CN115591586A - Application of metal catalyst loaded on super-crosslinked polymer in cyclic carbonate synthesis - Google Patents
Application of metal catalyst loaded on super-crosslinked polymer in cyclic carbonate synthesis Download PDFInfo
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- CN115591586A CN115591586A CN202211301562.0A CN202211301562A CN115591586A CN 115591586 A CN115591586 A CN 115591586A CN 202211301562 A CN202211301562 A CN 202211301562A CN 115591586 A CN115591586 A CN 115591586A
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- metal catalyst
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- hypercrosslinked polymer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 24
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 239000013315 hypercross-linked polymer Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- -1 aryl compound Chemical class 0.000 claims abstract description 30
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910001507 metal halide Inorganic materials 0.000 claims description 9
- 150000005309 metal halides Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 claims description 2
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003426 co-catalyst Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- VOZIDVYZYUQUPE-UHFFFAOYSA-N [diphenyl-(2-phenylphenyl)methyl]phosphanium bromide Chemical compound [Br-].C=1C=CC=CC=1C(C=1C(=CC=CC=1)C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 VOZIDVYZYUQUPE-UHFFFAOYSA-N 0.000 description 1
- OKGSCJANHYMPOU-UHFFFAOYSA-N [diphenyl-(2-phenylphenyl)methyl]phosphanium chloride Chemical compound [Cl-].C=1C=CC=CC=1C(C=1C(=CC=CC=1)C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 OKGSCJANHYMPOU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
- B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0269—Phosphorus containing compounds on mineral substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/135—Cross-linked structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
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Abstract
The invention provides an application of a metal-loaded catalyst of a hypercrosslinked polymer in cyclic carbonate synthesis. The hypercrosslinked polymer-based metal catalyst is prepared from a porous hypercrosslinked polymer-supported metal; the porous hypercrosslinked polymer is catalyzed by aryl compound as synthetic monomer, dimethoxymethane as cross-linking agent and anhydrous ferric trichlorideThe agent is prepared by Friedel-crafts alkylation reaction; the structural formula of the aryl compound is shown as a formula L 1 ‑L 5 One kind of (1). The super-crosslinked polymer catalyst provided by the invention has high catalytic efficiency, and no additional solvent, TBAB and other co-catalysts are needed in the reaction process, so that the separation and purification of the product are facilitated. CO catalysis using the catalyst provided by the invention 2 The yield of cyclic carbonate synthesized with propylene oxide can reach 99% optimally. Meanwhile, the use of the hypercrosslinked polymer catalyst can reduce CO 2 The catalytic reaction is carried out under the concentration, and technical support is provided for industrial application.
Description
Technical Field
The invention relates to the field of high-activity catalysts, in particular to an application of a hypercrosslinked polymer supported metal catalyst in cyclic carbonate synthesis.
Background
The cycloaddition of propylene oxide to carbon dioxide to form cyclic carbonates is to solve the problem of CO 2 One of the effective ways to solve the problem is that the reaction is an important way to achieve the goal of 'double carbon', and the product cyclic carbonate is an organic solvent and an organic synthesis intermediate with excellent performance. Thus, in recent years research various organometallic catalysts and metal complexes have been developed for CO 2 The cycloaddition reaction of (2) includes alkali metal salts, quaternary ammonium salts, lewis acids, schiff bases, metalloporphyrins and the like. However, the use of homogeneous catalysts poses great difficulties in the analysis of the products, and the separation and purification of cyclic carbonates from the homogeneous reaction system is a cumbersome and energy-consuming task.
In heterogeneous catalytic systems, porous organic polymers have attracted considerable attention from researchers, not only because of their high specific surface area, large pore volume, good chemical stability, etc., but also because of the ease with which the active sites of the catalyst are grafted into the backbone of the organic polymer material. However, most of these catalysts are high temperature, high CO 2 The excellent catalytic performance is exhibited under pressure, resulting in an increase in energy consumption, production cost, and the like. Porous material CO at room temperature 2 Conversion efficiency of material-dependent CO 2 Influence of Capacity, typical porous materials have lower CO 2 Capture capacity, resulting in CO near the active site of the catalyst 2 Lower concentration, thereby affecting the CO 2 Catalytic conversion ability of (1). The N, P doped super cross-linked organic polymer has higher CO due to the electron-donating active site 2 Adsorption capacity, can increase CO near the active site of the catalyst 2 And (4) concentration.
