CN115318338A - Porous polymer-based ionic liquid solid acid catalyst and preparation method and application thereof - Google Patents

Porous polymer-based ionic liquid solid acid catalyst and preparation method and application thereof Download PDF

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CN115318338A
CN115318338A CN202210846394.7A CN202210846394A CN115318338A CN 115318338 A CN115318338 A CN 115318338A CN 202210846394 A CN202210846394 A CN 202210846394A CN 115318338 A CN115318338 A CN 115318338A
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porous polymer
ionic liquid
solid acid
acid catalyst
liquid solid
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张甜
赵俊虎
蒋向阳
许梦莹
李明
吕昭锦
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Wuhan University of Technology WUT
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Abstract

The invention discloses a porous polymer-based ionic liquid solid acid catalyst and a preparation method and application thereof. The invention is characterized in that divinyl benzene and a nitrogen-containing ligand are subjected to one-step solvent thermal copolymerization to synthesize a porous polymer matrix without a template agent, and then the porous polymer matrix is grafted and ion-exchanged to obtain the solid acid catalyst. The synthesized solid acid has rich nano pores and strong acidity. Wherein, the introduction of functional groups can obviously improve the acidity and catalytic activity of the catalyst. The catalyst of the invention shows good catalytic activity in Friedel-crafts acylation reaction of various aryl ethers and different acid anhydrides, and has wide application range.

Description

Porous polymer-based ionic liquid solid acid catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of heterogeneous catalysis, in particular to preparation of a porous polymer-based ionic liquid solid acid catalyst and application of the porous polymer-based ionic liquid solid acid catalyst in Friedel-crafts acylation reaction for preparing aryl ketone compounds.
Background
Aromatic ketone is an important fine chemical intermediate, and can be used as a main raw material for synthesizing medicaments, dyes, spices, special plastics and pesticides. The Friedel-crafts acylation reaction using aromatic hydrocarbon and acid anhydride or acyl halide as reactants is one of the most direct and effective ways to prepare aromatic ketone, and is widely applied due to simple reaction and high selectivity. Such reactions typically use homogeneous Lewis acids such as anhydrous AlCl 3 、BF 3 、TiCl 4 Or
Figure BDA0003753005940000011
Liquid acids such as concentrated sulfuric acid, hydrochloric acid, etc. are used as catalysts, which greatly limits their wide use in industry. Therefore, in order to solve the environmental and safety problems caused by the homogeneous catalyst, the development of a green, recyclable and high-performance solid acid catalyst instead of the homogeneous catalyst is urgently needed to realize green cycle production.
Over the past several years, many different types of materials have been used as multi-phase solid acid catalysts. Mainly supported heteropolyacids, metal oxides, metal organic frameworks, zeolite molecular sieves, solid superacids and ionic liquids, etc., which show relatively high catalytic activity in different Friedel-crafts acylation reactions, show great potential to replace the traditional homogeneous Lewis acid catalysts (X.Meng, L.Wang, et al, J.Catal,2020,392,69-79 X.Yang, T.Yasukawa, et al, J.chemistry-An Asian Journal,2021,16 (3): 232-236 D.ZHEN, L.Dong, W.Huang, et al, recoverable Sustainable Energy Reg, 2014,37, 47-68. However, due to the strong solubilizing and complexing abilities of the HCl and aromatic ketones formed, these catalysts are susceptible to leaching of the active species and rapid deactivation or carrier collapse during the reaction. Accordingly, considerable effort remains to be expended in designing more stable, environmentally friendly solid acid catalysts.
