phenyl; r 1 and R 2 include any one of hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group of C 1～C12, a substituted silicon group, a substituted or unsubstituted phenyl group; or R 1 and R 2 can bond or form a ring with each other; m 1～M5、N1～N6 comprises any one of hydrogen, substituted or unsubstituted aliphatic hydrocarbon group of C 1～C12, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group, and substituted or unsubstituted phenyl group respectively.
In some embodiments of the present disclosure, the complex comprises Any one of them; x 'and Y' comprise any one of fluorine, chlorine, bromine, iodine, aliphatic hydrocarbon group of C 1～C12, aryl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group and tin-containing group; or the X 'and Y' moieties can be bonded to each other or form a ring; ar and R 1、R2、M1～M5、N1～N6 are as defined above.
In some embodiments of the present disclosure, the oxygen-containing group includes any one of an alkoxy group, a sulfone group, a carboxyl group; the nitrogen-containing group comprises any one of pyridyl, nitro, cyano, pyrrolyl, thiazolyl, imidazolyl, pyrazolyl and pyrimidinyl; the sulfur-containing group comprises any one of sulfonyl and thienyl; the boron-containing group includes phenyl boron; the aluminum-containing group comprises any one of alkyl aluminum and alkoxy aluminum; the phosphorus-containing group comprises any one of phenylphosphine and phenylphosphine; the silicon-containing groups include siloxyl groups.
In some embodiments of the present disclosure, any one of the structures shown in formulas (I 1) to (I 6) is included:
According to an embodiment of the present disclosure, there is also provided a method for preparing the above supported catalyst, including: under the anhydrous and anaerobic condition, the ionic liquid modified carrier is separated into an organic solvent to obtain an organic dispersion liquid; under the anhydrous and anaerobic condition, dissolving a ligand containing diimine or a complex containing phosphine sulfonic acid and coordinated post-transition metal into an organic solvent to obtain an organic solution; adding an organic solution into the organic dispersion liquid to react for 1-120 min under the anhydrous and anaerobic condition, for example, 26min, 58min, 76min, 96min and 118min; a supported catalyst was obtained.
In some embodiments of the present disclosure, the mass ratio of complex to ionic liquid modified support in the preparation of supported catalysts comprises 1:20 to 1:50000, e.g., 1:50, 1:120, 1:1200, 1:2600, 1:3600, 1:4800. The Metal Complex (Metal Complex) in this ratio range can be uniformly supported on the ionic liquid modified Support (IL Support) and a higher load is obtained.
In some embodiments of the present disclosure, the organic solvent comprises one or more of tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, 1, 4-dioxane, 1, 2-dichloroethane.
According to the embodiment of the disclosure, the application of the supported catalyst in preparing polyolefin is also provided, and under the action of the supported catalyst, olefin is polymerized to prepare polyolefin.
In some embodiments of the present disclosure, the use of the above supported catalyst in the preparation of a polyolefin, the olefin comprising any one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-octadecene, a polar group containing C 2～C20 -olefin derivative, a polar group containing cyclic olefin derivative; wherein the polar group comprises any one of oxygen-containing, nitrogen-containing, sulfur-containing and selenium-containing organic functional groups, and the organic functional groups comprise any one of hydroxyl, carboxyl, ester, alkoxy, amino, amido, thioether, silyl ether and selenoether groups. Wherein the oxygen-containing group comprises any one of alkoxy, sulfonyl and carboxyl; the nitrogen-containing group comprises any one of pyridyl, nitro, cyano, pyrrolyl, thiazolyl, imidazolyl, pyrazolyl and pyrimidinyl; the sulfur-containing group includes any one of a sulfone group and a thiophene group.
In some embodiments of the present disclosure, the polymerization temperature of the polymerization reaction in the use of the above supported catalyst in the preparation of polyolefin comprises 0 ℃ to 200 ℃, e.g., 36 ℃, 79 ℃, 106 ℃, 156 ℃, 189 ℃; the polymerization pressure includes 0.1MPa to 50MPa, for example, 2.6MPa, 10.6MPa, 26.8MPa, 38.9MPa, 46.8MPa.
In some embodiments of the present disclosure, slurry polymerization, loop polymerization, gas phase polymerization, or other forms of polymerization processes can be employed in the polymerization reaction to make the polyolefin, without limitation.
In some embodiments of the present disclosure, the polymerization reaction to produce the polyolefin is typically carried out in an organic solvent, such as a hydrocarbon, cyclic hydrocarbon, or aromatic hydrocarbon organic solvent. To further facilitate reactor operation and polymerization products, in some preferred embodiments, the organic solvent may use, for example, hydrocarbons of less than 12 carbons, including, but not limited to, hexane, toluene, chlorobenzene, and mixtures thereof.