The prior catalyst has the problems of harsh reaction conditions, difficult separation of reaction products and the like in a homogeneous catalyst, an ionic liquid catalyst and the like. The supported metal catalyst reaction system needs to add promoters such as tetrabutylammonium bromide (TBAB) and the like to improve the yield of cyclic carbonate, but the introduction of the promoters such as TBAB and the like brings new problems for the separation and purification of products, and greatly increases the production cost.
Disclosure of Invention
The first purpose of the invention is to provide a super cross-linked polymer supported metal catalyst, which can be used for efficiently catalyzing CO at normal temperature and normal pressure without adding a cocatalyst TBAB 2 With propylene oxide, cyclic carbonates were successfully synthesized.
The metal catalyst loaded by the super cross-linked polymer is prepared by porous metal loaded by the super cross-linked polymer; the porous hypercrosslinked polymer is prepared by taking an aryl compound as a synthetic monomer, dimethoxymethane as a cross-linking agent and anhydrous ferric chloride as a catalyst through Friedel-Crafts alkylation (Friedel-Crafts alkylation reaction) hypercrosslinking reaction;
the structural formula of the aryl compound is shown as the following formula L 1 -L 5 One of (1);
in a preferred embodiment of the present invention, the aryl compound is preferably of formula L 2 -L 5 Any of the above, more preferably an N, P onium salt-containing ligand, i.e., L 4 Or L 5 。
In a preferred embodiment of the present invention, the metal in the hypercrosslinked polymer supported metal catalyst may be a metal commonly used in the art, preferably cobalt, iron or aluminum, and more preferably cobalt.
In a particular embodiment of the invention, the hypercrosslinked polymerThe synthesis route of the supported metal catalyst can be (as L) 1 And metallic cobalt for example):
in one embodiment of the present invention, the content of phosphine, halogen and metal in the hypercrosslinked polymer supported metal catalyst is 0.1-5%, 0.1-5% and 0.1-5%. In a preferred embodiment of the present invention, in the hypercrosslinked polymer supported metal catalyst, the nitrogen content is 0.1 to 5%, the phosphine content is 0.1 to 5%, the halogen content is 0.1 to 5%, the metal content is 0.1 to 5%, and the balance is carbon and hydrogen. In the present invention, "%" is a mass percentage unless otherwise specified.
In a preferred embodiment of the present invention, the method for preparing the porous hypercrosslinked polymer specifically comprises the steps of:
1) Dissolving aryl compound and benzene in an organic solvent according to a proportion, and uniformly stirring; the aryl compound is one or more of triphenylphosphine, triphenyl benzyl phosphine bromide, triphenyl benzyl phosphine chloride, triphenyl (2-pyridylmethyl) phosphine bromide hydrochloride and triphenyl (2-pyridylmethyl) phosphine chloride hydrochloride;
2) Under the protection of nitrogen, respectively adding a cross-linking agent and ferric trichloride into the mixed solution obtained in the step 1), reacting for 4-6 h at 40-50 ℃, heating to 75-80 ℃, continuing to react for 19-43 h, cooling to room temperature after the reaction is finished, and performing Soxhlet extraction and vacuum drying on the obtained solid to obtain the material A.
In a preferred embodiment of the present invention, in order to improve the synthesis yield and the catalytic efficiency, the molar ratio of the aryl compound to benzene in step 1) is 1 (10-15). Among them, the organic solvent in the step 1) is preferably 1,2-dichloroethane. In this step, the mass-to-volume ratio of the aryl compound to the organic solvent is preferably (50 to 1000) mg/10mL.
