CN116920941B - Silica-based catalyst loaded with ionic liquid and preparation method and application thereof - Google Patents
Silica-based catalyst loaded with ionic liquid and preparation method and application thereof Download PDFInfo
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- CN116920941B CN116920941B CN202311195022.3A CN202311195022A CN116920941B CN 116920941 B CN116920941 B CN 116920941B CN 202311195022 A CN202311195022 A CN 202311195022A CN 116920941 B CN116920941 B CN 116920941B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 title claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000004593 Epoxy Chemical class 0.000 claims abstract description 11
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- -1 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene Chemical compound 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005956 quaternization reaction Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 9
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 9
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- 101150019148 Slc7a3 gene Proteins 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000779 smoke Substances 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
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an ionic liquid-loaded silicon oxide-based catalyst and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The silicon oxide-based catalyst containing amino and ionic liquid is prepared through grafting, aldehyde-amine condensation reaction and quaternization reaction, and the amino and the ionic liquid can be used for efficiently catalyzing cycloaddition reaction of carbon dioxide and epoxy compounds under the conditions of no solvent, no metal and no cocatalyst in a synergistic manner to prepare the cyclic carbonate. The preparation method of the catalyst is simple and easy to operate, and the obtained catalyst has rich pore channel structure and excellent carbon dioxide enrichment capacity, shows good catalytic performance in cycloaddition reaction of carbon dioxide and epoxy compounds, and has industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an ionic liquid-loaded silicon oxide-based catalyst, and a preparation method and application thereof.
Background
The cycloaddition reaction of carbon dioxide with an epoxy compound to prepare a cyclic carbonate is one of the effective ways of recycling carbon dioxide. Carbon dioxide is a very stable compound, and therefore, there is a need to develop a highly efficient catalyst for cycloaddition reaction of carbon dioxide with an epoxy compound. The ionic liquid has excellent catalytic activity in the cycloaddition reaction of carbon dioxide and an epoxy compound, but has the problems of difficult catalyst recovery, complex product purification process and the like. Therefore, the preparation of heterogeneous catalysts by compounding ionic liquids with porous materials has been widely studied. The Chinese patent document with publication number of CN114558620A discloses a metal-organic framework immobilized ionic liquid catalyst, which is prepared by immobilizing ionic liquid in a metal-organic framework by a chemical bonding method, wherein the obtained catalyst can catalyze carbon dioxide to react with propylene oxide to prepare propylene carbonate. However, the metal organic frame material has poor circulation stability, which is not beneficial to industrial production. The Chinese patent document with publication number of CN111957343B discloses an ionic liquid-loaded silicon oxide catalyst, which is prepared by quaternizing silicon tetrachloride and N-methylimidazole to obtain silicon-based ionic liquid, and then carrying out hydrolysis and condensation reaction. The obtained catalyst can catalyze the carbon dioxide cycloaddition reaction at 90 ℃ and 1 MPa. However, in the preparation process of the catalyst, tetrachlorosilane is used as a raw material, has corrosiveness, emits smoke when heated by water, emits toxic hydrogen chloride gas, and has potential safety hazard. The Chinese patent publication No. CN112844473A discloses an alumina-supported polyion liquid catalyst, which is prepared by polymerizing vinyl imidazole ionic liquid and alumina with the surface modified by a silane coupling agent, and the obtained catalyst can catalyze carbon dioxide to react with epoxy compounds at the temperature of 50-160 ℃ under the pressure of 0.5-6MPa to prepare cyclic carbonate. However, free radical polymerization tends to cause channel blockage, which is detrimental to the exposure of active sites, thereby limiting the activity of the catalyst. Therefore, there is a need to develop an ionic liquid supported catalyst with a simple and safe preparation method and a rich pore structure.
