CN112169836A - Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same - Google Patents
Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same Download PDFInfo
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Abstract
The invention discloses a porous ionic polymer heterogeneous catalyst and a method for catalyzing and synthesizing N-formamide by using the same, and provides a method for catalyzing carbon dioxide, organic amine and hydrosilane epoxide to carry out N-formylation reaction to prepare an N-formamide compound by using the porous ionic polymer catalyst as the heterogeneous catalyst. The preparation method is green, environment-friendly, simple and efficient, and low in raw material cost; the catalyst has excellent pore structure, good physical and chemical stability, strong carbon dioxide enrichment capacity and highly dispersed ionic liquid active center; the invention has simple and efficient process, very mild conditions and safe operation; the catalytic reaction process does not need to add any organic solvent and auxiliary agent, and is environment-friendly; the low-concentration carbon dioxide can be directly used as a raw material, so that the cost and the energy consumption for obtaining the high-purity carbon dioxide are reduced; the product separation and purification process is simple, the catalyst is easy to recover and has good stability, and the catalyst can be recycled for many times.
Description
Technical Field
The invention relates to a heterogeneous catalysis method of an N-formamide compound, in particular to a method for preparing the N-formamide compound by taking carbon dioxide and organic amine as raw materials and taking a porous ionic polymer as a heterogeneous catalyst.
Background
Carbon dioxide is a major greenhouse gas, and its emission in large quantities leads to an exacerbation of the greenhouse effect. At the same time, carbon dioxide is also a cheap, abundant and safe carbon-resource. With the deep mind of the concept of sustainable development, the reasonable resource utilization of carbon dioxide has received more attention in recent years. In recent years, carbon dioxide capture, conversion, utilization and storage (CCUS) strategies have evolved into the mainstream of artificial recycling of carbon resources (acc. chem. res.2017,50,472-. Especially, the method for converting carbon dioxide into fine chemicals and fuels with high added values by using a chemical method has great significance for theoretical research and industrial application fields.
Owing to the rapid development of organic chemistry, chemical reactions such as the construction of C-C bonds, C-O bonds, C-N bonds, and C-H bonds from carbon dioxide by chemical means have been greatly developed. Among them, the preparation of methylamine or formamide compounds by reacting carbon dioxide with organic amines and reducing agents is widely regarded as an extremely potential high-value carbon dioxide utilization route (Green chem.2015,17, 157-168). Formamide compounds are a chemical substance with extremely wide application and are also basic materials for inorganic synthesis. For example, N' -dimethylformamide is widely used as a solvent and reagent for chemical reactions. In recent years, studies on a synthesis method for producing a carboxamide compound by N-formylating carbon dioxide, hydrogen and an organic amine have been matured. Although hydrogen gas is used as a reducing agent, it has the advantages of cleanness and atom economy, but the reaction conditions are harsh, and high temperature and high pressure conditions are required, so that the industrial application thereof is hindered (chem. rev.,2007,107(6): 2365-. Furthermore, use of H2As reducing agent, the substrate has a narrow application range and only applies to Me2NH、Et2NH、PhNH2Three types of substrates and relatively poor catalytic activity towards aromatic amines. For this situation, hydrosilanes (R) have been developed3Si-H) and hydroboranes (R)2B-H) as a candidate reducing agent for reducing carbon dioxide, the easier activation of Si-H and B-H bonds relative to the non-polar strong H-H bonds can expand the range of active substrates.
Based onN-formylation of carbon dioxide, organic amines and hydrosilanes, scientists have developed metal-based catalytic systems including ruthenium, iron, copper, zinc and nickel and including 1,5, 7-triazabicyclo [ 4.4.0%]Non-metal organic catalytic systems such as dec-5-ene (TBD), azacarbene (NHCs) and ionic liquids, etc. (Angew. chem. int. Ed.,2017,56, 7425-7429). Compared with a metal catalyst, the non-metal catalyst better meets the requirement of green chemistry. In particular, catalytic systems developed based on ionic liquids are receiving attention because of their good stability, excellent catalytic activity and mild reaction conditions. For example, Liu Shi Ming task group utilized discovery of 1-alkyl-3-methylimidazole ionic liquid as catalyst with CO at room temperature2And phenylsilane catalyzed N-formylation of the amine, N-formylated products (ACS Catal.,2015,5, 4989-. However, most of the above catalytic systems are homogeneous catalytic systems, and although they exhibit advantages such as high activity, they have problems such as difficulty in recovering and reusing the catalyst, complicated product separation and purification processes, and the like, and are common problems in most of the homogeneous catalytic systems, and they become one of important hindering factors for the industrial application of ionic liquids as catalysts.
