Imidazolidinone compound, porous organic polymer gel as well as preparation method and application of porous organic polymer gel

Abstract

The invention belongs to the field of functional porous materials, and particularly relates to imidazolidinone compounds, porous organic polymer gel and a preparation method and application of the imidazolidinone compounds and the porous organic polymer gel. The porous organic polymer gel with positive charges is prepared by taking an amino acid amide monomer and a pyridine aldehyde monomer as raw materials in one step. The porous organic polymer gel has relatively good processing performance and relatively high conductivity.

Description

Technical Field

[0001] The invention belongs to the field of functional porous materials, and in particular relates to imidazolidinone compounds, porous organic polymer gels, and preparation methods and applications thereof. Background Art

[0002] The development of materials with efficient ion conduction is important for high-performance electrochemical applications, such as fuel cells, electrolytes, and supercapacitors. A fuel cell is an electrochemical device that directly converts the chemical energy of a fuel (e.g., hydrogen or methanol) into electrical energy. Alkaline fuel cells use anion conduction, which has many advantages over proton-conducting acidic fuel cells, including fast reaction kinetics and no need for precious metal catalysts. Despite these advantages, the development of materials that can achieve efficient anion conduction remains a challenge.

[0003] At present, most porous organic polymers used for anion conduction are in the form of membranes. For example, in 2023, Jiang et al. prepared a series of self-supporting COF membranes through phase transfer polymerization. The prepared QA-COF membrane has high hydroxide ion conductivity. It can efficiently conduct anions (such as OH − and Cl − ) polymers usually contain positively charged groups in their molecular structure, and cationic functional groups can be directly or indirectly bonded to the polymer backbone through covalent bonds. In 2024, Zhu et al. successfully prepared a continuous porous aromatic framework (PAF) membrane with adjustable thickness by liquid-solid interfacial polymerization, in which the rigid skeleton and stable C-C coupling gave it excellent chemical stability, showing 356.6mS∙cm at 80°C and 98% relative humidity. 1 OH − The conductivity is the highest among anion exchange membranes (AEMs) reported so far.

[0004] However, for membranes, a balance between ion exchange capacity and dimensional stability needs to be considered, because the presence of water is conducive to anion conduction and can make anion exchange membrane (AEM) have a high degree of dissociation and ion exchange capacity (IEC), thereby improving the mobility and conductivity of anions. However, in most of the chain polymer anion conductors reported so far, excessive water content will lead to the problem of chain polymer swelling, while low water content will lead to slow hydroxyl migration. Gels do not need to consider this, because gels randomly generate voids of different shapes and sizes during the formation process, which provides the possibility of promoting the migration and diffusion of guest molecules.

[0005] Ionic porous organic polymers (iPOPs) are a new type of porous organic polymers with ionic sites in the framework or pores. Compared with neutral porous organic polymers, the introduction of charges in the polymer structure can provide electrostatic interactions for these materials and enhance their molecular recognition and conduction capabilities. Currently, most iPOPs are obtained by direct polymerization of charged monomers or post-synthesis modification with charged molecules. Many synthesis methods have problems such as unsatisfactory reaction efficiency, limited tunability of monomer structure, and post-synthesis modification of charged molecules that block porous channels. In addition, most iPOPs exist in the form of powders with poor processability, which limits their practical applications. In general, solution processing methods can make iPOPs have certain processability, but require tedious sample handling, and some methods are highly dependent on pH adjustment to maintain ionic properties, limiting their potential uses. Therefore, the development of efficient synthetic chemistry methods for the in situ preparation of processable iPOP gels with adjustable chemical structures can bring new opportunities for the potential applications of iPOPs. Summary of the invention

[0006] The purpose of the present invention is to provide a preparation method using amino acid amide and pyridine aldehyde as raw materials and to prepare positively charged imidazolidinone compounds using the method. The present invention further introduces this type of reaction into the synthesis of polymers to obtain a five-membered ring-shaped positively charged ionic porous organic polymer gel, which exhibits good processability and hydroxide conductivity.