Disclosure of Invention
The invention aims to provide an ionic liquid-loaded silicon oxide-based catalyst, and a preparation method and application thereof. Amino and tertiary amine groups are introduced into silicon oxide through grafting and aldehyde amine condensation reaction, and then the silicon oxide based catalyst loaded with ionic liquid is obtained through quaternization reaction. The silicon oxide-based catalyst contains amino and ionic liquid, and under the synergistic effect of the amino and the ionic liquid, the carbon dioxide and the epoxy compound can be efficiently catalyzed to react under the conditions of no solvent, no cocatalyst and no metal to prepare the cyclic carbonate.
Therefore, the invention provides an ionic liquid-loaded silica-based catalyst, and the structural general formula of the ionic liquid-loaded silica-based catalyst is shown as formula (1):
wherein X is one of Cl, br and I; n=1, 2 or 3.
The invention also provides a preparation method of the ionic liquid-loaded silicon oxide-based catalyst, which is characterized by comprising the following steps:
(1) Adding silicon oxide, aminosilane and 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene into a dry organic solvent, ultrasonically treating for 5-30min, adding acetic acid, then under the protection of nitrogen, controlling the temperature to be 80-140 ℃ for reacting for 12-48h, carrying out suction filtration on the reaction finished product, washing the obtained solid, and drying to obtain solid N-SiO 2 。
(2) Solid N-SiO 2 With halogenated alkanes to tolueneAnd (3) reacting under the protection of nitrogen, controlling the reaction temperature to be 80-140 ℃, reacting for 12-48 hours, carrying out suction filtration on a reaction finished product, washing the obtained solid with ethanol, and drying to obtain the silica-based catalyst loaded with the ionic liquid.
Further, in the step (1), the silicon oxide is one of SBA-15, MCM-41 or tubular silicon oxide; 1-3mmol of aminosilane, 0.25-1.0mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene and 0.2-1mL of acetic acid are added per 1g of silicon oxide.
In the step (1), the aminosilane is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane, and the organic solvent is one of toluene, DMF and N-methylpyrrolidone.
Further, in the step (1), the solvent used for washing is DMF, dichloromethane and ethanol in sequence; the drying method is that under the vacuum condition, the drying is carried out for 8-24 hours at 60-100 ℃.
Further, in the step (2), the chemical formula of the halogenated alkane is CH 3 (CH 2 ) n X, wherein X is one of Cl, br and I; n=1, 2 or 3.
Further, in the step (2), every 1g of solid N-SiO 2 1-4mmol of halogenated alkane is added, and the drying method is that the drying is carried out for 8-24 hours at 60-100 ℃ under vacuum.
The ionic liquid-loaded silicon oxide-based catalyst can catalyze carbon dioxide to react with an epoxy compound to prepare cyclic carbonate.
Compared with the prior art, the invention has the following beneficial effects:
the silica-based catalyst loaded with ionic liquid is prepared through grafting, aldehyde-amine condensation reaction and quaternization reaction. The amino group in the catalyst and the ionic liquid cooperate to efficiently react the catalyst carbon dioxide with epoxide under the conditions of no solvent, no cocatalyst and no metal. The method adopted by the invention can avoid the blockage of the pore canal, improve the exposure degree of the active site, and is beneficial to the diffusion of reactants and the contact of the reactants with the active site. The amino group contained in the catalyst is favorable for enriching carbon dioxide, and has more excellent catalytic activity than the catalyst singly grafted with ionic liquid.
Drawings
FIG. 1 is a graph showing the adsorption of carbon dioxide at 303K for Cat2 obtained in example 2.
FIG. 2 is a graph showing the adsorption of carbon dioxide at 303K for Cat7 obtained in comparative example 1.
FIG. 3 is a graph showing the isothermal adsorption and desorption of nitrogen at 77K for Cat2 obtained in example 2.