Based on the above considerations, ionic liquid heterogenization becomes a key strategy to solve the above problems. In particular, the porous ionic polymer catalyst constructed by using the emerging porous organic polymer as a framework material attracts extensive attention. Besides high specific surface area, high porosity and excellent physicochemical stability, the porous organic polymer has more advantages in the fields of carbon dioxide adsorption and separation and catalytic conversion (ACS Catal.2018,8, 6961-. Therefore, the porous ionic polymer catalyst is designed and prepared, which is beneficial to the exposure of the active site of the ionic liquid, the enrichment of carbon dioxide and the diffusion of reactant and product molecules, and can realize the simple separation and the effective reuse of the catalyst. However, the development of a method for synthesizing an N-formamide compound from pure carbon dioxide, even low-concentration carbon dioxide, organic amine and hydrosilane under mild conditions with high activity and high selectivity is still a technical problem to be further solved by those skilled in the art.
Disclosure of Invention
The invention aims to solve the problems of metal catalyst, harsh reaction conditions, complex product separation and purification, difficult catalyst recovery and reuse and the like in the existing process of synthesizing an N-formamide compound by taking carbon dioxide as a raw material, provide a porous ionic polymer heterogeneous catalyst with the characteristics of high specific surface area, high porosity, high stability, easy recovery and reuse, and realize the capture of carbon dioxide and the high-efficiency and high-selectivity catalytic conversion of the carbon dioxide into the N-formamide compound under the condition of no solvent at normal temperature and normal pressure.
The technical scheme provided by the invention is as follows:
a porous ionic polymer heterogeneous catalyst has a structure shown in a general formula (I):
wherein, in the general formula (I), the
The part of H on the hydroxyl group is removed from one of 1-naphthol, 2-naphthol, 4 ' -isopropylidenediphenol, 1' -bi-2-naphthol, 2' -dihydroxybiphenyl, 2, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene and 4-hydroxybiphenyl;
x is halogen; n is an integer of 1 to 10, the IL+One selected from the general formulas (II) -1-5:
r in the general formula (II)1Selected from methyl, ethyl, n-butyl, phenyl and benzyl.
The preparation method of the porous ionic polymer heterogeneous catalyst comprises the following steps:
(1) dissolving a phenolic compound (III) in an organic solvent, adding a cross-linking agent and a catalyst Lewis acid, sealing under the helium condition, placing a reaction system at room temperature, stirring, heating to 30-120 ℃ in an oil bath, carrying out a first contact reaction, cooling after 0.5-72 h, filtering, washing, Soxhlet extraction and vacuum drying to obtain a porous organic polymer containing phenolic hydroxyl with the structure shown in a general formula (IV);
(2) the porous organic polymer (IV) containing phenolic hydroxyl group obtained in the step (1) and- (CH) in the general formula (V)2)n-IL+X-Adding the bromide and the carbonate into an anhydrous organic solvent, stirring at 40-150 ℃, carrying out a second contact reaction, cooling after 0.5-48 h, filtering, washing a filter cake for 3-5 times by using deionized water, methanol, tetrahydrofuran and methanol in sequence, and then carrying out vacuum drying. Obtaining the porous ionic polymer heterogeneous catalyst shown in the general formula (I); the reaction formula is as follows:
preferably, in the above method for preparing a porous ionic polymer heterogeneous catalyst, the ratio of the amount of the phenolic compound to the amount of the charge material of the crosslinking agent is 1: (0.5 to 50); the charging mass ratio of the porous organic polymer IV containing phenolic hydroxyl groups to the ionic liquid V is 1: (0.5 to 30).
Preferably, in the above method for preparing the porous ionic polymer heterogeneous catalyst, the organic solvent in step (1) is one or two selected from 1, 2-dichloroethane, dichloromethane, chloroform and carbon tetrachloride;
the cross-linking agent is selected from 1, 4-dibromomethylbenzene, dimethanol formal, dichloromethane and dibromomethane;
the catalyst Lewis acid is selected from anhydrous ferric trichloride and anhydrous aluminum chloride.