In recent years, ionic liquids composed of organic cations and inorganic anions have attracted much attention as organic reaction solvents or catalysts due to their negligible vapor pressure, significant solubility, structural diversity, excellent chemical and thermal stability, potential recoverability, easy separation of products, and the like. To achieve the desired effect, the appropriate cations and anions can be selected to obtain a particular ionic liquid to meet the needs of the reaction. Of these specific ionic liquids, cole et al for the first time published a report of sulfonic acid functionalized ionic liquids, opening a new window for the use of various acid-based ionic liquids in acid catalyzed reactions (a.c. Cole, j.l. jensen, I, et al, j.am. Chem. Soc.2002,124, 5962). However, the use of only ionic liquids as catalysts for organic transformations has certain limitations in view of severe environmental problems and increasing demand for sustainable development. Therefore, supported ionic liquid catalysts are an emerging concept in the field of heterogeneous catalysis. However, in practical applications, there still exist some problems in the application of supported ionic liquid catalysts, such as complicated preparation process, low specific surface area, low grafting density and few reaction sites. Therefore, in designing a supported ionic liquid catalyst, it is necessary to maximize the catalytic performance of the catalyst.
Porous organic polymers are one of the most advanced materials and have received considerable research interest in the field of catalysis in recent years due to their unique properties, such as building block diversity, rich nanoporosity, flexible networks, excellent water resistance, programmable chemical function and large BET specific surface area. Polydivinylbenzene (PDVB) is a typical nanoporous polymer resin due to its large specific surface area and excellent propertiesGood chemical stability, and wide application in the fields of environment, separation, adsorption, catalysis, etc. For example, yuan et al use PDVB and SO 3 CF 3 (OTf) sulfonation to form a solid acid catalyst that dehydrates sorbitol to isosorbide at a much higher reaction rate than commercial acid resins (D.Yuan, L.Li, F.Li, et al. ChemSusChem 20112 (22): 4986-95. Similarly, the porous polymer-based ionic liquid as a high-activity solid acid catalyst should have the characteristics of large BET specific surface area, high acid strength, high active site exposure and the like. Therefore, it is necessary to provide a catalyst which is excellent in friedel-crafts acylation reaction for preparing arone compounds.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a porous polymer-based ionic liquid solid acid catalyst, and a preparation method and application thereof. The invention provides a solid acid catalyst-functionalized porous polymer-based ionic liquid solid acid catalyst which is suitable for Friedel-crafts acylation reaction of aryl ether and anhydride which are used as raw materials, has stable structure and is easy to recycle.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a porous polymer-based ionic liquid solid acid catalyst comprises the following steps:
(1) Ultrasonically dispersing divinylbenzene and a nitrogen-containing ligand into an organic solvent, stirring to obtain a uniformly dispersed solution, then adding an initiator, and continuously stirring at room temperature for 2-5 hours to obtain a mixed solution, wherein the mass ratio of the divinylbenzene to the nitrogen-containing ligand is 1: x, x =0.05 to 0.6;
(2) Carrying out hydrothermal reaction on the mixed solution obtained in the step (1) at the temperature of 80-160 ℃ for 1-4 days, and volatilizing an organic solvent to obtain a porous polymer matrix containing a nitrogen ligand;
(3) Fully dispersing the porous polymer matrix containing the nitrogen ligand in the step (2) in an organic solvent, then adding lactone, refluxing for 1-2 days at 100-140 ℃, filtering, collecting, and washing with ethanol to obtain a quaternized porous polymer;
(4) Fully dispersing the quaternized porous polymer in the step (3) in an organic solvent, adding an organic strong acid, exchanging at room temperature for 1-3 days, and washing to obtain a crude product;
(5) And (4) extracting and purifying the crude product obtained in the step (4) to obtain the porous polymer-based ionic liquid solid acid catalyst.
Preferably, the nitrogen-containing ligand in step (1) is N-vinylimidazole.
Preferably, the organic solvent in step (1) is at least one of N, N' -dimethylformamide, tetrahydrofuran and acetonitrile.
Preferably, the initiator in step (1) is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and dibenzoyl peroxide.
Preferably, the mass ratio of the initiator to the nitrogen-containing ligand in the step (1) is 6.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 120 ℃, and the time of the hydrothermal reaction is 2 days.
