CN116920940B - Catalyst based on porous organic polymer and preparation method and application thereof - Google Patents
Catalyst based on porous organic polymer and preparation method and application thereof Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- -1 1, 4-di (4-formylphenoxy) -2, 5-di (dimethylaminomethyl) benzene Chemical compound 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 2
- 239000005416 organic matter Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000012434 nucleophilic reagent Substances 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract description 7
- 125000000879 imine group Chemical group 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 21
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 21
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000006352 cycloaddition reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000352 supercritical drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 2
- 101150019148 Slc7a3 gene Proteins 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- RKAMCQVGHFRILV-UHFFFAOYSA-N 1-chlorononane Chemical compound CCCCCCCCCCl RKAMCQVGHFRILV-UHFFFAOYSA-N 0.000 description 1
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- CQVWOJSAGPFDQL-UHFFFAOYSA-N 3-iodopropan-1-ol Chemical compound OCCCI CQVWOJSAGPFDQL-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 101100342039 Halobacterium salinarum (strain ATCC 29341 / DSM 671 / R1) kdpQ gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
Classifications
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst based on a porous organic polymer, and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The invention reacts melamine with 1, 4-di (4-formylphenoxy) -2, 5-di (dimethylaminomethyl) benzene to obtain a porous organic polymer, and then introduces nucleophilic reagent sites through alkylation reaction with halogenated organics to obtain the catalyst based on the porous organic polymer. The nucleophilic reagent site is introduced through post-synthesis modification, so that the porous structure of the porous organic polymer can be well maintained. Meanwhile, the obtained catalyst contains rich imine groups, which is beneficial to the adsorption of carbon dioxide. The imine group in the catalyst cooperates with nucleophilic reagent site, and can catalyze the reaction of carbon dioxide and epoxy compound to prepare cyclic carbonate under the conditions of no solvent, no metal and no cocatalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst based on a porous organic polymer, and a preparation method and application thereof.
Background
The carbon dioxide resource utilization is an important technical means for realizing carbon peak and carbon neutralization. Chemical products such as cyclic carbonate for methanol and lithium battery electrolyte, degradable polymers and the like and high-end materials produced by taking carbon dioxide as raw materials become research hot spots for recycling carbon dioxide at present. The cyclic carbonate is prepared by reacting carbon dioxide with an epoxy compound, no by-product is generated, the atomic utilization rate is 100%, the requirements of green chemistry and atomic economy are met, and the cyclic carbonate is one of ideal ways of recycling carbon dioxide. Since carbon dioxide is a very stable compound, it is desirable to develop efficient catalysts for catalyzing the cycloaddition reaction of carbon dioxide with epoxy compounds.
The porous organic polymer has the characteristics of various synthesis modes, excellent stability, rich pore canal structure, adjustable functions and structures and the like, and is widely applied to the field of carbon dioxide capturing and utilizing. Zhou Yang et al in the article Amino Acid Anion Paired Mesoporous Poly (ionic liquids) as Metal-/Halogen-Free Heterogeneous Catalysts for Carbon Dioxide Fixation (ACS sustaiable chem. Eng. 2019, 7, 9387) report a series of mesoporous polyionic liquids containing amino acid anions capable of catalyzing carbon dioxide cycloaddition reactions. However, the specific surface area of the catalyst is relatively low, and the active sites are limitedIs limited, the activity of the catalyst is limited. Chen Jian et al, article The cooperation of porphyrin-based porous polymer and thermal-responsive ionic liquid forefficient CO 2 cycloaddition reaction (Green chem., 2018, 20, 903) a porous organic polymer containing metalloporphyrin units was prepared by polymerization and metal coordination, and was capable of efficiently catalyzing carbon dioxide cycloaddition at 120℃and 3 MPa. But tetrabutylammonium bromide is required to be added as a cocatalyst, and in addition, metal sites in the catalyst are easy to run off in the circulating process, so that the catalyst is not beneficial to industrial application.
Disclosure of Invention
The invention aims to provide a catalyst based on a porous organic polymer, a preparation method and application thereof, wherein melamine is reacted with 1, 4-di (4-formylphenoxy) -2, 5-di (dimethylaminomethyl) benzene to obtain the porous organic polymer, and nucleophilic reagent sites are introduced through alkylation reaction to obtain the catalyst. The nucleophilic reagent site is introduced through post-synthesis modification, so that the porous structure of the polymer can be well maintained. Meanwhile, the obtained catalyst contains rich imine groups, which is beneficial to the adsorption of carbon dioxide. The imine group in the catalyst cooperates with nucleophilic reagent site, and can catalyze the reaction of carbon dioxide and epoxy compound to prepare cyclic carbonate under the conditions of no solvent, no metal and no cocatalyst.