Preferably, in the above method for preparing a porous ionic polymer heterogeneous catalyst, the carbonate in step (2) is selected from potassium carbonate, sodium carbonate; the anhydrous organic solvent in the step (2) is one or two of anhydrous N, N-dimethylformamide, anhydrous dimethyl sulfoxide, anhydrous tetrahydrofuran and anhydrous methanol.
A method for synthesizing N-formamide by taking carbon dioxide as a raw material comprises the following steps:
adding a porous ionic polymer heterogeneous catalyst, an organic amine compound and hydrogen-containing silane into a stainless steel reaction kettle, sealing, slowly filling and discharging carbon dioxide gas for multiple times, replacing air in the kettle, filling carbon dioxide under certain pressure, and sealing; placing the reaction device in constant-temperature stirring for reaction to obtain an N-formamide compound; the catalyst is recovered by filtering, washing and drying for reuse.
Preferably, in the above preparation method, the organic amine compound is an organic primary amine compound or an organic secondary amine compound, and the organic primary amine compound is selected from compounds represented by the general formula (VI):
wherein R is2Selected from ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, benzyl, cyclohexyl; the organic secondary amine compound is selected from compounds shown in a general formula VII, or is selected from piperidine, 2,6, 6-tetramethyl piperidine, 1-methyl piperazine, 1-phenyl piperazine, indoline, 1,2,3, 4-tetrahydroisoquinoline and morpholine;
wherein R is3Selected from phenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, p-acetylphenyl; r4Selected from methyl, ethyl, n-butyl, isopropyl, phenyl, allyl, benzyl, cyclohexyl.
Preferably, in the above preparation method, the hydrogen-containing silane is selected from the group consisting of phenylsilane, methylphenylsilane, dimethylphenylsilane, diphenylsilane, triphenylsilane, polymethylhydrosilane, diethylmethylsilane, trimethoxysilane, triethoxysilane, triethylsilane, and dimethylethylsilane.
Preferably, in the above production method, the ratio of the amounts of the organic amine compound, the hydrosilane, and the substance of the porous ionic polymer heterogeneous catalyst is 1000: (100-5000): (1-25).
Preferably, in the preparation method, the reaction temperature is 5-120 ℃, and the reaction time is 0.5-96 hours; the concentration of the carbon dioxide is 5-100%, and the pressure of the carbon dioxide is 0.1-12 MPa.
In the present invention, the heterogeneous catalyst (I) can be recovered and regenerated by simple filtration, washing and drying, and can maintain catalytic activity and selectivity after repeated use for many times.
In the invention, the prepared porous organic polymer IV containing phenolic hydroxyl can realize the regulation and control of the specific surface area and the pore characteristics by regulating the type of the polymerized monomer III, the charging ratio of the polymerized monomer III to the cross-linking agent and the type of the organic solvent, and further realize the regulation and control of the structure and the activity of the porous ionic polymer catalyst VI by regulating the types of the porous organic polymer IV containing phenolic hydroxyl and the ionic liquid V and the charging ratio of the porous organic polymer IV to the ionic liquid V.
Compared with the prior art, the invention has the following beneficial effects:
the porous ionic polymer prepared by the invention is used as a heterogeneous catalyst, has an excellent pore structure, good physical and chemical stability, strong carbon dioxide enrichment capacity and a highly dispersed ionic liquid active center, can be used for efficiently and selectively catalyzing carbon dioxide, organic amine and hydrogen-containing silane to synthesize an N-formamide compound under the conditions of no solvent and no auxiliary agent, can be recovered through simple filtration, washing and drying particularly after the catalytic reaction is finished, and can still keep the high activity and the high selectivity after being repeatedly used for many times. Particularly, the porous ionic polymer catalyst can successfully convert low-concentration carbon dioxide into an N-formamide compound under mild conditions, and provides a path with great industrial application potential for realizing the enrichment and conversion of carbon dioxide in the real world.