Preferably, the organic solvent in step (3) is at least one of toluene, tetrahydrofuran, N-dimethylformamide, ethyl acetate and N-hexane.
Preferably, the lactone in the step (3) is at least one of 1, 3-propane sultone, 1, 4-butane sultone, N- (1-naphthalene) -3-aminopropanesulfonic acid sodium salt and 3- (N, N-dimethyloctylammonium) propane-1-sulfonic acid inner salt.
Preferably, the mass ratio of the lactone to the porous polymer matrix in the step (3) is 0.5-1.2: 1, more preferably 0.8.
Preferably, the organic solvent in step (4) is at least one of dichloromethane, chloroform, benzene and dimethyl sulfoxide.
Preferably, the strong organic acid in step (4) is at least one of trifluoromethanesulfonic acid, trifluoroacetic acid and hemisquaric acid.
Preferably, the volume mass ratio of the strong organic acid to the quaternized porous polymer in the step (4) is 4-10 mL/g, and more preferably 8mL/g.
Preferably, the washing manner in step (4) is: washing with a mixed solution of ethanol and dichloromethane several times.
Preferably, the solvent used in the extraction and purification in the step (5) is ethyl acetate, and the time for extraction and purification is 1 to 4 days.
The porous polymer-based ionic liquid solid acid catalyst prepared by the preparation method of the porous polymer-based ionic liquid solid acid catalyst is provided.
The method for testing the acid capacity of the porous polymer-based ionic liquid solid acid catalyst comprises the following steps:
(1) Dispersing the porous polymer-based ionic liquid solid acid catalyst in an organic solvent, and carrying out ultrasonic treatment for 5-10 min to obtain a first mixed solution;
(2) Adding the mixed solution obtained in the step (1) into a saturated NaCl solution, and fully stirring at room temperature for 2-3 days to obtain a second mixed solution;
(3) And (3) filtering the second mixed solution in the step (2), and titrating by using a NaOH solution in the presence of a phenol-phthalein indicator to determine the acid capacity of the catalyst.
Preferably, the organic solvent in step (1) is methanol.
Preferably, the concentration of the NaOH solution in the step (3) is 0.1mol/L.
The porous polymer-based ionic liquid solid acid catalyst is used as a catalyst for Friedel-crafts acylation reaction to prepare the arone compound.
The porous polymer-based ionic liquid solid acid catalyst is used in Friedel-crafts acylation reaction, has high catalytic activity, and can be recycled for many times by centrifuging, washing, activating and drying the catalyst, such as: in the Friedel-crafts acylation reaction which takes the aryl ether as a substrate and the acid anhydride as an acylation reagent, the conversion rate of the aryl ether of the optimal catalyst can reach more than 80 percent.
In a Friedel-crafts acylation reaction with aryl ether as a substrate and acid anhydride as an acylation reagent, the mass of the porous polymer-based ionic liquid solid acid catalyst accounts for 10-80% of the mass of the aryl ether substrate, the molar ratio of the substrate to the acylation reagent is 1-5, the reaction temperature is 60-180 ℃, the reaction time is 2-48 h, and the rotation speed is 800-1200rpm.
Preferably, in the Friedel-crafts acylation reaction using the aromatic ether as the substrate and the anhydride as the acylation agent, the molar ratio of the anhydride to the aromatic ether is preferably 2.
Preferably, the aryl ether is one of anisole, o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, beta-methoxynaphthalene, nitrobenzene, bromobenzene, benzene, toluene, m-xylene, 1,3, 5-mesitylene, furan and thiophene.
Preferably, the acylating agent is one of acetic anhydride, propionic anhydride, butyric anhydride and benzoic anhydride.