In a preferred embodiment of the invention, in step 2), the crosslinking agent is dimethoxymethane, dichloromethane, 1,2-dichloroethane or carbon tetrachloride. In the step 2) of the invention, the hypercrosslinked polymer prepared by the Friedel-crafts alkylation reaction with dimethoxymethane participated has high micropore ratio and large specific surface area, and can stabilize the metal active center, so the cross-linking agent in the preparation method is more preferably dimethoxymethane. The molar ratio of the crosslinking agent to the aryl compound is preferably (30 to 50): 1. In the embodiment of the present invention, the molar ratio of ferric trichloride to the aryl compound is preferably (100 to 120): 1. The conditions for vacuum drying are preferably as follows: drying for 12-48 h at 30-150 ℃. The reaction in step 2) is generally carried out in a round-bottomed flask equipped with a condenser.
In the invention, the material A obtained in the step 2) is the porous hypercrosslinked polymer of the invention. The metal can be supported on the porous hypercrosslinked polymer by methods common in the art. In a preferred embodiment of the present invention, the hypercrosslinked polymer supported metal catalyst comprises the steps of:
3) Soaking the material A into ethanol to obtain a material B;
4) And (3) immersing the material B into a metal halide aqueous solution, stirring for 12-48 h, taking a solid phase, and drying to obtain the super cross-linked polymer supported metal catalyst.
In the present invention, immersing a material a in ethanol before immersing a material a in an aqueous solution of a metal halide is a critical step, and in a preferred embodiment of the present invention, in the step 3), the mass-to-volume ratio of the material a to the ethanol is (50-100) mg:5mL.
In a preferred embodiment of the present invention, in order to obtain a catalyst having better catalytic activity and stability, the concentration of the aqueous solution of the metal halide in step 4) is 0.5 to 4mg/mL. In a preferred embodiment of the invention, the mass-to-volume ratio of the material a to the aqueous solution of the metal halide is 100mg: (3-19) mL. Within this range, the catalytic effect of the resulting catalyst can be optimized. In step 4), the drying is preferably vacuum drying, and the conditions of the vacuum drying are preferably as follows: drying for 12-48 hours at 30-150 ℃.
In a preferred embodiment of the invention, where the metal is cobalt, iron or aluminium, the corresponding metal halide is preferably cobalt chloride, iron chloride or aluminium chloride, preferably cobalt chloride. In the present embodiment, steps 3) and 4) are preferably carried out at room temperature.
The preparation method of the super cross-linked polymer supported metal catalyst is simple and high in yield. Another object of the present invention is to provide a method for preparing the metal catalyst supported on the hypercrosslinked polymer, which comprises the following steps:
1) Dissolving aryl compound and benzene in a solvent 1,2-dichloroethane according to a ratio, and uniformly stirring;
2) Under the protection of nitrogen, adding dimethoxymethane and ferric trichloride into the mixed solution obtained in the step 1) respectively, reacting for 4-6 h at 40-50 ℃, heating to 75-80 ℃, continuing to react for 19-43 h, cooling to room temperature after the reaction is finished, and performing Soxhlet extraction and vacuum drying on the obtained solid to obtain a material A;
3) Dispersing the material A in ethanol to obtain a material B;
4) And (3) immersing the material B into a metal halide aqueous solution, stirring for 12-48 h, taking a solid phase, and drying to obtain the super cross-linked polymer supported metal catalyst.
The parameters in the above steps are preferably referred to above, and detailed description is not repeated here.
The super-crosslinked polymer supported metal catalyst prepared by the preparation method has high catalytic efficiency, does not need to be additionally added with auxiliary catalysts such as TBAB and the like, and is particularly suitable for being used for CO at normal temperature and normal pressure 2 And propylene oxide as raw material to synthesize cyclic carbonate.
Namely, another object of the present invention is to provide the above-mentioned metal catalyst supported on a hypercrosslinked polymer at normal temperature and pressure with CO 2 And propylene oxide as raw material in the synthesis of cyclic carbonate.
In a specific embodiment of the present invention, the "reaction for synthesizing a cyclic carbonate at normal temperature and pressure" comprises the following specific steps: with CO 2 And propylene oxide as raw materials, the super cross-linked polymer supported cobalt material as a catalyst, and reacting for 12-48 h at the temperature of 25-50 ℃ under the pressure of 0.01-1 MPa to obtain the cyclic carbonate.