The preparation method of the catalyst is green, environment-friendly, simple and efficient, and low in raw material cost; the N-formylation reaction process of the carbon dioxide is simple, the conditions are very mild, and the operation is safe; the catalytic reaction process does not need to add any organic solvent and auxiliary agent, and is environment-friendly; the low-concentration carbon dioxide can be directly used as a raw material, so that the cost and the energy consumption for obtaining the high-purity carbon dioxide are reduced; the product separation and purification process is simple, the catalyst is easy to recover and has good stability, and the catalyst can be recycled for many times.
Drawings
FIG. 1 is (a) the nitrogen desorption pattern of polymers IV and I and (b) the pore size distribution;
FIG. 2 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of Polymer I.
Detailed Description
The present invention is further illustrated in the following examples, which are intended to be illustrative only and should not be construed as limiting the practice of the invention.
Example 1: porous ionic polymer catalyst preparation
(1) Adding 5mmol of 1,1' -bi-2-naphthol, 20mmol of anhydrous ferric trichloride and 20mL of anhydrous 1, 2-dichloroethane into a 50mL Schlenk tube, repeatedly replacing air in the tube with nitrogen, adding 20mmol of dimethanol formal under the condition of nitrogen, sealing, placing the reaction system at room temperature, stirring for 30min, heating in an oil bath to 100 ℃, carrying out first contact reaction, cooling after 24h, filtering, washing, Soxhlet extraction and vacuum drying to obtain a porous organic polymer containing phenolic hydroxyl;
(2) adding 300mg of the porous organic polymer containing phenolic hydroxyl groups obtained in the step (1), 414mg of potassium carbonate and 634mg of bromobutyl triethyl ammonium bromide into 15mL of anhydrous N, N' -dimethylformamide, heating to 140 ℃, continuously stirring for reacting for 24h, filtering the obtained precipitate, washing the filter cake with methanol, acetone and ionized water for 3-5 times in sequence, and then freeze-drying for 48h to obtain 0.61g of the porous ionic polymer catalyst.
Example 2: porous ionic polymer catalyst preparation
(1) Adding 10mmol of 2, 3-dihydroxynaphthalene, 20mmol of anhydrous ferric trichloride and 40mL of anhydrous trichloromethane into a 100mL Schlenk tube, repeatedly replacing air in the tube with nitrogen, adding 20mmol of dimethanol formal under the condition of nitrogen, sealing, placing a reaction system at room temperature, stirring for 30min, heating in an oil bath to 80 ℃, carrying out first contact reaction, cooling after 36h, filtering, washing, Soxhlet extraction and vacuum drying to obtain a porous organic polymer containing phenolic hydroxyl;
(2) adding 150mg of the porous organic polymer containing phenolic hydroxyl groups obtained in the step (1), 360mg of sodium carbonate and 380mg of 1- (4-bromoethyl) pyridinium chloride into 20mL of anhydrous tetrahydrofuran, heating to 100 ℃, continuing stirring for reaction for 48h, filtering the obtained precipitate, washing the filter cake with methanol, acetone and deionized water for 3-5 times in sequence, and then freeze-drying for 48h to obtain 0.26g of the porous ionic polymer catalyst.
Example 3: porous ionic polymer catalyst preparation
(1) Adding 2mmol of 4, 4' -isopropylidene diphenol, 10mmol of anhydrous aluminum trichloride and 20mL of anhydrous dichloromethane into a 100mL Schlenk tube, repeatedly replacing air in the tube with nitrogen, sealing under the condition of nitrogen, placing a reaction system at room temperature, stirring for 30min, heating to 80 ℃ in an oil bath, carrying out a first contact reaction, cooling after 48h, filtering, washing, carrying out Soxhlet extraction and vacuum drying to obtain a porous organic polymer containing phenolic hydroxyl;
(2) adding 200mg of the phenolic hydroxyl group-containing porous organic polymer obtained in the step (1), 580mg of potassium carbonate and 620mg of bromobutyl triethyl ammonium bromide into 25mL of anhydrous N, N' -dimethylformamide, heating to 80 ℃, continuing stirring for reaction for 48h, filtering the obtained precipitate, washing the filter cake with methanol, acetone and deionized water for 3-5 times in sequence respectively, and then freeze-drying for 48h to obtain 0.37g of the porous ionic polymer catalyst.