[0007] The first technical problem to be solved by the present invention is to provide a method for preparing an imidazolidinone compound. The preparation method comprises the following steps: reacting amino acid amide hydrochloride with pyridine aldehyde in an organic solvent to obtain the imidazolidinone compound. ; Wherein, the amino acid amide hydrochloride structural formula is , R1 is selected from H, C 1-8 Alkyl, phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500; the pyridine aldehyde structural formula is , R3 is selected from H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Haloalkyl, amide, ester, phenyl.

[0008] Further, in the preparation method of the above imidazolidinone compounds, R1 is selected from H, methyl, isopropyl, i-Bu, hydroxymethyl, benzyl, and R2 is selected from methyl, -CH2CF3, cyclopropyl, phenyl, p-methoxyphenyl, p-nitrophenyl, , .

[0009] Preferably, in the preparation method of the above-mentioned imidazolidinone compounds, the amino acid amide hydrochloride is selected from: glycine-N-methylamide hydrochloride, (S)-2-amino-N-methylpropionamide hydrochloride, (S)-2-amino-3-methyl-N-phenylbutanamide hydrochloride, (S)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, (R)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride, 2-amino-N-cyclopropylacetamide hydrochloride, N1-phenylglycinamide hydrochloride, 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride, L-leucine-4-nitroaniline hydrochloride, L-alanine-4-nitroaniline hydrochloride, and glycylglycine hydrochloride.

[0010] Furthermore, in the above-mentioned method for preparing imidazolidinone compounds, R3 is selected from H, methyl, Cl, methoxy, and -CF3.

[0011] Preferably, in the preparation method of the above-mentioned imidazolidinone compounds, the pyridine aldehyde is selected from: pyridine-2-carboxaldehyde, 5-methylpyridine-2-carboxaldehyde, 5-methoxypyridine-2-carboxaldehyde, 5-chloropyridine-2-carboxaldehyde, and 5-trifluoromethylpyridine-2-carboxaldehyde.

[0012] Furthermore, in the above-mentioned method for preparing imidazolidinone compounds, the molar ratio of the amino acid amide hydrochloride to pyridine aldehyde is 1: 1-10.

[0013] Furthermore, in the above-mentioned method for preparing imidazolidinone compounds, the organic solvent is selected from acetic acid (HOAC), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), ethanol (EtOH), n-butanol (n-BuOH), preferably acetic acid (HOAC).

[0014] Furthermore, in the above-mentioned method for preparing imidazolidinone compounds, the molar volume ratio of the amino acid amide hydrochloride to the organic solvent is 1 mmol: 1-15 mL.

[0015] Furthermore, in the above-mentioned method for preparing imidazolidinone compounds, the reaction temperature is 25-80° C. and the reaction time is 10 minutes to 24 hours, preferably 10 minutes to 12 hours.

[0016] The second technical problem to be solved by the present invention is to provide an imidazolidinone compound prepared by the above-mentioned method for preparing an imidazolidinone compound.

[0017] Specifically, the above-mentioned imidazolidinone compound has a structural formula as shown in Formula ( ) as shown:

[0018] Mode( ) Wherein, R1 is selected from H, C 1-8 Alkyl, phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500, R3 is selected from H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Haloalkyl, amide, ester, phenyl.

[0019] Preferably, in the above-mentioned imidazolidinone compounds, R1 is selected from H, methyl, isopropyl, i-Bu, hydroxymethyl, benzyl, and R2 is selected from methyl, -CH2CF3, cyclopropyl, phenyl, p-methoxyphenyl, p-nitrophenyl, , , R3 is selected from H, methyl, Cl, methoxy, -CF3.

[0020] Furthermore, the above-mentioned imidazolidinone compound is selected from the following specific structures: .

[0021] The present invention also provides a formula ( ) or its stereoisomers:

[0022] Mode( ) Wherein, R1 is selected from H, C 1-8 Alkyl, phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500, R3 is selected from H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Haloalkyl, amide, ester, phenyl.