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
Preparation of silica-based catalyst Cat1 carrying ionic liquid
1g of SBA-15, 1mmol of 3-aminopropyl triethoxysilane, 0.25mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene are added into 40mL of dry toluene, after 5min of ultrasound, 0.2mL of acetic acid is added, the reaction is carried out for 48h under the protection of nitrogen at a temperature of 80 ℃, the reaction completion is filtered by suction, washed sequentially with DMF, dichloromethane and ethanol, and then dried for 24h under vacuum at 60 ℃ to obtain solid N-SiO 2 。
(2) 1g of solid N-SiO 2 1mmol of bromoethane is dispersed in 10mL of toluene, then the reaction is carried out for 48 hours under the protection of nitrogen and at 80 ℃, the reaction completion is filtered, washed by ethanol and dried for 24 hours under the vacuum condition at 60 ℃, and the silicon oxide-based catalyst Cat1 loaded with ionic liquid is obtained.
The structure of the resulting Cat1 is as follows:
wherein, the silicon oxide is SBA-15, X is Br, and n is 1.
Example 2
Preparation of silica-based catalyst Cat2 carrying ionic liquid
(1) 1g of tubular silica, 1.5mmol of 3-aminopropyl triethoxysilane, 0.5mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene are added to 40mL of dry toluene, after 10min of ultrasound, 0.4mL of acetic acid is added, the reaction is carried out for 36h under the protection of nitrogen at a controlled temperature of 100 ℃, the reaction product is filtered off with suction, washed successively with DMF, dichloromethane and ethanol, and then dried for 16h under vacuum at 80 ℃ to obtain N-SiO 2 。
(2) 1g of solid N-SiO 2 Dispersing 2mmol of bromo-n-butane in 10mL of toluene, then reacting for 36h under the protection of nitrogen and at 100 ℃, filtering the reaction completion, washing with ethanol, and drying for 16h at 80 ℃ under vacuum condition to obtain the ionic liquid-loaded silicon oxide-based catalyst Cat2.
The structure of the resulting Cat2 differs from Cat1 in that SBA-15 is replaced by tubular silica and n is 3.
Carbon dioxide adsorption test (figure 1) was performed on Cat2, and the carbon dioxide adsorption amount was 1.5mmol/g at 303K,1bar, which indicates that Cat2 has good carbon dioxide adsorption performance.
Cat2 was subjected to N at 77K 2 Adsorption and desorption test (figure 3), nitrogen adsorption and desorption isotherm is IV type, and has two hysteresis back rings, which shows that Cat2 contains a double-pore structure, and BET specific surface area is 464m 2 /g。
Example 3
Preparation of silica-based catalyst Cat3 carrying ionic liquid
(1) 1g of MCM-41, 3mmol of 3-aminopropyl triethoxysilane, 1mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene are added to 40mL of dry DMF, after 20min of ultrasound, 0.8mL of acetic acid is added, the reaction is carried out for 24h under nitrogen protection at a temperature of 120 ℃, the reaction product is filtered off with suction, washed successively with DMF, dichloromethane and ethanol, then under vacuum,drying at 100deg.C for 8 hr to obtain solid N-SiO 2 。
(2) 1g of solid N-SiO 2 4mmol of n-propyl iodide is dispersed in 10mL of toluene, then the reaction is carried out for 24 hours under the protection of nitrogen and at 120 ℃, the reaction completion is filtered, washed by ethanol and dried for 8 hours under the vacuum condition at 100 ℃, and the silicon oxide-based catalyst Cat3 loaded with ionic liquid is obtained.
The structure of the resulting Cat3 differs from Cat1 in that SBA-15 is replaced by MCM-41, X is I, and n is 2.
Example 4
Preparation of silica-based catalyst Cat4 carrying ionic liquid
(1) 1g of MCM-41, 3mmol of 3-aminopropyl trimethoxysilane, 1mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene were added to 40mL of dry DMF, after 30min of sonication, 1mL of acetic acid was added, followed by reaction at 140℃under nitrogen protection for 8h. Filtering the reaction finished product, washing with DMF, dichloromethane and ethanol in turn, and drying for 8h at 100 ℃ under vacuum condition to obtain solid N-SiO 2 。
(2) 1g of solid N-SiO 2 3mmol of chloro-n-butane is dispersed in 10mL of toluene, then the reaction is carried out for 12 hours under the protection of nitrogen and at the temperature of 140 ℃, the reaction completion is filtered, washed by ethanol and dried for 8 hours under the vacuum condition at the temperature of 100 ℃ to obtain the silicon oxide-based catalyst Cat4 loaded with the ionic liquid.