No cocatalyst is required in the reaction.
Wherein, the propylene oxide can be selected from one of the compounds with the following structures:
in this reaction, the amount of propylene oxide to be added is preferably 5 to 100mmol, and more preferably 50mmol. CO 2 2 The output pressure is more preferably 0.1MPa. CO 2 2 The concentration of (c) may be 10% to 99%.
Compared with the existing catalyst, the invention has the following characteristics:
1. the super-crosslinked polymer supported metal catalyst provided by the invention has high catalytic efficiency, and no auxiliary catalyst such as TBAB and the like and solvent are required to be added, so that the separation and purification of the product are convenient.
2. The preparation process of the super-crosslinked polymer supported metal catalyst provided by the invention is simple, the super-crosslinked polymer supported metal catalyst can be prepared in a large scale, and the cost is low.
3. The catalytic reaction system using the super-crosslinked polymer supported metal catalyst provided by the invention is simple, and the catalyst is directly added into a catalyst filled with CO 2 The epoxy of (3) does not require a heat treatment and activation step.
4. CO catalysis using the hypercrosslinked polymer supported metal catalyst provided by the invention 2 The cyclic carbonate is selectively synthesized with the epoxypropane, and the yield can reach 99% optimally. Meanwhile, the use of the super-crosslinked polymer supported metal catalyst can realize low-concentration CO 2 The catalytic reaction provides technical support for industrial application.
5. The super-crosslinked polymer supported metal catalyst provided by the invention has high catalytic activity. The active center of the catalyst is a supported metal ion (preferably Co ion), and the quaternary phosphine halide salt on the catalyst carrier has the function of replacing a cocatalyst. The concentration of the formed alkali phosphine cations is high, so that the catalytic activity of the metal is increased; meanwhile, the formed halide anions have higher electronegativity, and the catalytic action is further enhanced.
6. The metal component loss rate of the super cross-linked polymer supported metal catalyst provided by the invention is low, and the service life of the catalyst is long. The invention still keeps higher catalytic activity after being used for 10 times under the condition of laboratory use. The good recycling performance of the catalyst is attributed to the following aspects: (1) The super-high specific surface area and pore volume of the super-crosslinked polymer can form a confinement effect on the adsorbed metal ions, and the stability of the metal active component is improved. (2) Meanwhile, in an optimized ligand structure, N and P heteroatoms can form M-P and M-N bonds, and the carrier and the active center are greatly improved through the bonding force of valence bonds, so that the stability of metal ions is further improved.
Drawings
FIG. 1 shows a metal catalyst C supported on a hypercrosslinked polymer obtained in example 1 1 SEM characterization of (a);
FIG. 2 shows a metal catalyst C supported on a hypercrosslinked polymer obtained in example 2 2 SEM characterization of (d);
FIG. 3 shows a metal catalyst C supported on a hypercrosslinked polymer obtained in example 3 3 SEM characterization of (d);
FIG. 4 shows a metal catalyst C supported on a hypercrosslinked polymer obtained in example 4 4 SEM characterization of (a);
FIG. 5 shows a metal catalyst C supported on a hypercrosslinked polymer obtained in example 5 5 SEM characterization of (d).
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention. In addition, because of space and word number limitations, the comparative examples and comparative examples given in the summary of the invention are not specifically listed in the document of the present invention.
Triphenylphosphine, benzene, 1,2 Dichloroethane (DCE), dimethoxymethane (FDA), etc., used in the examples were obtained from Allantin reagents, inc. The elemental analysis and detection of the catalyst were carried out by an elemental analysis spectrometer manufactured by Japan science and Co. The M-N, M-P bonds in the hypercrosslinked polymer are determined by infrared spectroscopy.
Example 1
The embodiment of the invention provides a hypercrosslinked polymer supported metal catalyst C 1 The preparation method comprises the following steps:
(1) Triphenylphosphine (0.1mmol, 0.26g), and benzene (1.5mmol, 0.12g) were dissolved in 1,2-dichloroethane (DCE, 5 mL).