Compared with the prior art, the invention has the beneficial effects that:
(1) The raw material cost for preparing the catalyst substrate is low, a template agent is not required to be introduced, the structure is stable, and the preparation process is simple;
(2) The introduction of the functional component (OTf) increases the catalytic activity of the catalyst;
(3) On the premise of no additional metal, the prepared catalyst shows high catalytic activity in a Friedel-crafts acylation reaction taking acid anhydride as an acylation reagent;
(4) The catalyst after reaction can be recovered by simple centrifugation, washing, activation and drying, so that compared with the traditional catalyst, the reuse rate of the catalyst is improved, and the separation cost of liquid-phase catalytic reaction is reduced;
(5) The catalyst has high thermal stability and chemical stability, and can keep high activity and stability in the catalytic reaction process;
(6) The catalyst shows high catalytic activity in the acylation reaction of various aryl ethers and various acid anhydrides serving as acylation reagents, and has a wide application range.
Drawings
Fig. 1 is a high-resolution projection electron microscope image of the porous polymer-based ionic liquid solid acid catalyst prepared in example 1.
FIG. 2 is a high-resolution SEM image of the porous polymer-based ionic liquid solid acid catalyst prepared in example 2.
FIG. 3 is a high-resolution SEM image of the porous polymer-based ionic liquid solid acid catalyst prepared in example 3.
Fig. 4 is a high-resolution transmission electron micrograph of the catalyst prepared in comparative example 1.
Fig. 5 is a high-resolution transmission electron micrograph of the catalyst prepared in comparative example 2.
FIG. 6 is a bar graph comparing the catalytic activity effect of PDvm-OTf-0.1 catalyst repeated 5 times.
FIG. 7 is a schematic representation of the Friedel-crafts acylation of anisole with acetic anhydride in the presence of a catalyst to produce ketones.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The conversion rate mentioned in the examples is the conversion rate of anisole, and the selectivity is the proportion of the target product in all the products, and is calculated by gas chromatographic analysis.
Example 1
A preparation method of a porous polymer-based ionic liquid solid acid catalyst comprises the following steps:
(1) Dispersing 2g of divinylbenzene and 0.1g of N-vinyl imidazole in tetrahydrofuran, performing ultrasonic treatment for 5min, and stirring at room temperature for 30min to obtain a uniformly dispersed solution; then adding 0.6g of azobisisobutyronitrile as an initiator, and continuously stirring for 3 hours at room temperature to obtain a mixed solution;
(2) Placing the mixed solution obtained in the step (1) in a high-pressure hydrothermal reaction kettle, curing for 2 days at 120 ℃, and volatilizing an organic solvent to obtain a porous polymer matrix containing a nitrogen ligand;
(3) Taking 1g of the porous polymer matrix obtained in the step (2), fully dispersing the porous polymer matrix in a flask containing 45ml of toluene, violently stirring, then adding 0.8g of 1, 3-propane sultone, refluxing for 1 day at the temperature of 120 ℃, filtering, collecting, washing with a large amount of ethanol, and obtaining a quaternized porous polymer;
(4) Fully dispersing 1g of the quaternized porous polymer obtained in the step (3) in a beaker containing dichloromethane, adding 8mL of trifluoromethanesulfonic acid, exchanging at room temperature for 2 days, and washing the obtained precipitate with a mixed solvent of ethanol and dichloromethane (the volume ratio of ethanol to dichloromethane is 3;
(5) And (3) loading 0.8g of the crude product obtained in the step (4) into a Soxhlet extractor, adding 35mL of ethyl acetate serving as an extracting agent, and purifying for 24 hours to obtain the porous polymer-based ionic liquid solid acid catalyst which is recorded as P DVm-OTf-0.1.
Example 2
A preparation method of a porous polymer-based ionic liquid solid acid catalyst comprises the following steps:
the amount of N-vinylimidazole "added in step (1) was replaced with 0.4g, and the procedure was the same as in example 1. The product obtained in example 2 was designated PDvm-OTf-0.4.