The invention provides a catalyst based on a porous organic polymer, wherein the structural general formula of the porous organic polymer is shown as a formula (1):
wherein X is one of Cl, br and I; n is more than or equal to 1 and is an integer; r is one of OH, COOH, H.
In another aspect, the present invention provides a method for preparing the porous organic polymer-based catalyst, comprising the steps of:
(1) Dispersing melamine and 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in a first organic solvent, reacting for 48-72 hours at the temperature of 100-170 ℃ under the protection of inert gas, filtering the reaction finished product, washing the obtained solid to remove unreacted micromolecules, and then vacuumizing and drying for 8-24 hours at the temperature of 80-120 ℃ to obtain a porous organic polymer;
(2) Dispersing the porous organic polymer and halogenated organic matters obtained in the step (1) into a second organic solvent under the protection of inert gas, controlling the reaction temperature to be 80-140 ℃, reacting for 12-48 hours, filtering the reaction finished product, washing and drying the obtained solid, and obtaining the catalyst based on the porous organic polymer.
Further, in the step (1), the molar ratio of melamine to 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene is 1:0.75-2.
Further, in the step (1), the inert gas is nitrogen or argon, and the first organic solvent is dimethyl sulfoxide or N-methylpyrrolidone; the solvent used for washing is dichloromethane, N-dimethylformamide, deionized water and ethanol in sequence.
Further, in the step (2), the inert gas is nitrogen or argon, and the structural general formula of the halogenated organic matters is as follows:
wherein X is one of Cl, br and I; n is more than or equal to 1 and is an integer; r is one of OH, COOH, H.
Further, in the step (2), the second organic solvent is one of halogenated organic matters, toluene and acetonitrile.
Further, in the step (2), when the second organic solvent is a reactant halogenated organic substance, 20-50mL of halogenated organic substance is added per 1g of porous organic polymer; when the second organic solvent is toluene or acetonitrile, 4-8mmol of halogenated organics and 15-30mL of toluene or acetonitrile are added per 1g of porous organic polymer.
Further, in the step (2), the drying method is carbon dioxide supercritical drying or vacuum drying.
The catalyst based on the porous organic polymer is applied to cycloaddition reaction of carbon dioxide and epoxy compounds.
Compared with the prior art, the invention has the following beneficial effects:
the invention selects 1, 4-di (4-formylphenoxy) -2, 5-di (dimethylaminomethyl) benzene to react with melamine to prepare porous organic polymer rich in imine groups, and then the porous organic polymer-based catalyst is prepared by introducing nucleophilic reagent sites through post-synthesis modification. The imine group in the catalyst cooperates with nucleophilic reagent site, and can efficiently catalyze carbon dioxide cycloaddition reaction under the conditions of no metal, no solvent and no cocatalyst. The active site is introduced by modification after synthesis and a supercritical drying method is adopted, so that the pore canal structure of the polymer can be well maintained. When the catalyst is applied to the reaction of carbon dioxide and an epoxy compound, a solvent, a cocatalyst and metal are not required to be added, the separation and purification of a product are simple, the catalyst is easy to recycle, and the catalyst has good application prospect in actual production.
Drawings
FIG. 1 is a graph showing isothermal adsorption and desorption of nitrogen at 77K for Cat1 obtained in example 1.
FIG. 2 is a transmission electron micrograph of Cat1 obtained in example 1.
Detailed Description
The following detailed description of the invention refers to the accompanying drawings and examples, which are not intended to limit the scope of the invention, but it is apparent that the examples in the following description are only some of the examples of the invention, and that other similar examples are obtained by those skilled in the art without inventive work and fall within the scope of the invention.
Example 1
(1) Dispersing 4mmol of melamine and 3mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in 40mL of dimethyl sulfoxide, reacting for 48 hours at the temperature of 170 ℃ under the protection of nitrogen, filtering the reaction finished product, washing the obtained solid by dichloromethane, N-Dimethylformamide (DMF), deionized water and ethanol in sequence, and then vacuumizing and drying for 24 hours at the temperature of 80 ℃ to obtain a porous organic polymer;
(2) Under the protection of nitrogen, 1g of the porous organic polymer obtained in the step (1) is reacted with 50mL of bromon-butane (X=Br, n=4, R=H), the reaction temperature is controlled to 140 ℃, the reaction is carried out for 12 hours, the reaction completion is filtered by suction, ethanol is used for washing, and then supercritical carbon dioxide supercritical drying is carried out, so that the catalyst Cat1 based on the porous organic polymer is obtained.
The structural formula of the obtained Cat1 is as follows:
wherein X is Br, n is 4, and R is H.
FIG. 1 is a nitrogen adsorption and desorption isothermal graph of Cat1 at 77K with an H1-type hysteresis loop, showing that Cat1 has a micro/mesoporous multi-stage structure, and the BET specific surface area of Cat1 is 452m 2 And/g. Fig. 2 is a transmission electron micrograph of Cat1.