Example 4: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.05mmol of a catalyst (in the general formula (I), n ═ 4, X ═ Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1N-butyl), 1.5mmol of 2-methoxy-N-methylaniline and 3mmol of benzeneSilane, 100 percent of carbon dioxide is introduced to ensure that the initial pressure is 1MPa, the mixture is stirred for 24 hours at the temperature of 35 ℃, the catalyst is separated by filtration after the residual carbon dioxide is slowly released, a proper amount of filtrate is taken for gas chromatography analysis, and the yield of the 2-methoxy-N-methylformanilide obtained by a plurality of parallel tests is 98 percent.
Example 5: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.06mmol of a catalyst (in the general formula (I), n ═ 6, X ═ Br,
from 2,2' -dihydroxybiphenyl, IL+Is of the general formula (VII) -3, R1Phenyl) 2mmol of 4-bromo-N-methylaniline and 5mmol of diphenylsilane, introducing 100% of carbon dioxide to make the initial pressure of the mixture be 1MPa, stirring the mixture for 12 hours at the temperature of 80 ℃, then placing the mixture into ice water for cooling, slowly releasing the residual carbon dioxide, filtering and separating out the catalyst, taking a proper amount of filtrate for gas chromatography analysis, and obtaining the yield of the 4-bromo-N-methylformanilide by multiple parallel tests, wherein the yield is 99%.
Example 6: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.1mmol of a catalyst (in the general formula (I), n ═ 8, X ═ Br,
derived from 2, 3-dihydroxynaphthalene, IL+Is of the general formula (II) -4, R1Methyl), 2mmol of 4-bromo-N-methylaniline and 5mmol of diphenylsilane, introducing 100% of carbon dioxide to make the initial pressure be 4MPa, stirring for 18h at the temperature of 100 ℃, filtering to separate out the catalyst after slowly releasing the residual carbon dioxide, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the 4-bromo-N-methylformanilide by multiple parallel tests to be 96%.
Example 7: synthesis of N-formamide by using carbon dioxide as raw material
Into a 10mL stainless steel high-pressure reaction kettle in turn0.04mmol of a catalyst (in the general formula (I), n ═ 4, X ═ Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1Ethyl), 2mmol of morpholine and 2mmol of phenylsilane, 100 percent of carbon dioxide is introduced to keep the pressure of the mixture to be 0.1MPa all the time, the mixture is stirred for 24 hours at the temperature of 40 ℃, the residual carbon dioxide is slowly released, the catalyst is separated by filtration, a proper amount of filtrate is taken for gas chromatography analysis, and the yield of morpholine-4-formaldehyde obtained by a plurality of parallel tests is 99 percent.
Example 8: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.08mmol of a catalyst (in the general formula (I), n ═ 6, X ═ Cl,
derived from 2, 3-dihydroxynaphthalene, IL+Is of the general formula (II) -1, R1N-butyl), 1mmol of di-n-butylamine and 2mmol of phenylsilane, introducing 100% of carbon dioxide to ensure that the initial pressure is 3MPa, stirring for 36 hours at the temperature of 25 ℃, filtering to separate out the catalyst after slowly releasing the residual carbon dioxide, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the di-n-butylformamide of 96% by multiple parallel tests.
Example 9: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.1mmol of a catalyst (in the general formula (I), n ═ 4, X ═ Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1Ethyl group), 1mmol N-methylaniline and 2mmol phenylsilane, introducing 100% carbon dioxide to maintain the pressure at 0.1MPa, stirring at 25 deg.C for 72 hr, slowly releasing residual carbon dioxide, filtering to separate catalyst, collecting appropriate amount of filtrate, and performing gas chromatographyThe yield of N-methylformanilide obtained in the sub-parallel test was 95%.
Example 10: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.075mmol of a catalyst (formula (I) wherein n is 4, X is Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1N-butyl group), 1mmol of N-methylaniline and 1mmol of phenylsilane, introducing 100% of carbon dioxide to make the initial pressure of the mixture be 3MPa, stirring the mixture for 16 hours at the temperature of 35 ℃, filtering the mixture to separate out the catalyst after slowly releasing the residual carbon dioxide, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the N-methylformanilide by a plurality of parallel tests to be 99%.