(2) After the substrate was completely dissolved, FDA (4.0 mmol, 0.30g) and anhydrous FeCl were added at room temperature under nitrogen protection 3 (12mmol，2.0g)。
(3) And reacting the mixture at 45 ℃ for 5 hours under the protection of nitrogen, and heating to 80 ℃ to continue reacting for 19 hours to complete the hypercrosslinking reaction.
(4) The solid product obtained was washed several times with methanol until the filtrate was almost colorless, and the product was further subjected to soxhlet extraction with methanol until colorless and then dried in a vacuum oven at 60 ℃ for 12 hours. The catalyst obtained was a dark powdery solid A 1 。
(5) Mixing 100mg of A 1 Immersing in 5mL of absolute ethyl alcohol, and stirring and dispersing uniformly for later use to obtain B 1 。
(6) Mixing the materials B 1 The mixture was immersed in 5mL of an aqueous solution of cobalt chloride at a concentration of 1mg/mL and stirred for 12 hours. After cooling, the catalyst obtained by filtration is washed three times by ethanol and dried in vacuum at 60 ℃ for 12h to prepare the catalyst C 1 。
(7) Catalyst C 1 The composition of (A) is shown in Table 1, wherein C 1 SEM characterization of (a) is shown in figure 1.
Example 2
The embodiment of the invention provides a super cross-linked polymer supported metal catalyst C 2 The preparation method comprises the following steps:
(1) Triphenylbenzylphosphonium bromide (0.1mmol, 0.43g), and benzene (1.5mmol, 0.12g) were dissolved in 1,2-dichloroethane (5 mL).
(2) After the substrate was completely dissolved, FDA (4.0 mmol, 0.30g) and anhydrous FeCl were added at room temperature under nitrogen protection 3 (12mmol，2.0g)。
(3) And reacting the obtained mixture at 45 ℃ for 5 hours under the protection of nitrogen, and heating to 80 ℃ to continue reacting for 19 hours to complete the hypercrosslinking reaction.
(4) The solid product obtained was washed several times with methanol until the filtrate was almost colorless, and the product was further soxhlet extracted with methanol until colorless and then dried in a vacuum oven at 60 ℃ for 12 hours. The catalyst obtained was a dark powdery solid A 2 。
(5) Mixing 100mg of A 2 Immersing into 5mL of absolute ethyl alcohol, and stirring and dispersing uniformly for later use to obtain B 2 。
(6) Material B 2 The resulting solution was immersed in 5mL of an aqueous solution of 1mg/mL cobalt chloride and stirred for 12 hours. After cooling, the catalyst obtained by filtration is washed three times by ethanol and dried in vacuum at 60 ℃ for 12h to prepare the catalyst C 2 。
(7) Catalyst C 2 The composition of (A) is shown in Table 1, wherein C 2 SEM characterization of (d) is shown in figure 2.
Example 3
The embodiment of the invention provides a super cross-linked polymer supported metal catalyst C 3 The preparation method comprises the following steps:
(1) Triphenylbenzyl phosphonium chloride (0.1mmol, 0.39g), and benzene (1.5mmol, 0.12g) were dissolved in 1,2-dichloroethane (5 mL).
(2) After the substrate was completely dissolved, FDA (4.0 mmol, 0.30g) and anhydrous FeCl were added at room temperature under nitrogen protection 3 (12mmol，2.0g)。
(3) And reacting the obtained mixture at 45 ℃ for 5 hours under the protection of nitrogen, and heating to 80 ℃ to continue reacting for 19 hours to complete the hypercrosslinking reaction.
(4) The solid product obtained was washed several times with methanol until the filtrate was almost colorless, and the product was further soxhlet extracted with methanol until colorless and then dried in a vacuum oven at 60 ℃ for 12 hours. The catalyst obtained was a dark powdery solid A 3 。
(5) Mixing 100mg of A 3 Immersing in 5mL of absolute ethyl alcohol, and stirring and dispersing uniformly for later use to obtain B 3 。
(6) Mixing the materials B 3 The resulting solution was immersed in 5mL of an aqueous solution of 1mg/mL cobalt chloride and stirred for 12 hours. After cooling, the mixture is passedWashing the filtered catalyst with ethanol for three times, and vacuum drying at 60 ℃ for 12h to obtain the catalyst C 3 。
(7) Catalyst C 3 The composition of (A) is shown in Table 1, wherein C 3 SEM characterization of (d) is shown in figure 3.