[0023] Preferably, in the above-mentioned imidazolidinone compound or its stereoisomer, R1 is selected from H, methyl, isopropyl, i-Bu, hydroxymethyl, benzyl, and R2 is selected from methyl, -CH2CF3, cyclopropyl, phenyl, p-methoxyphenyl, p-nitrophenyl, , , R3 is selected from H, methyl, Cl, methoxy, -CF3.

[0024] Furthermore, the above-mentioned imidazolidinone compound or its stereoisomer is selected from the following specific structures: .

[0025] The third technical problem to be solved by the present invention is to provide a method for preparing an ionic porous organic polymer gel. The preparation method comprises the following steps: reacting an amino acid amide monomer and a pyridine aldehyde monomer in an organic solvent to prepare the ionic porous organic polymer gel; wherein the amino acid amide monomer has a structural formula of , R1 is selected from H, C 1-8 Alkyl, phenyl substituted C1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500; the pyridine aldehyde monomer is selected from [3,3'-bipyridine]-6,6'-dicarboxaldehyde or 1,3,5-tri(2-formylpyridin-5-yl)benzene.

[0026] Furthermore, in the preparation method of the above-mentioned ionic porous organic polymer gel, R1 is selected from H, methyl, isopropyl, i-Bu, hydroxymethyl, benzyl, and R2 is selected from methyl, -CH2CF3, cyclopropyl, phenyl, p-methoxyphenyl, p-nitrophenyl, , , .

[0027] Preferably, in the preparation method of the above-mentioned ionic porous organic polymer gel, the amino acid amide monomer is selected from: glycine-N-methylamide hydrochloride, (S)-2-amino-N-methylpropionamide hydrochloride, (S)-2-amino-3-methyl-N-phenylbutyramide hydrochloride, (S)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, (R)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride, 2-amino-N-cyclopropylacetamide hydrochloride, N1-phenylglycineamide hydrochloride, 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride, L-leucine-4-nitroaniline hydrochloride, L-alanine-4-nitroaniline hydrochloride, , glycine hydrochloride.

[0028] Preferably, in the method for preparing the above-mentioned ionic porous organic polymer gel, the pyridine aldehyde monomer is selected from: [3,3'-bipyridine]-6,6'-dicarboxaldehyde (structural formula: ) or 1,3,5-tri(2-formylpyridin-5-yl)benzene (structural formula: ).

[0029] Furthermore, in the method for preparing the ionic porous organic polymer gel, the molar ratio of the amino acid amide monomer to the pyridine aldehyde monomer is 1-4:2, preferably 3:2, 1:2 or 3:4.

[0030] Furthermore, in the method for preparing the ionic porous organic polymer gel, the organic solvent is dimethyl sulfoxide (DMSO).

[0031] Furthermore, in the method for preparing the above-mentioned ionic porous organic polymer gel, the molar volume ratio of the amino acid amide monomer to the organic solvent is 0.1 - 0.3 mmol: 1 mL.

[0032] Furthermore, in the method for preparing the ionic porous organic polymer gel, the reaction temperature is 90-120° C. and the reaction time is 3 hours to 3 days.

[0033] The fourth technical problem to be solved by the present invention is to provide an ionic porous organic polymer gel prepared by the above-mentioned method for preparing the ionic porous organic polymer gel.

[0034] The fifth technical problem to be solved by the present invention is to provide a dry gel prepared from the above-mentioned ionic porous organic polymer gel.

[0035] Furthermore, the obtained ionic porous organic polymer wet gel is processed into a dry gel. The dry gel can be obtained by solvent exchange and supercritical carbon dioxide drying. For example, the wet gel containing organic solvent is placed in a solvent (such as DMF) and soaked for a period of time (such as 2 days), taken out and then placed in a solvent (such as ethanol) for a period of time (such as 2 days), and then supercritical carbon dioxide drying is performed to obtain the dry gel.

[0036] The sixth technical problem to be solved by the present invention is to use the ionic porous organic polymer gel or dry gel obtained above for anion conduction, heavy metal adsorption or gas separation.