Example 11: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.05mmol of a catalyst (in the general formula (I), n ═ 4, X ═ Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1Ethyl), 1mmol of N-methylaniline and 1mmol of phenylsilane, 15 percent of carbon dioxide is introduced to keep the pressure of the N-methylaniline and the 1mmol of phenylsilane always at 1MPa, the mixture is stirred for 72 hours at the temperature of 60 ℃, the residual carbon dioxide is slowly released, the catalyst is separated by filtration, a proper amount of filtrate is taken for gas chromatography analysis, and the yield of the N-methylformanilide obtained by a plurality of parallel tests is 99 percent.
Example 12: synthesis of N-formamide by using carbon dioxide as raw material
To a 10mL stainless steel autoclave, 0.06mmol of a catalyst (in the general formula (I), n ═ 4, X ═ I,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -5, R1Methyl group), 1mmIntroducing 15% of carbon dioxide into the alcohol N-methylaniline and 1mmol of phenylsilane to keep the pressure of the N-methylaniline and the 1mmol of phenylsilane always at 10MPa, stirring the mixture for 48 hours at the temperature of 25 ℃, slowly releasing the residual carbon dioxide, filtering and separating the catalyst, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the N-methylformanilide by multiple parallel tests of 98 percent.
Example 13: method for synthesizing N-formamide by taking carbon dioxide as raw material under catalysis of recovered catalyst
To a 10mL stainless steel autoclave, 0.075mmol of the catalyst recovered in the 6 th pass (formula (I), where n is 4, X is Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1N-butyl group), 1mmol of N-methylaniline and 1mmol of phenylsilane, introducing 100% of carbon dioxide to make the initial pressure of the mixture be 0.5MPa, stirring the mixture for 16 hours at the temperature of 35 ℃, filtering the mixture to separate out the catalyst after slowly releasing the residual carbon dioxide, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the N-methylformanilide of 99 percent by multiple parallel tests.
Example 14: method for synthesizing N-formamide by taking carbon dioxide as raw material under catalysis of recovered catalyst
To a 10mL stainless steel autoclave, 0.075mmol of the catalyst recovered in the 6 th pass (formula (I), wherein n is 4, X is Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1N-butyl group), 1mmol of N-methylaniline and 1mmol of phenylsilane, introducing 100% of carbon dioxide to make the initial pressure 0.5MPa, stirring for 16h at the temperature of 35 ℃, filtering to separate out the catalyst after slowly releasing the residual carbon dioxide, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the N-methylformanilide by a plurality of parallel tests to be 99%.
Example 15: method for synthesizing N-formamide by taking carbon dioxide as raw material under catalysis of recovered catalyst
To a 10mL stainless steel autoclave, 0.075mmol of the catalyst recovered in the 8 th pass (formula (I), wherein n is 4, X is Br,
derived from 1,1' -bi-2-naphthol, IL+Is of the general formula (II) -1, R1N-butyl group), 1mmol of N-methylaniline and 1mmol of phenylsilane, introducing 100% of carbon dioxide to make the initial pressure of the mixture be 0.5MPa, stirring the mixture for 16 hours at the temperature of 35 ℃, filtering the mixture to separate out the catalyst after slowly releasing the residual carbon dioxide, taking a proper amount of filtrate to perform gas chromatography analysis, and obtaining the yield of the N-methylformanilide by a plurality of parallel tests to be 97%.
It should be understood that in light of the foregoing description, as will be evident to those skilled in the art from the foregoing description, various changes and modifications can be made without departing from the principles of the invention, and such changes and modifications are to be considered as within the scope of the appended claims.
Claims (10)
1. A porous ionic polymer heterogeneous catalyst has a structure shown in a general formula (I):
wherein, in the general formula (I), the
The part of H on the hydroxyl group is removed from one of 1-naphthol, 2-naphthol, 4 ' -isopropylidenediphenol, 1' -bi-2-naphthol, 2' -dihydroxybiphenyl, 2, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene and 4-hydroxybiphenyl;
x is halogen; n is an integer of 1 to 10, the IL+One selected from the general formulas (II) -1-5:
r in the general formula (II)1Selected from methyl, ethyl, n-butyl, phenyl and benzyl.