The present disclosure is further illustrated by the following comparative examples and examples. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough explanation of the disclosed embodiments. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the various embodiments below may be arbitrarily combined into other viable embodiments without conflict.
The catalyst ligand synthesis, catalyst synthesis and polymerization processes in the following examples and comparative examples were all carried out under anhydrous and anaerobic conditions, all sensitive materials were stored in a glove box, all solvents were strictly dried to remove water, ethylene gas was purified by a water removal and deoxygenation column, and polar monomers were purified by a water removal and deoxygenation and reduced pressure distillation method. All materials were used as purchased unless otherwise specified.
Silica gel with 200-300 meshes is used for separation by a silica gel column; the nuclear magnetic detection adopts a Bruker 400MHz nuclear magnetic instrument; elemental analysis was measured by the university of science and technology center of china; molecular weight and molecular weight distribution were determined by GPC (polystyrene columns, HR2 and HR4, tank temperature 45 ℃, using Water 1515 and Water 2414 pumps; mobile phase trichlorobenzene, flow rate 1.0 ml/min, standard with polydisperse polystyrene); mass spectra were determined using Thermo LTQ Orbitrap XL (ESI+) or P-SIMS-Gly of Bruker Daltonics Inc (EI+). The metal content is determined by inductively coupled plasma emission spectrometry (ICP) (Prodigy ICP, li Man laboratory in the United states), the wavelength range is 165-800 nm, and the resolution is less than or equal to 0.005nm.
Example 1
Preparation of ionic liquid Carrier (IL Support) 1:
S1: 17.47g of 1-methyl-3-butylimidazolyl chloride and 26.67g of anhydrous AlCl 3 are added into a round bottom flask under an inert atmosphere, and the mixture is stirred overnight to obtain an ionic liquid;
S2: the ionic liquid obtained in S1 was added to the calcined silica, stirred overnight, followed by washing with hot dichloromethane to give ionic liquid carrier (IL Support) 1.
A scanning electron microscope image of the prepared ionic liquid carrier (IL Support) 1 is shown in figure 3; as shown in the FT-IR characterization of the ionic liquid vehicle (IL Support) 1 of FIG. 4, 1104cm -1,804cm-1,473cm-1 is Si-O stretching vibration and 1628cm -1 is C-N stretching vibration.
Example 2
Preparation of Ionic liquid Carrier (IL Support) 2
S1: adding 1-methyl-3- [3- (triethylsiloxy) propyl ] imidazole chloride in a round bottom flask under an inert atmosphere, adding the mixture into the roasted silicon dioxide, and stirring the mixture overnight;
s2: to the mixed solution obtained in S1, 2-fold equivalent of aluminum trichloride was added and stirred overnight, followed by washing with hot methylene chloride to obtain ionic liquid carrier 2 (IL Support 2).
Example 3
Preparation of Supported catalyst of formula (I 1)
S1: in an inert atmosphere, diimine type metal complex10Mg dissolved in dichloromethane;
s2: adding the mixed solution obtained in the step S1 to an IL Support dispersed with 1g in an inert atmosphere Stirring the mixture in a dichloromethane solution of a carrier for 60min, filtering, leaching the solid, and pumping the solid to obtain the supported catalyst shown in the formula (I 1).
The scanning electron microscope (SEM-EDS) diagram of the supported catalyst shown in formula (I 1) is shown in FIG. 5.
Example 4
Preparation of Supported catalyst of formula (I 2)
S1: in an inert atmosphere, diimine type metal complex10Mg dissolved in dichloromethane;
s2: adding the mixed solution obtained in the step S1 to an IL Support dispersed with 1g in an inert atmosphere Stirring the mixture in a dichloromethane solution of a carrier for 60min, filtering, leaching the solid, and pumping the solid to obtain the supported catalyst shown in the formula (I 2).
Example 5
Preparation of Supported catalyst of formula (I 3)
S1: in an inert atmosphere, the diimine type metal complex C10Mg dissolved in dichloromethane;
s2: adding the mixed solution obtained in the step S1 to IL Support1 dispersed with 1g in an inert atmosphere Stirring the mixture in a dichloromethane solution of a carrier for 60min, filtering, leaching the solid, and pumping the solid to obtain the supported catalyst shown in the formula (I 3).