The structure of the resulting Cat4 differs from Cat1 in that SBA-15 is replaced by MCM-41, X is Cl, and n is 3.
Example 5
Preparation of silica-based catalyst Cat5 carrying ionic liquid
(1) 1g of tubular silica, 1.5mmol of 3-aminopropyl trimethoxysilane, 0.5mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene are added to 40mL of dry N-methylpyrrolidone, after 20min of ultrasound, 0.8mL of acetic acid are added, the reaction is carried out under nitrogen protection at 120℃for 24h, the reaction mixture is filtered off with DMF, dichloromethane and ethanol in succession and is subsequently washed under vacuumDrying at 80deg.C for 16 hr to obtain solid N-SiO 2 。
(2) 1g of solid N-SiO 2 Dispersing 2mmol of chloro-n-propane in 10mL of toluene, then reacting for 16h under the protection of nitrogen and at 80 ℃, filtering the reaction completion, washing with ethanol, and drying for 16h at 80 ℃ under vacuum condition to obtain the ionic liquid-loaded silicon oxide-based catalyst Cat5.
The structure of the resulting Cat5 differs from Cat1 in that SBA-15 is replaced by tubular silica, X is Cl, and n is 2.
Example 6
Preparation of silica-based catalyst Cat6 carrying ionic liquid
(1) 1g of SBA-15, 1mmol of 3-aminopropyl trimethoxysilane, 0.25mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene were added to 40mL of dry N-methylpyrrolidone, after sonication for 10min, 0.6mL of acetic acid were added, followed by reaction at 100℃under nitrogen for 36h. Filtering the reaction finished product, washing the reaction finished product with DMF, dichloromethane and ethanol in sequence, and then drying the reaction finished product for 24 hours at 60 ℃ under vacuum condition to obtain solid N-SiO 2 。
(2) 1g of solid N-SiO 2 Dispersing 2mmol of n-butyl iodide in 10mL of toluene, then reacting for 36h under the protection of nitrogen and at 100 ℃, filtering the reaction completion, washing with ethanol, and drying for 24h at 60 ℃ under vacuum condition to obtain the ionic liquid-loaded silicon oxide-based catalyst Cat6.
The structure of the resulting Cat6 differs from Cat1 in that X is I and n is 3.
Comparative example 1
Preparation of silica-based catalyst Cat7 carrying ionic liquid
(1) 1g of tubular silica, 1.5mmol of 3-aminopropyl triethoxysilane, 3mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene (in excess, fully reacted with amino groups) are added to 40mL of dry toluene, after sonication for 10min, 0.4mL of acetic acid is added, followed by reaction at a temperature of 100℃under nitrogen protection for 36h, the reaction mixture is filtered off with suction, DMF, dichloromethane, ethanol are addedSequentially washing, and drying at 80deg.C under vacuum for 16 hr to obtain solid N-SiO 2 。
(2) 1g of solid N-SiO 2 2mmol of bromo-n-butane is dispersed in 10mL of toluene, then the reaction is carried out for 36h under the protection of nitrogen and at the temperature of 100 ℃, the reaction completion is filtered, washed by ethanol and dried for 16h at the temperature of 80 ℃ under the vacuum condition, and the silicon oxide-based catalyst Cat7 loaded with the ionic liquid is obtained.
The structure of the resulting Cat7 differs from Cat1 in that SBA-15 is replaced by tubular silica, n is 3, and the excess aldehyde monomer causes complete conversion of the primary amino groups in the catalyst to imine bonds.