Example 4
The embodiment of the invention provides a super cross-linked polymer supported metal catalyst C 4 The preparation method comprises the following steps:
(1) Triphenyl (2-pyridylmethyl) phosphine bromide hydrochloride (0.1mmol, 0.55g), and benzene (1.5mmol, 0.12g) were dissolved in 1,2-dichloroethane (5 mL).
(2) After the substrate was completely dissolved, FDA (4.0 mmol, 0.30g) and anhydrous FeCl were added at room temperature under nitrogen protection 3 (12mmol，2.0g)。
(3) And reacting the obtained mixture at 45 ℃ for 5 hours under the protection of nitrogen, and heating to 80 ℃ to continue reacting for 19 hours to complete the hypercrosslinking reaction.
(4) The solid product obtained was washed several times with methanol until the filtrate was almost colorless, and the product was further soxhlet extracted with methanol until colorless and then dried in a vacuum oven at 60 ℃ for 12 hours. The catalyst obtained was a dark powdery solid A 4 。
(5) Mixing 100mg of A 4 Immersing in 5mL of absolute ethyl alcohol, and stirring and dispersing uniformly for later use to obtain B 4 。
(6) Mixing the materials B 4 The mixture was immersed in 5mL of an aqueous solution of cobalt chloride at a concentration of 1mg/mL and stirred for 12 hours. After cooling, the catalyst obtained by filtration is washed three times by ethanol and dried in vacuum at 60 ℃ for 12h to prepare the catalyst C 4 。
(7) Catalyst C 4 The composition of (A) is shown in Table 1, wherein C 4 SEM characterization of (d) is shown in fig. 4.
Example 5
The embodiment of the invention provides a hypercrosslinked polymer supported metal catalyst C 5 The preparation method comprises the following steps:
(1) Triphenyl (2-pyridylmethyl) phosphine chloride hydrochloride (0.1mmol, 0.43g), and benzene (1.5mmol, 0.12g) were dissolved in 1,2-dichloroethane (5 mL).
(2) After the substrate was completely dissolved, FDA (4.0 mmol, 0.30g) and anhydrous FeCl were added at room temperature under nitrogen protection 3 (12mmol，2.0g)。
(3) And reacting the mixture at 45 ℃ for 5 hours under the protection of nitrogen, and heating to 80 ℃ to continue reacting for 19 hours to complete the hypercrosslinking reaction.
(4) The solid product obtained was washed several times with methanol until the filtrate was almost colorless, and the product was further soxhlet extracted with methanol until colorless and then dried in a vacuum oven at 60 ℃ for 12 hours. The catalyst obtained was a dark powdery solid A 5 。
(5) Mixing 100mg of A 5 Immersing in 5mL of absolute ethyl alcohol, and stirring and dispersing uniformly for later use to obtain B 5 。
(6) Mixing the materials B 5 The resulting solution was immersed in 5mL of an aqueous solution of 1mg/mL cobalt chloride and stirred for 12 hours. Cooling, filtering to obtain catalyst, washing with ethanol for three times, vacuum drying at 60 deg.C for 12 hr to obtain catalyst C 5 。
(7) Catalyst C 5 The composition of (A) is shown in Table 1, wherein C 5 SEM characterization of (d) is shown in figure 5.
Example 6
The embodiment of the invention provides a super cross-linked polymer supported metal catalyst C 6 The preparation method comprises the following steps:
(1) Triphenyl (2-pyridylmethyl) phosphine chloride hydrochloride (0.1mmol, 0.43g), and benzene (1mmol, 0.078g) were dissolved in 1,2-dichloroethane (5 mL).