Example 6
Preparation of Supported catalyst of formula (I 4)
S1: in an inert atmosphere, the diimine type metal complex A10Mg dissolved in dichloromethane;
s2: adding the mixed solution obtained in the step S1 to IL Support2 dispersed with 1g in an inert atmosphere Stirring the mixture in a dichloromethane solution of a carrier for 60min, filtering, leaching the solid, and pumping the solid to obtain the supported catalyst shown in the formula (I 4).
Example 7
Preparation of Supported catalyst of formula (I 5)
S1: in an inert atmosphere, the diimine type metal complex B10Mg dissolved in dichloromethane;
s2: adding the mixed solution obtained in the step S1 to IL Support2 dispersed with 1g in an inert atmosphere Stirring the mixture in a dichloromethane solution of a carrier for 60min, filtering, leaching the solid, and pumping the solid to obtain the supported catalyst shown in the formula (I 5).
Example 8
Preparation of Supported catalyst of formula (I 6)
S1: in an inert atmosphere, the diimine type metal complex C10Mg dissolved in dichloromethane;
s2: adding the mixed solution obtained in the step S1 to IL Support2 dispersed with 1g in an inert atmosphere Stirring the mixture in a dichloromethane solution of a carrier for 60min, filtering, leaching the solid, and pumping the solid to obtain the supported catalyst shown in the formula (I 6).
Example 9
The ethylene polymerization was carried out using the supported catalysts, diimine type metal complexes a, diimine type metal complexes B and diimine type metal complexes C prepared in examples 3 to 5, respectively, and the specific polymerization method was as follows:
S1: in a glove box, 15mL of n-heptane was added to a 350mL autoclave (with a magnetic stirring device, an oil bath heating device and a thermometer) under nitrogen atmosphere, then the vessel was connected to a high-pressure line and evacuated to a pipeline, and the vessel temperature was set to 30 ℃ and kept for 5min;
S2: the supported catalysts (containing 1. Mu. Mol of nickel), diimine-type metal complex A, diimine-type metal complex B and diimine-type metal complex C prepared in examples 3 to 5 were each dispersed in 5mL of n-heptane, and injected into an autoclave via syringe, followed by injection of the desired equivalent of diethylaluminum chloride. Then an ethylene valve is opened, ethylene is introduced into the autoclave, the ethylene pressure is regulated to 8 standard atmospheric pressure, and the reaction is carried out for 10min. Stopping the reaction, opening the autoclave, adding ethanol to precipitate solid, filtering under reduced pressure, and drying in a vacuum drying oven to obtain white solid, wherein the result is shown in Table 1;
s3: the polymers obtained with the numbers 2 and 5 were photographed, and the obtained pictures are shown in fig. 6.
Comparative example 1
The diimine type metal complex A, the diimine type metal complex B and the diimine type metal complex C are adopted to carry out ethylene polymerization reaction respectively, and the specific polymerization method is as follows:
Except that "the diimine type metal complex a, the diimine type metal complex B and the diimine type metal complex C in step S2 were dispersed in 5mL of n-heptane, respectively; the procedure of example 9 is repeated except that the polymer obtained in step S3, having the number 1, is photographed.
TABLE 1
Remarks:
a Polymerization conditions: the catalyst is 1 mu mol, the n-heptane is 20mL, the ethylene is 8 standard atmospheric pressure, and the reaction time is 15min; b The unit of activity is 10 6g·mol-1·h-1;
c The melting point is measured by a differential scanning calorimeter;
d The number average molecular weight is 10 4g mol-1, the molecular weight is determined by GPC using polystyrene as a standard and trichlorobenzene as a solvent at 150 ℃;
e Degree of branching: the degree of branching is determined by nuclear magnetic hydrogen spectroscopy.
From the data analysis in table 1, the following conclusions can be drawn: compared with the catalyst of the post-transition metal complex, when the catalyst of the post-transition metal complex supported by the carrier modified by the ionic liquid catalyzes the polymerization reaction of ethylene under certain conditions, the activity of the catalyst is improved, the number average molecular weight of the polymer is improved, the molecular weight distribution of the polymer is reduced, and the branching degree of the polymer is also reduced. Wherein the highest polymerization activity can reach 16.8X10 6g·mol-1·h-1, the melting point can reach 123.5 ℃, the number average molecular weight distribution is 0.33-224.1X10. 10 4 g/mol, and the molecular weight distribution is 1.5-3.9.
From the analysis in fig. 6, the following can be concluded: when catalyzing the polymerization reaction of ethylene under certain conditions, when the diimine type metal complex A is used as a catalyst, the prepared polymer is amorphous; when the supported catalyst shown in the formula (I 1) is used as a catalyst, the polymers prepared under different conditions are semi-crystalline polymers.