Carbon dioxide adsorption test (FIG. 2) was conducted on Cat7, and the carbon dioxide adsorption amount was 0.56mmol/g at 303K,1bar, which indicates that the carbon dioxide adsorption performance of Cat7 obtained in the comparative example was significantly lower than that of Cat2.
Example 7
Performance study of Cat1-Cat7 in catalyzing cycloaddition reaction of carbon dioxide and propylene oxide
10mmol of propylene oxide and 30mg of catalyst are placed in a 15mL stainless steel reaction kettle, the reaction kettle is sealed, 2MPa of carbon dioxide is filled, and then the reaction 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, depositing catalyst on the bottom of the tube, taking supernatant, performing gas chromatography analysis, and determining the yield of propylene carbonate, wherein the reaction result is shown in Table 1. The catalysts are sequentially tested by Cat1-Cat 7.
Example 8
Cat 2-catalyzed carbon dioxide cycloaddition reaction performance research of other epoxy compounds
Similar to example 7, except that 30mg Cat2, 10mmol propylene oxide was used as the catalyst instead of the other epoxy compound as the reaction substrate. The catalyst still showed excellent catalytic performance, and the reaction results are shown in table 2 below.
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 (8)
1. The ionic liquid-loaded silica-based catalyst is characterized in that the structural general formula of the ionic liquid-loaded silica-based catalyst is shown as the formula (1):
,
wherein X is one of Cl, br and I; n=1, 2 or 3.
2. The preparation method of the ionic liquid-loaded silicon oxide-based catalyst is characterized by comprising the following steps of:
(1) Adding silicon oxide, aminosilane and 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene into a dry organic solvent, ultrasonically treating for 5-30min, adding acetic acid, then under the protection of nitrogen, controlling the temperature to be 80-140 ℃ for reacting for 12-48h, carrying out suction filtration on the reaction finished product, washing the obtained solid, and drying to obtain solid N-SiO 2 ;
(2) Solid N-SiO 2 Reacting with halogenated alkane under the protection of nitrogen, controlling the reaction temperature to be 80-140 ℃, reacting for 12-48 hours, and carrying out suction filtration on the reaction finished product to obtain solidWashing with ethanol, and drying to obtain the silica-based catalyst loaded with the ionic liquid.
3. The method for preparing a silica-based catalyst carrying an ionic liquid according to claim 2, wherein in the step (1), the silica is one of SBA-15, MCM-41 or tubular silica; 1-3mmol of aminosilane, 0.25-1.0mmol of 1, 4-bis (4-formylphenoxy) -2, 5-bis (dimethylaminomethyl) benzene and 0.2-1mL of acetic acid are added per 1g of silicon oxide.
4. The method for preparing the ionic liquid-supported silica-based catalyst according to claim 2, wherein the aminosilane is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane, and the organic solvent is one of toluene, N-dimethylformamide and N-methylpyrrolidone.
5. The method for preparing a silica-based catalyst carrying an ionic liquid according to claim 2, wherein in the step (1), the solvent used for washing is DMF, dichloromethane, ethanol in this order; the drying method is that under the vacuum condition, the drying is carried out for 8-24 hours at 60-100 ℃.
6. The method for preparing an ionic liquid-supported silica-based catalyst according to claim 2, wherein in the step (2), the haloalkane has a chemical formula of CH 3 (CH 2 ) n X, wherein X is one of Cl, br and I; n=1, 2 or 3.
7. The method for preparing an ionic liquid-supported silica-based catalyst according to claim 2, wherein in said step (2), N-SiO is added per 1g of solid 2 1-4mmol of halogenated alkane is added, and the drying method is that the drying is carried out for 8-24h at 60-100 ℃ under vacuum.
8. The application of the ionic liquid-loaded silica-based catalyst is characterized in that the ionic liquid-loaded silica-based catalyst as claimed in claim 1 is applied to the preparation of cyclic carbonate by the reaction of carbon dioxide and an epoxy compound.
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