[0037] The seventh technical problem to be solved by the present invention is to provide an anion conducting material. The anion conducting material is obtained by subjecting the above-prepared ionic porous organic polymer gel or xerogel to solvent exchange in a solution containing hydroxide. Preferably, the hydroxide-containing solution is a sodium hydroxide solution (1 mol / L) or a potassium hydroxide solution (1 mol / L).

[0038] Beneficial effects of the present invention:

[0039] The present invention provides a methodology that is generally applicable to the synthesis of a new five-membered cyclic positively charged substance. The method has the advantages of one-pot reaction, simple reaction operation, short reaction time, mild reaction conditions, no need for harsh conditions such as anhydrous and oxygen-free conditions, and a yield of up to 95%. The method is further used to synthesize a five-membered cyclic positively charged ionic porous organic polymer gel. The synthesized gel not only has excellent processability, but also is an in-situ generated charged substance, without the need for post-modification, and the synthesis method is simple. The polymer skeleton is positively charged, and its counter ion is a chloride ion. The chloride ion can be replaced by a hydroxide ion through a simple solvent exchange, and it exhibits excellent anion conductivity. The obtained anion conductive material has an anion conductivity of 186 mS cm at 80 °C and 100%RH. -1 , and its electrical conductivity is at the leading level among the amorphous porous organic polymer materials reported so far. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The amide and pyridine aldehyde raw material structures used in the imidazolidinone compounds of the present invention are listed as follows:

[0041] Figure 2 The raw material structures of the amide monomer and pyridine aldehyde monomer used in the ionic porous organic polymer of the present invention are listed as follows:

[0042] Figure 3 The imidazolidinone compounds and ionic porous organic polymer structures of the present invention are listed as follows:

[0043] Figure 4 Examples 7, 10-13 Physical images of ionic porous organic polymer gels

[0044] Figure 5 Infrared images corresponding to monomers and polymers of Examples 7, 10-13

[0045] Figure 6 N2 adsorption-desorption and pore size distribution diagrams corresponding to polymers 7, 10-13

[0046] Figure 7 Example 7 Impedance graphs of polymer MeG1-Tpy at 100% RH and different temperatures

[0047] Figure 8 Impedance graphs of polymer MeG1-Tpy with different monomer concentrations in Examples 8 and 9 at different temperatures at 100% RH

[0048] Fig. 9 Impedance graphs of the polymers obtained in Examples 10-13 at different temperatures at 100% RH

[0049] Fig.10Conductivity graphs of the polymers obtained in Examples 7-13 at different temperatures at 100% RH

[0050] Fig.11 Example 1 Hydrogen NMR spectrum of the product

[0051] Fig.12 Example 1 Carbon NMR spectrum of the product

[0052] Fig.13 Example 2 Hydrogen NMR spectrum of the product

[0053] Fig.14 Example 2 Carbon NMR spectrum of the product

[0054] Fig.15 Example 3 Hydrogen NMR spectrum of the product

[0055] Fig.16 Example 3 Carbon NMR spectrum of the product

[0056] Fig.17 Example 4 Hydrogen NMR spectrum of the product

[0057] Fig.18 Example 4 Carbon NMR spectrum of the product

[0058] Fig.19 Example 5 Hydrogen NMR spectrum of the product

[0059] Fig. 20 Example 5 Carbon NMR spectrum of the product

[0060] Fig.21 Example 6 Carbon NMR spectrum of the product

[0061] Fig. 22 Example 6 Carbon NMR spectrum of the product DETAILED DESCRIPTION

[0062] The present invention first provides a method for preparing an imidazolidinone compound, wherein amino acid amide hydrochloride and pyridine aldehyde are used as raw materials to react in an organic solvent to prepare the imidazolidinone compound. The reaction can obtain a positively charged imidazolidinone compound in a one-pot reaction, and the operation is simple, the reaction time is short, the reaction conditions are mild, and no harsh conditions such as anhydrous and oxygen-free are required. The yield is basically as high as 95%, and the pure product can be obtained by simply removing the solvent.