(2) After the substrate was completely dissolved, FDA (4.0 mmol, 0.30g) and anhydrous FeCl were added at room temperature under nitrogen protection 3 (12mmol，2.0g)。
(3) And reacting the mixture at 45 ℃ for 5 hours under the protection of nitrogen, and heating to 75 ℃ to continue reacting for 43 hours to complete the hypercrosslinking reaction.
(4) The solid product obtained is washed several times with methanol until the filtrate is almost colourless, the product is continued to be soxhlet extracted with methanol until colourless and then dried in a vacuum oven at 30 ℃ for 48h. The catalyst obtained was a dark powdery solid A 6 。
(5) 50mg of A 6 Immersing in 5mL of absolute ethyl alcohol, and stirring and dispersing uniformly for later use to obtain B 6 。
(6) Mixing the materials B 6 The mixture was immersed in 19mL of an aqueous solution of cobalt chloride having a concentration of 4mg/mL and stirred for 12 hours. Cooling, filtering to obtain catalyst, washing with ethanol for three times, vacuum drying at 60 deg.C for 12 hr to obtain catalyst C 6 。
(7) Catalyst C 6 The compositions of (A) are shown in Table 1.
Elemental analyses of the catalysts prepared in examples 1-6 are shown in Table 1.
TABLE 1 elemental analysis of the catalysts
Examples of the experiments
The activity of the catalyst prepared by the invention is evaluated on a micro reaction kettle device. 20mg of catalyst (the metal catalyst supported on the hypercrosslinked polymer obtained in examples 1 to 6) was charged into a polytetrafluoroethylene liner (15 ml), 25mmol of propylene oxide was added, and CO was introduced at 0.1MPa 2 Checking airtightness, then stirring and reacting at 25 ℃, controlling the reaction rotating speed and preventing temperature runaway. And opening the reaction kettle after 48 hours to analyze the reaction result, and recovering the catalyst for recycling for multiple times. The cyclic carbonate is extracted by ethyl acetate in the high-pressure reaction kettle after the reaction, and the pure cyclic carbonate is obtained by a reduced pressure distillation method. The evaluation results are shown in Table 2.
TABLE 2 evaluation results of catalysts
As can be seen from table 2, the reaction results show that the catalyst of the present invention has high activity and stability, the conversion rate and selectivity of the reaction both reach above 90% at normal temperature and normal pressure, and the preparation method provided by the present invention has a higher yield (the yield = conversion rate/selectivity of the present invention). When the elements in the catalyst after reaction are analyzed, the contents of the P element and the Co element are not reduced, the loss of the surface metal active component is very small, and the surface catalyst has good stability. The catalyst has the advantages of low metal loss rate, excellent catalytic activity stability and obvious advantage over the prior art.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A metal catalyst supported by a hypercrosslinked polymer, wherein the metal catalyst supported by a hypercrosslinked polymer is made of a porous metal supported by a hypercrosslinked polymer; the porous hypercrosslinked polymer is prepared by taking an aryl compound as a synthetic monomer, dimethoxymethane as a cross-linking agent and anhydrous ferric chloride as a catalyst through Friedel-crafts alkylation reaction;
the structural formula of the aryl compound is shown as the following formula L 1 -L 5 One of (1);
2. the hypercrosslinked polymer supported metal catalyst as claimed in claim 1, wherein the aryl compound has the structural formula of a N, P onium salt-containing ligand.
3. The hypercrosslinked polymer-supported metal catalyst according to claim 1 or 2, characterized in that the metal is cobalt, iron or aluminium, preferably cobalt.