Example 10
The supported catalysts prepared in example 3 and example 5 were used for the copolymerization of ethylene with polar monomers, and the specific polymerization method was as follows:
s1: 15mL of n-heptane and the required amount of polar monomer were added to a 350mL autoclave (equipped with a magnetic stirring device, an oil bath heating device and a thermometer) under nitrogen atmosphere in a glove box, and then the vessel was connected to a high-pressure line and evacuated to a tube, and the vessel temperature was set to 30℃and kept for 5 minutes;
S2: the supported catalysts prepared in example 3 and example 5 (containing 10. Mu. Mol of nickel) were each dispersed in 5mL of n-heptane and injected into the autoclave via syringe, followed by injection of the desired equivalent of diethylaluminum chloride. Then an ethylene valve is opened, ethylene is introduced into the autoclave, the ethylene pressure is regulated to 8 standard atmospheric pressure, and the reaction is carried out for 10min. After that, the reaction was stopped, the autoclave was opened, and ethanol precipitated solid was added to the autoclave, filtered under reduced pressure, and dried in a vacuum oven to obtain a white solid, the results of which are shown in Table 2.
TABLE 2
Remarks:
a Polymerization conditions: the catalyst is 10 mu mol, the n-heptane is 20mL, the ethylene is 8 standard atmospheric pressure, the polymerization temperature is 30 ℃, and the reaction time is 30min;
b The unit of activity is 10 5g·mol-1·h-1;
c The polar monomer insertion ratio was determined by nuclear magnetic resonance hydrogen spectroscopy;
d The melting point is measured by a differential scanning calorimeter;
e The number average molecular weight was 10 4g mol-1, the molecular weight was determined by GPC using polystyrene as standard and trichlorobenzene as solvent at 150 ℃.
From the data analysis in table 2, the following conclusions can be drawn: when the ionic liquid modified carrier-supported late transition metal complex catalyst catalyzes the polymerization reaction of olefin (particularly polar monomer) copolymerization under certain conditions, the highest polymerization activity can reach 3.1 multiplied by 10 5g·mol-1·h-1, and the highest polar monomer insertion ratio can reach 5.1%; the melting point can reach 124.2 ℃, the number average molecular weight is distributed at 0.3-4.9X10 4 g/mol, and the molecular weight is distributed at 2.1-4.4.
According to the supported catalyst, the preparation method and the application thereof, the ionic liquid is introduced into the carrier in a mode that anions or cations of the ionic liquid react with chemical groups on the surface of the carrier, so that the morphological characteristics of the surface of the carrier are changed, and a medium which is covered on the surface of the carrier and can anchor the metal complex is formed; and further, the direct interaction between the surface of the carrier and the metal complex can be prevented, the steric hindrance and poisoning effect of the carrier on the active center of the metal complex are reduced, and the insertion of the comonomer into the active center of the metal complex in the ionic liquid medium is facilitated. The ionic liquid modified carrier is applied to the supported late transition metal catalyst, which is favorable for improving the activity of the catalyst, improving the thermal stability, the melting point and the molecular weight of the polymer and preventing kettle scale from being generated when the polymer is stuck to a kettle; in the aspect of copolymerization, the catalyst is beneficial to improving the poisoning resistance of polar monomers, improving the insertion ratio of the polar monomers and being beneficial to catalyzing the copolymerization of ethylene and the polar monomers by the supported post-transition catalyst. In addition, the ionic liquid has the characteristics of low price, wide source, safety, environmental protection, easy separation and recovery and environmental protection, is applied to a heterogeneous polymerization system of a supported transition metal catalyst, and is favorable for the application of the heterogeneous catalyst in the aspect of olefin polymerization industrialization.
While the foregoing is directed to embodiments of the present disclosure, other and further details of the invention may be had by the present application, it is to be understood that the foregoing description is merely exemplary of the present disclosure and that no limitations are intended to the scope of the disclosure, except insofar as modifications, equivalents, improvements or modifications may be made without departing from the spirit and principles of the present disclosure.
Claims (10)
1. A supported catalyst, comprising:
an ionic liquid modified support, wherein an anion or cation of the ionic liquid reacts with a chemical group on the surface of the support to modify the support, and the cation of the ionic liquid contains an atom capable of providing an electron; and
A complex of a diimine-containing ligand or a phosphine sulfonic acid-containing ligand coordinated late transition metal supported on the ionic liquid modified support, wherein the empty orbitals provided by the heteroatom N or O in the complex ligand interact with electrons provided by the carbon atoms in the cation of the ionic liquid, thereby being anchored to the support by the ionic liquid.