2. A process for preparing a porous ionic polymer heterogeneous catalyst according to claim 1, comprising the steps of:
(1) dissolving a phenolic compound (III) in an organic solvent, adding a cross-linking agent and a catalyst Lewis acid, sealing under the helium condition, placing a reaction system at room temperature, stirring, heating to 30-120 ℃ in an oil bath, carrying out a first contact reaction, cooling after 0.5-72 h, filtering, washing, Soxhlet extraction and vacuum drying to obtain a porous organic polymer containing phenolic hydroxyl with the structure shown in a general formula (IV);
(2) the porous organic polymer (IV) containing phenolic hydroxyl group obtained in the step (1) and- (CH) in the general formula (V)2)n-IL+X-Adding the bromide and the carbonate into an anhydrous organic solvent, stirring at 40-150 ℃, carrying out a second contact reaction, cooling after 0.5-48 h, filtering, washing a filter cake for 3-5 times by using deionized water, methanol, tetrahydrofuran and methanol in sequence, and then carrying out vacuum drying. Obtaining the porous ionic polymer heterogeneous catalyst shown in the general formula (I); the reaction formula is as follows:
3. the method of claim 2, wherein the ratio of the amount of phenolic compound to crosslinker charge material is from 1: (0.5 to 50); the charging mass ratio of the porous organic polymer IV containing phenolic hydroxyl groups to the ionic liquid V is 1: (0.5 to 30).
4. The method for preparing a porous ionomer heterogeneous catalyst according to claim 2, wherein the organic solvent in the step (1) is one or two selected from the group consisting of 1, 2-dichloroethane, dichloromethane, chloroform and carbon tetrachloride;
the cross-linking agent is selected from 1, 4-dibromomethylbenzene, dimethanol formal, dichloromethane and dibromomethane;
the catalyst Lewis acid is selected from anhydrous ferric trichloride and anhydrous aluminum chloride.
5. The method of preparing a porous ionic polymer heterogeneous catalyst according to claim 2,
the carbonate in the step (2) is selected from potassium carbonate and sodium carbonate; the anhydrous organic solvent in the step (2) is one or two of anhydrous N, N-dimethylformamide, anhydrous dimethyl sulfoxide, anhydrous tetrahydrofuran and anhydrous methanol.
6. A method for synthesizing N-formamide by taking carbon dioxide as a raw material is characterized by comprising the following steps:
adding the porous ionic polymer heterogeneous catalyst according to claim 1 or the porous ionic polymer heterogeneous catalyst prepared by the preparation method according to any one of claims 2 to 5, an organic amine compound and hydrosilane into a stainless steel reaction kettle, sealing, slowly filling and exhausting carbon dioxide gas for a plurality of times, replacing air in the kettle, filling carbon dioxide under a certain pressure, and sealing; placing the reaction device in constant-temperature stirring for reaction to obtain an N-formamide compound; the catalyst is recovered by filtering, washing and drying for reuse.
7. The method of claim 6, wherein the organic amine compound is a primary or secondary organic amine compound selected from the group consisting of compounds of formula (VI):
wherein R is2Selected from ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, benzyl, cyclohexyl; selection of organic secondary amine compoundsA compound shown in a general formula VII, or piperidine, 2,6, 6-tetramethyl piperidine, 1-methyl piperazine, 1-phenyl piperazine, indoline, 1,2,3, 4-tetrahydroisoquinoline and morpholine;
wherein R is3Selected from phenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, p-acetylphenyl; r4Selected from methyl, ethyl, n-butyl, isopropyl, phenyl, allyl, benzyl, cyclohexyl.
8. The method of claim 6, wherein the hydrogen-containing silane is selected from the group consisting of phenylsilane, methylphenylsilane, dimethylphenylsilane, diphenylsilane, triphenylsilane, polymethylhydrosilane, diethylmethylsilane, trimethoxysilane, triethoxysilane, triethylsilane, and dimethylethylsilane.
9. The method of claim 6, wherein the ratio of the amounts of the organic amine compound, the hydrosilane, and the porous ionic polymer heterogeneous catalyst is from 1000: (100-5000): (1-25).
10. The method of claim 6, wherein the reaction temperature is 5-120 ℃ and the reaction time is 0.5-96 h; the concentration of the carbon dioxide is 5-100%, and the pressure of the carbon dioxide is 0.1-12 MPa.
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