Example 3
A preparation method of a porous polymer-based ionic liquid solid acid catalyst comprises the following steps:
the amount of "N-vinylimidazole" added in step (1) was replaced with 1.2g, and the other steps were the same as in example 1. The product obtained in example 2 was designated PDvm-OTf-1.2.
Example 4
The method for testing the acid capacity of the porous polymer-based ionic liquid solid acid catalyst comprises the following steps:
(1) Dispersing 0.1g of the porous polymer-based ionic liquid solid acid catalyst prepared in example 1 in 10mL of methanol, and performing ultrasonic treatment for 5min to obtain a first mixed solution;
(2) Adding the mixed solution obtained in the step (1) into 30mL of saturated NaCl solution, and fully stirring at room temperature for 48h to obtain a second mixed solution;
(3) And (3) filtering the second mixed solution in the step (2), and titrating by using a 0.1mol/L NaOH solution in the presence of a phenol-phthalein indicator to determine the acid capacity of the catalyst.
For the convenience of comparison of catalytic performance, two types of solid acid catalysts, PDSH-0.8 and Al-SBA-15-8, are exemplified.
Comparative example 1
The preparation method of the PDSH-0.8 solid acid comprises the following steps:
1.2g of divinylbenzene and 0.8g of 4-styrene sodium sulfonate are copolymerized under the condition of solvothermal (tetrahydrofuran is used as a solvent, the heating temperature is 120 ℃, and the heating time is 24 hours) to synthesize the PDSNa. To obtain a PDSH sample, PDSNa was subjected to ion exchange with 8ml of concentrated sulfuric acid for 48 hours to finally obtain PDSH-0.8 solid acid.
Comparative example 2
The preparation method of the Al-SBA-15-8 solid acid catalyst comprises the following steps:
0.8g of P 123 Dissolved in 25ml of 2mol/L hydrochloric acid, 1.8g of Tetraethoxysilane (TEOS) was added thereto, and the mixture was stirred at 40 ℃ for 4 hours to obtain a mixed solution, after which 0.8g of Al was added 2 (SO 4 ) 3 ·18H 2 Adding O into the mixed solution, and continuously stirring for 20 hours at 40 ℃ to obtain a mixture; transferring the mixture into an autoclave, carrying out hydrothermal reaction at 120 ℃ for 48h, then adjusting the pH value of a synthesis system to 7.5 by adding ammonia water, transferring the mixed solution into the autoclave, and carrying out hydrothermal reaction at 120 ℃ for 48h; and finally, filtering and collecting, washing with a large amount of water to be neutral, drying, and removing the surfactant through calcination (the calcination temperature is 500 ℃, and the calcination time is 4 hours) to obtain the catalyst Al-SBA-15-8.
The products of examples 1 to 3 and comparative examples 1 to 2 were physically characterized, and the characterization results are shown in Table 1.
TABLE 1 summary of the results of physical characterization of the products of examples 1 to 3 and comparative examples 1 to 2
Figure BDA0003753005940000071
As can be seen from Table 1: the acid capacity of the sample is adjustable between 0.76 mmol/g and 3.82mmol/g and is higher than that of a comparative sample. Notably, PDvm-OTf-x samplesThe S contents of (A) are 1.34mmol/g, 3.12mmol/g and 6.20mmol/g, respectively. This result is significantly higher than the acid-base titration method, indicating successful grafting of the electron withdrawing group of the OTf. The grafted OTf group provides only sulfur and no acid sites. While the sulfur content in PDSH-0.8 is basically consistent with the acid capacity. In the Al-SBA-15-8 sample, the Si/Al ratio, determined by ICP (7.6), was slightly lower than in the initial gel, probably due to incomplete digestion of the sample. In addition, PDvm-OTf-x gives BET specific surface areas of 617, 324 and 62m, respectively 2 In terms of/g (Table 1). It is to be noted that, under the same conditions, the BET specific surface area tends to decrease as the VIm content increases. The large number of OTf groups increases the density and weight of the network and blocks the mesopores of the sample, which has a negative effect on the specific surface.