4. The hypercrosslinked polymer-supported metal catalyst according to any one of claims 1 to 3, characterized in that the preparation method of the hypercrosslinked polymer-supported metal catalyst comprises the steps of:
1) Dissolving aryl compound and benzene in an organic solvent according to a proportion, and uniformly stirring; the aryl compound is one or more of triphenylphosphine, triphenyl benzyl phosphonium bromide, triphenyl benzyl phosphonium chloride, triphenyl (2-pyridylmethyl) phosphine bromide hydrochloride and triphenyl (2-pyridylmethyl) phosphine chloride hydrochloride;
2) Under the protection of nitrogen, respectively adding a cross-linking agent and ferric trichloride into the mixed solution obtained in the step 1), reacting for 4-6 h at 40-50 ℃, heating to 75-80 ℃, continuing to react for 19-43 h, cooling to room temperature after the reaction is finished, and performing Soxhlet extraction and vacuum drying on the obtained solid to obtain a material A;
3) Soaking the material A into ethanol to obtain a material B;
4) And (3) immersing the material B into a metal halide aqueous solution, stirring for 12-48 h, taking a solid phase, and drying to obtain the super cross-linked polymer supported metal catalyst.
5. The hypercrosslinked polymer supported metal catalyst according to claim 4, wherein in step 1), the molar ratio of the aryl compound to benzene is 1 (10-15); the solvent is 1,2-dichloroethane.
6. The preparation of the hypercrosslinked polymer supported metal catalyst according to claim 4 or 5 wherein in step 2) the crosslinking agent is dimethoxymethane, dichloromethane, 1,2-dichloroethane or carbon tetrachloride; preferably dimethoxymethane;
and/or in the step 2) and/or the step 4), the vacuum drying conditions are as follows: drying for 12-48 hours at 30-150 ℃.
7. The hypercrosslinked polymer-supported metal catalyst according to any one of claims 4 to 6, wherein the concentration of the aqueous solution of the metal halide is 0.5 to 4mg/mL;
and/or the mass volume ratio of the material A to the aqueous solution of the metal halide is 100mg: (3-19) mL.
8. The hypercrosslinked polymer supported metal catalyst of any one of claims 1 to 7 catalyzing CO at ambient temperature and pressure 2 Application in the synthesis of cyclic carbonates.
9. The use of claim 8, wherein said "catalyzing CO at ambient temperature and pressure 2 The specific steps of the cyclic carbonate synthesis reaction "include: with CO 2 And propylene oxide compounds as raw materials, the hypercrosslinked polymer load metal catalyst of any one of claims 1 to 7 reacts for 12 to 48 hours at the temperature of 25 to 50 ℃ under 0.01 to 1Mpa to obtain cyclic carbonate.
10. Use according to claim 8 or 9, characterized in that the propylene oxide based compound is selected from one having the following structure:
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| GB9909756D0 (en) * | 1999-04-29 | 1999-06-23 | Secr Defence | Synthesis of polycarbonates |
| US20140066533A1 (en) * | 2011-12-19 | 2014-03-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Conjugated microporous macromolecule catalyst complexed with cobalt, chromium, zinc, copper or aluminium, preparation and use thereof |
| KR20200020441A (en) * | 2018-08-17 | 2020-02-26 | 충남대학교산학협력단 | process for preparing cyclic carbonate using hyper crosslinked polymers and hyper crosslinked polymers for selective formation of cyclic carbonates |
| CN113578357A (en) * | 2020-04-30 | 2021-11-02 | 华东师范大学 | Super-crosslinked nitrogen-doped microporous carbonaceous material in-situ supported noble metal catalyst and synthesis and application thereof |
| CN114669332A (en) * | 2022-04-24 | 2022-06-28 | 齐齐哈尔大学 | Preparation method of ionic type ultrahigh cross-linked porous organic polymer supported cobalt catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB9909756D0 (en) * | 1999-04-29 | 1999-06-23 | Secr Defence | Synthesis of polycarbonates |
| US20140066533A1 (en) * | 2011-12-19 | 2014-03-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Conjugated microporous macromolecule catalyst complexed with cobalt, chromium, zinc, copper or aluminium, preparation and use thereof |
| KR20200020441A (en) * | 2018-08-17 | 2020-02-26 | 충남대학교산학협력단 | process for preparing cyclic carbonate using hyper crosslinked polymers and hyper crosslinked polymers for selective formation of cyclic carbonates |
| CN113578357A (en) * | 2020-04-30 | 2021-11-02 | 华东师范大学 | Super-crosslinked nitrogen-doped microporous carbonaceous material in-situ supported noble metal catalyst and synthesis and application thereof |
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