Example 2
(1) Dispersing 4mmol of melamine and 4mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in 40 mLN-methylpyrrolidone, reacting for 72 hours under the protection of argon and at the temperature of 100 ℃, filtering the reaction finished product, washing the obtained solid by dichloromethane, DMF, deionized water and ethanol in sequence, and then carrying out vacuum drying at the temperature of 100 ℃ for 12 hours to obtain a porous organic polymer;
(2) Under the protection of argon, 1g of the porous organic polymer obtained in the step (1) is reacted with 4mmol of 3-iodopropanol (X=I, n=3, R=OH) in 15mL of toluene, the reaction temperature is controlled to be 110 ℃, the reaction is carried out for 24 hours, the reaction completion is filtered by suction, the ethanol is used for washing, and then vacuum drying is carried out, so that the catalyst Cat2 based on the porous organic polymer is obtained.
The structural formula of the obtained Cat2 is different from that of Cat1 in that: x is I, n is 3, and R is OH.
Example 3
(1) Dispersing 4mmol of melamine and 6mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in 40mL of dimethyl sulfoxide, reacting for 56h under the protection of nitrogen at 150 ℃, filtering the reaction completion, washing the obtained solid with dichloromethane, DMF, deionized water and ethanol in sequence, and then vacuumizing and drying for 8h at 120 ℃ to obtain a porous organic polymer;
(2) Under the protection of argon, 1g of the porous organic polymer obtained in the step (1) is reacted with 20mL of n-butyl chloride (X=Cl, n=4, R=H), the reaction temperature is controlled to be 100 ℃, the reaction is carried out for 36 hours, the reaction completion is filtered by suction, the ethanol is used for washing, and then supercritical carbon dioxide drying is carried out, so that the catalyst Cat3 based on the porous organic polymer is obtained.
The structural formula of the obtained Cat3 is different from Cat1 in that: x is Cl.
Example 4
(1) Dispersing 4mmol of melamine and 8mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in 40mL of N-methylpyrrolidone, reacting for 64h under the protection of argon and at the temperature of 130 ℃, filtering the reaction completion, washing the obtained solid by dichloromethane, DMF, deionized water and ethanol in sequence, and then carrying out vacuum drying at 120 ℃ for 8h to obtain a porous organic polymer;
(2) Under the protection of nitrogen, 1g of the porous organic polymer obtained in the step (1) is reacted with 8mmol of bromoacetic acid (X=Br, n=1, R=COOH) in 30mL of acetonitrile, the reaction temperature is controlled to 120 ℃, the reaction is carried out for 24 hours, the reaction completion is filtered by suction, the reaction completion is washed by ethanol, and then vacuum drying is carried out, so that the catalyst Cat4 based on the porous organic polymer is obtained.
The structural formula of the obtained Cat4 is different from Cat1 in that: n is 1, R is COOH.
Example 5
(1) Dispersing 4mmol of melamine and 3mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in 40mL of dimethyl sulfoxide, reacting for 60h under the protection of nitrogen at 140 ℃, filtering the reaction completion, washing the obtained solid with dichloromethane, DMF, deionized water and ethanol in sequence, and then vacuumizing and drying for 12h at 100 ℃ to obtain a porous organic polymer;
(2) Under the protection of argon, 1g of the porous organic polymer obtained in the step (1) is reacted with 6mmol of iodohexane (X=I, n=6, R=H) in 25mL of toluene, the reaction temperature is controlled to 120 ℃, the reaction is carried out for 36H, the reaction completion is filtered by suction, the ethanol is used for washing, and then vacuum drying is carried out, so that the catalyst Cat5 based on the porous organic polymer is obtained.
The structural formula of the obtained Cat5 is different from Cat1 in that: x is I, n is 6.
Example 6
(1) Dispersing 4mmol of melamine and 8mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in 40mL of N-methylpyrrolidone, reacting for 52h under the protection of argon and at 160 ℃, filtering the reaction completion, washing the obtained solid with dichloromethane, DMF, deionized water and ethanol in sequence, and then carrying out vacuum drying at 80 ℃ for 24h to obtain a porous organic polymer;
(2) Under the protection of nitrogen, 1g of the porous organic polymer obtained in the step (1) is reacted with 4mmol of chlorononane (R=H, n=9, X=Cl) in 15mL of acetonitrile, the reaction temperature is controlled to be 100 ℃, the reaction is carried out for 36H, the reaction completion is filtered by suction, the reaction completion is washed by ethanol, and then vacuum drying is carried out, so that the catalyst Cat6 based on the porous organic polymer is obtained.
The structural formula of the obtained Cat6 is different from Cat1 in that: x is Cl and n is 9.