Fig. 1 to 3 are high-resolution projection electron microscope images of the porous polymer-based ionic liquid solid acid catalysts with different nitrogen contents prepared in examples 1 to 3, respectively, and it can be seen from fig. 1 to 3 that the prepared solid acid catalysts have rough surfaces, a large number of well-developed pores are formed in fluffy sponge-like structures, and the microscopic morphology does not change significantly with the change of the content of N-vinyl imidazole in the initial carrier, and abundant macropores are still visible. In combination with table 1, it was found that the high number of OTf groups increased the density and weight of the network, clogging the mesopores of the sample, and adversely affecting the contrast surface.
Fig. 4 to 5 are high-resolution transmission electron micrographs of the catalysts prepared in comparative examples 1 to 2, as can be seen from fig. 4: the prepared catalyst has rich pore canals which are arranged in disorder. As can be seen from fig. 5: the catalyst has a large amount of mesopores, is orderly arranged into a hexagonal array, has one-dimensional pore channels and is a two-dimensional hexagonal (P6 mm) mesoscopic structure.
In order to examine the catalytic activity of the catalysts prepared in the above examples and comparative examples in the friedel-crafts acylation of anisole and acetic anhydride, the following experiments were carried out:
the catalyst was evaluated for its performance in a round bottom flask fitted with a reflux condenser, using an oil bath with a magnetic stirrer in order to keep the reaction temperature constant.
The specific reaction process of the Friedel-crafts acylation reaction is as follows: mixing anisole and acetic anhydride according to the proportion of 1:2 into a 50ml three-necked bottle, continuously adding 10ml dichloromethane into the reaction vessel, and stirring until the dichloromethane is completely dissolved; then 0.2g of solid acid catalyst is added, and the reaction is carried out for 10 hours at 353K; after the reaction was completed, the reaction mixture was cooled to room temperature.
The solid acid catalysts were sequentially replaced with the products prepared in examples 1 to 3 and comparative examples 1 to 2, and the conversion rates of the reactants and the selectivity of the products were analyzed using a gas chromatograph, a nonpolar column and a FID detector, and the analysis results are shown in table 2.
TABLE 2 statistical summary of catalytic activity of different types of solid acid catalysts in Friedel-crafts acylation
Figure BDA0003753005940000081
Note: the Selectivity of p-MAP represents the proportion of the target product in all the products.
As can be seen from Table 2, PDvm-OTf-0.1 exhibits the optimum catalytic activity. It is worth noting that all catalysts have selectivity of more than 80% to the target product, which is consistent with the characteristics of friedel-crafts acylation (no multiple acylation of the reaction product (ketone), and relatively pure product).
Further, the repeatable performance of the PDvm-OTf-0.1 catalyst which is the optimal catalyst is examined.
The specific operation is as follows: mixing anisole and acetic anhydride according to the proportion of 1:2 into a 50ml three-necked bottle, continuously adding 10ml dichloromethane into the reaction vessel, and stirring until the dichloromethane is completely dissolved; thereafter, 0.2g of a solid acid catalyst was added and the reaction was allowed to react at 353K for 10h. After each reaction, cooling to room temperature, recovering the catalyst from the reaction solution by a filtration separation mode, washing (washing with diethyl ether), drying and directly using in the next reaction (the reaction condition is unchanged). The catalyst has little loss in the recovery process, and new catalyst is not added in the next reaction. The catalytic activity of the PDvm-OTf-0.1 catalyst is counted, and the statistical result is shown in figure 6.
As can be seen from fig. 6: after 5 times of circulation, the conversion rate of anisole is not obviously reduced, and the selectivity of the target product is still kept above 80 percent, which indicates that the stability of PDVm-OTf-0.1 is enough to be used for Friedel-crafts acylation reaction.