2. The supported catalyst of claim 1, wherein the catalyst is,
The ionic liquid modified carrier comprisesAny one of them;
Wherein R 'in the-OR' comprises any one of hydrogen, substituted OR unsubstituted aliphatic hydrocarbon group of C 1～C6, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon-based and substituted OR unsubstituted phenyl, and a is an integer of 1-20;
R in- (AlCl nR3-n) m comprises a hydrocarbon group of C 1～C12, n is an integer from 0 to 3, and m is an integer from 1 to 20;
Y comprises any one of substituted pyrrolidinium and substituted imidazolium, wherein the substituent of the substituted pyrrolidinium and the substituted imidazolium comprises any one of hydrogen, substituted or unsubstituted aliphatic hydrocarbon group of C 1～C6, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group and substituted or unsubstituted phenyl;
The carrier comprises any one of silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate and carbon black;
the post-transition metal comprises any one of nickel and palladium;
the ionic liquid comprises Any one of the following.
3. The supported catalyst of claim 1, wherein the catalyst is,
The diimine-containing ligands include Any one of them;
The phosphine sulfonic acid-containing ligand comprises
Ar comprises any one of substituted phenyl and substituted naphthyl, wherein the substituents in the substituted phenyl and substituted naphthyl comprise hydrogen, substituted or unsubstituted C 1～C12 aliphatic hydrocarbon, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon, and substituted or unsubstituted phenyl;
R 1 and R 2 include any one of hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group of C 1～C12, a substituted silicon group, a substituted or unsubstituted phenyl group; or alternatively
R 1 and R 2 can be bonded to each other or form a ring;
M 1～M5、N1～N6 comprises any one of hydrogen, substituted or unsubstituted aliphatic hydrocarbon group of C 1～C12, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group, and substituted or unsubstituted phenyl group respectively.
4. The supported catalyst of claim 1, wherein the catalyst is,
The complex comprises Any one of them;
X 'and Y' comprise any one of fluorine, chlorine, bromine, iodine, aliphatic hydrocarbon group of C 1～C12, aryl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group and tin-containing group; or alternatively
The X 'and Y' moieties can be bonded to each other or form a ring;
Ar, R 1、R2、M1～M5、N1～N6 are as defined in claim 3.
5. The supported catalyst of claim 4, wherein the catalyst comprises,
The oxygen-containing group comprises any one of alkoxy, sulfonyl and carboxyl;
the nitrogen-containing group comprises any one of pyridyl, nitro, cyano, pyrrolyl, thiazolyl, imidazolyl, pyrazolyl and pyrimidinyl;
The sulfur-containing group comprises any one of sulfonyl and thienyl;
the boron-containing group comprises phenyl boron;
The aluminum-containing group comprises any one of aluminum alkyl and aluminum alkoxy;
the phosphorus-containing group comprises any one of phenylphosphine and phenylphosphine;
the silicon-containing group includes a siloxy group.
6. The supported catalyst according to claim 5, comprising any one of structures represented by formulas (I 1) to (I 6):
7. a method for preparing the supported catalyst according to any one of claims 1 to 6, comprising:
Under the anhydrous and anaerobic condition, the ionic liquid modified carrier is separated into an organic solvent to obtain an organic dispersion liquid;
Under the anhydrous and anaerobic condition, dissolving a ligand containing diimine or a complex containing phosphine sulfonic acid and coordinated post-transition metal into an organic solvent to obtain an organic solution;
and adding the organic solution into the organic dispersion liquid to react for 1-120 min under the anhydrous and anaerobic condition to obtain the supported catalyst.
8. The method for preparing a supported catalyst according to claim 7, wherein the mass ratio of the complex to the ionic liquid modified support is 1:20 to 1:50000.
9. The use of a supported catalyst according to any one of claims 1 to 6 for the preparation of polyolefins,
Under the action of the supported catalyst, olefin is polymerized to prepare polyolefin.
10. The use of a supported catalyst according to claim 9 for the preparation of polyolefins,
The olefin comprises any one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-octadecene, polar group-containing C 2～C20 -olefin derivatives and polar group-containing cycloolefin derivatives;
wherein the polar group comprises any one of oxygen-containing, nitrogen-containing, sulfur-containing and selenium-containing organic functional groups, and the organic functional groups comprise any one of hydroxyl, carboxyl, ester, alkoxy, amino, amido, thioether, silyl ether and selenoethyl groups.
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