Example 7
10mmol of propylene oxide and 30mg of Cat1 obtained in example 1 are placed in a 15mL stainless steel reaction kettle, the kettle is sealed, 1.5MPa of carbon dioxide is filled, the kettle is transferred into an oil bath at 120 ℃ and stirred for reaction for 12h. After the reaction was completed, the reaction vessel was cooled with an ice-water bath. Then, unreacted carbon dioxide is released, the reacted liquid is transferred to a centrifuge tube containing a certain internal standard (butyl acetate), the reaction kettle is washed by ethanol for multiple times, and the washing liquid is transferred to the centrifuge tube containing the internal standard. Centrifuging, collecting supernatant (catalyst in bottom layer, and dissolving product in supernatant) and subjecting to gas chromatography analysis, wherein propylene carbonate yield is 95%.
Example 8
Similar to example 7, cat2 obtained in example 2 was used instead of Cat1 in example 5, and the other reaction conditions and the process were unchanged, so that the yield of propylene carbonate was 92%.
Example 9
Similar to example 7, cat3 obtained in example 3 was used instead of Cat1 in example 5, and the other reaction conditions and the process were unchanged, and the yield of propylene carbonate was 85%.
Example 10
Similar to example 7, cat4 obtained in example 4 was used instead of Cat1 in example 5, and the other reaction conditions and the process were unchanged, and the yield of propylene carbonate was 89%.
Example 11
Similar to example 7, cat5 obtained in example 5 was used instead of Cat1 in example 7, and the other reaction conditions and the process were unchanged, and the yield of propylene carbonate was 80%.
Example 12
Similar to example 7, cat6 obtained in example 6 was used instead of Cat1 in example 7, and the other reaction conditions and the process were unchanged, so that the yield of propylene carbonate was 73%.
Example 13
Testing catalyst Cat1 for universality: similar to example 7, epichlorohydrin, 1, 2-epoxyhexane and styrene oxide were used as reaction substrates, respectively, instead of propylene oxide in example 7, the conversion of the substrates used was measured as shown in the following table.
Table 1. Example 13 Cat1 catalyzes the reaction results of cycloaddition of other epoxy compounds with carbon dioxide:
finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The catalyst based on the porous organic polymer is characterized in that the structural general formula of the catalyst based on the porous organic polymer is shown as a formula (1):
,
wherein X is one of Cl, br and I; n is more than or equal to 1 and is an integer; r is one of OH, COOH, H.
2. A method for preparing a porous organic polymer-based catalyst according to claim 1, comprising the steps of:
(1) Dispersing melamine and 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in a first organic solvent, reacting for 48-72 hours at the temperature of 100-170 ℃ under the protection of inert gas, filtering the reaction finished product, washing the obtained solid, removing unreacted micromolecules, and then vacuumizing and drying for 8-24 hours at the temperature of 80-120 ℃ to obtain a porous organic polymer;
(2) Dispersing the porous organic polymer and halogenated organic matters obtained in the step (1) into a second organic solvent under the protection of inert gas, controlling the reaction temperature to be 80-140 ℃, reacting for 12-48 hours, filtering the reaction finished product, washing and drying the obtained solid to obtain the catalyst based on the porous organic polymer; the structural general formula of the halogenated organic matters is as follows:
,
wherein X is one of Cl, br and I; n is more than or equal to 1 and is an integer; r is one of OH, COOH, H.
3. The method for preparing a porous organic polymer-based catalyst according to claim 2, wherein the molar ratio of melamine to 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene in step (1) is 1:0.75-2.
4. The method for preparing a porous organic polymer-based catalyst according to claim 2, wherein in the step (1), the inert gas is argon, and the first organic solvent is dimethyl sulfoxide or N-methylpyrrolidone; the solvent used for washing is dichloromethane, N-dimethylformamide, deionized water and ethanol in sequence.
5. The method for preparing a porous organic polymer-based catalyst according to claim 2, wherein in the step (2), the inert gas is argon.
6. The method for preparing a porous organic polymer-based catalyst according to claim 2, wherein in the step (2), the second organic solvent is one of halogenated organic matter, toluene and acetonitrile.
7. The method for preparing a porous organic polymer-based catalyst according to claim 6, wherein in the step (2), when the second organic solvent is a halogenated organic compound, 20 to 50mL of the halogenated organic compound is added per 1g of the porous organic polymer; when the second organic solvent is toluene or acetonitrile, 4-8mmol of halogenated organics and 15-30mL of toluene or acetonitrile are added per 1g of porous organic polymer.
8. The method for preparing a porous organic polymer-based catalyst according to claim 2, wherein in the step (2), the drying method is supercritical carbon dioxide drying or vacuum drying.
9. Use of a catalyst based on a porous organic polymer, characterized in that the catalyst according to claim 1 is used in the preparation of cyclic carbonates by reacting carbon dioxide with an epoxide compound.
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