Thirdly, the application of the PDVm-OTf-0.1 catalyst in the Friedel-crafts acylation reaction of different substrates of aryl ether and different acid anhydrides as acylation agents is examined.
The Friedel-crafts acylation reaction process and analysis conditions are consistent with the investigation of 'the repeatability performance of PDVm-OTf-0.1 catalyst', the difference is that the substrate is different from the acylation reagent, and the rest steps are consistent. Table 3 shows the catalytic activity effect of the PDvm-OTf-0.1 catalyst in Friedel-crafts acylation of different substrates with different anhydrides.
TABLE 3 Friedel-crafts acylation of different substrates with different anhydrides (partial list)
Figure BDA0003753005940000091
Figure BDA0003753005940000101
As can be seen from table 3: when the substrate contains an electron-withdrawing group, the reactivity is poor, and the conversion rate is not high, because the electron-withdrawing group greatly reduces the pi electron density on the benzene ring, so that the reaction is slow. However, when the benzene ring is substituted with an electron-donating group weaker than the methoxy group, the conversion of the substrate is gradually increasing because the introduction of the electron-donating group increases the electron density of the aromatic ring. Finally, we also applied the catalyst to heterocycles with high electron cloud density, which also showed high conversion and selectivity to the target product, probably because the electron cloud density on the five-membered heterocyclic ring is large and easily oxidized.
The above description is only a preferred embodiment of the present invention, and the above examples are for illustrating the detailed synthesis and application of the catalyst in the friedel-crafts acylation reaction, but the scope of the present invention is not limited thereto, and the selection of the raw materials, the ratio of each component, and the preparation method of the catalyst of the present invention are all within the scope of the present invention. Any person skilled in the art should also be able to substitute or change the technical solutions and their inventive concepts in the present disclosure within the scope of the present disclosure.

Claims (10)

1. A preparation method of a porous polymer-based ionic liquid solid acid catalyst is characterized by comprising the following steps:
(1) Ultrasonically dispersing divinylbenzene and a nitrogen-containing ligand in an organic solvent, stirring to obtain a uniformly dispersed solution, then adding an initiator, and continuously stirring at room temperature for 2-5 hours to obtain a mixed solution, wherein the mass ratio of the divinylbenzene to the nitrogen-containing ligand is 1: x, x =0.05 to 0.6;
(2) Carrying out hydrothermal reaction on the mixed solution obtained in the step (1) at the temperature of 80-160 ℃ for 1-4 days, and volatilizing an organic solvent to obtain a porous polymer matrix containing a nitrogen ligand;
(3) Fully dispersing the porous polymer matrix containing the nitrogen ligand in the step (2) in an organic solvent, then adding lactone, refluxing for 1-2 days at 100-140 ℃, filtering, collecting, and washing with ethanol to obtain a quaternized porous polymer;
(4) Fully dispersing the quaternized porous polymer in the step (3) in an organic solvent, adding organic strong acid, exchanging at room temperature for 1-3 days, and washing to obtain a crude product;
(5) And (4) extracting and purifying the crude product obtained in the step (4) to obtain the porous polymer-based ionic liquid solid acid catalyst.
2. The method for preparing the porous polymer-based ionic liquid solid acid catalyst according to claim 1, wherein the mass ratio of the lactone to the porous polymer matrix in the step (3) is 0.5-1.2: 1; the volume-mass ratio of the strong organic acid to the quaternized porous polymer in the step (4) is 4-10 mL/g.
3. The method for preparing the porous polymer-based ionic liquid solid acid catalyst according to claim 2, wherein the volume-to-mass ratio of the strong organic acid to the quaternized porous polymer in the step (4) is 8mL/g; the mass ratio of the lactone to the porous polymer matrix in the step (3) is 0.8.
4. The method for preparing the porous polymer-based ionic liquid solid acid catalyst according to any one of claims 1 to 3, wherein the mass ratio of the initiator to the nitrogen-containing ligand in the step (1) is 6;
the temperature of the hydrothermal reaction in the step (2) is 120 ℃, and the time of the hydrothermal reaction is 2 days;
and (5) adopting ethyl acetate as a solvent for extraction and purification, wherein the extraction and purification time is 1-4 days.
5. The method for preparing the porous polymer-based ionic liquid solid acid catalyst according to claim 4, wherein the nitrogen-containing ligand in the step (1) is N-vinylimidazole;
the organic solvent in the step (1) is at least one of N, N' -dimethylformamide, tetrahydrofuran and acetonitrile;
the initiator in the step (1) is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and dibenzoyl peroxide.
6. The method for preparing the porous polymer-based ionic liquid solid acid catalyst according to any one of claims 1 to 3, wherein the organic solvent in the step (3) is at least one of toluene, tetrahydrofuran, N-dimethylformamide, ethyl acetate and N-hexane;
the lactone in the step (3) is at least one of 1, 3-propane sultone, 1, 4-butane sultone, N- (1-naphthalene) -3-aminopropanesulfonic acid sodium salt and 3- (N, N-dimethyl octyl ammonium) propane-1-sulfonic acid inner salt;
and (4) the organic solvent is at least one of dichloromethane, chloroform, benzene and dimethyl sulfoxide.
7. The method for preparing the porous polymer base ionic liquid solid acid catalyst according to the claim 6, wherein the organic strong acid in the step (4) is at least one of trifluoromethanesulfonic acid, trifluoroacetic acid and hemisquaric acid;
the washing mode in the step (4) is as follows: washing with a mixed solution of ethanol and dichloromethane several times.
8. The porous polymer-based ionic liquid solid acid catalyst prepared by the method for preparing the porous polymer-based ionic liquid solid acid catalyst according to any one of claims 1 to 7.
9. Use of the porous polymer-based ionic liquid solid acid catalyst of claim 8 as a catalyst for friedel-crafts acylation to prepare arone compounds.
10. Use according to claim 9, characterized in that it comprises the following steps: in a Friedel-crafts acylation reaction with aryl ether as a substrate and acid anhydride as an acylation reagent, the mass of the porous polymer-based ionic liquid solid acid catalyst accounts for 10-80% of the mass of the aryl ether substrate.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698812A (en) * 2012-06-04 2012-10-03 大连理工大学 Solid super acid-ionic liquid composite solid supported catalyst and preparation method thereof
CN108620124A (en) * 2018-05-24 2018-10-09 绍兴文理学院 A kind of porous polymer solid acid catalyst for alkynes hydration reaction
EP3632889A1 (en) * 2018-10-05 2020-04-08 Evonik Operations GmbH Process for hydroformylation of short-chain olefins without intermediate partial separation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698812A (en) * 2012-06-04 2012-10-03 大连理工大学 Solid super acid-ionic liquid composite solid supported catalyst and preparation method thereof
CN108620124A (en) * 2018-05-24 2018-10-09 绍兴文理学院 A kind of porous polymer solid acid catalyst for alkynes hydration reaction
EP3632889A1 (en) * 2018-10-05 2020-04-08 Evonik Operations GmbH Process for hydroformylation of short-chain olefins without intermediate partial separation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FUJIAN LIU ET AL: "Transesterification Catalyzed by Ionic Liquids on Superhydrophobic Mesoporous Polymers: Heterogeneous Catalysts That Are Faster than Homogeneous Catalysts", J. AM. CHEM. SOC., vol. 134, pages 16948, XP055456671, DOI: 10.1021/ja307455w *
康艳慧等: "-SO3H功能化Bronsted酸性离子液体[MIM-BS][TsO]的制备及其催化性能研究", 精细石油化工, vol. 33, no. 3, pages 11 *

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