[0063] The specific reaction pathway is as follows: (1) Amino acid amide hydrochloride reacts with pyridine aldehyde to form an imine intermediate (the first step); (2) The amide of the imine intermediate undergoes isomerization to obtain an imine alcohol intermediate (the second step); (3) The imine alcohol intermediate undergoes an intramolecular cyclization reaction to generate an imidazolidinone intermediate with a secondary amine (the third step); (4) The imidazolidinone product with an imine cation can be obtained by a second Schiff base condensation with pyridine aldehyde (the fourth step).

[0064]

[0065] According to the above mechanism diagram, the structural formula of amino acid amide hydrochloride is , it is necessary to ensure that the amino acid amide raw materials are α-amino acids, and contain primary amine and amide functional groups. The substituents at the R1 and R2 positions do not participate in the formation of the final product and do not affect the reaction. R1 is suitable for the side groups of natural amino acids such as H, C 1-8 Alkyl (preferably C 1-4 Alkyl), phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl, etc.; R2 is selected from C 1-12 Alkyl (preferably C 1-8 Alkyl, more preferably C 1-4 Alkyl), C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, etc., n=1-500, preferably n=1-400. n=1-300. n=1-200. n=1-100. n=1-50. n=1-20. n=1-10. The structural formula of pyridine aldehyde is , R3 is selected from H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Further, R1 is selected from H, methyl, isopropyl, i-Bu, hydroxymethyl, benzyl, and R2 is selected from methyl, -CH2CF3, cyclopropyl, phenyl, p-methoxyphenyl, p-nitrophenyl, -CH2COOH, . Most preferably, the amino acid amide hydrochloride is selected from: glycine-N-methylamide hydrochloride, (S)-2-amino-N-methylpropionamide hydrochloride, (S)-2-amino-3-methyl-N-phenylbutanamide hydrochloride, (S)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, (R)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride, 2-amino-N-cyclopropylacetamide hydrochloride, N1-phenylglycinamide hydrochloride, 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride, L-leucine-4-nitroaniline hydrochloride, L-alanine-4-nitroaniline hydrochloride, glycine hydrochloride. Most preferably, the pyridine aldehyde is selected from: pyridine-2-carboxaldehyde, 5-methylpyridine-2-carboxaldehyde, 5-methoxypyridine-2-carboxaldehyde, 5-chloropyridine-2-carboxaldehyde, 5-trifluoromethylpyridine-2-carboxaldehyde.

[0066] For the raw material amino acid amide hydrochloride of the present invention , amino acid raw materials with tert-butyloxycarbonyl (Boc) protection at the N-terminus can be used and amino-containing raw materials It is obtained by condensation by conventional methods in the art and desalting Boc under acidic conditions. Therefore, for R2, any raw material with an amino group can be used. , can be a single amino acid or a polypeptide formed by multiple amino acids, preferably 2-10 amino acids, 2-8 amino acids, 2-6 amino acids, 2-4 amino acids. Therefore, R2 can be a single amino acid group with one amino group removed or a polypeptide group with one amino acid removed.

[0067] In the above-mentioned preparation method of imidazolidinone compounds, the reaction temperature is generally room temperature to 80°C. For raw materials with less steric hindrance, the reaction can be carried out at room temperature, while for raw materials with greater steric hindrance, the reaction needs to be carried out at 80°C. The reaction temperature can be reasonably selected according to the raw materials. The reaction time is 10 minutes to 24 hours. Preferably, it is 10 minutes to 12 hours.

[0068] In the above-mentioned method for preparing imidazolidinone compounds, the organic solvent used in the reaction is selected from acetic acid, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and n-butanol, preferably acetic acid.

[0069] The present invention uses small molecules as raw materials to carry out reactions to verify the feasibility of the tandem condensation-cyclization-condensation reaction, thereby further using the reaction to prepare a positively charged ionic porous organic polymer gel, and further providing an ionic porous organic polymer gel and a preparation method thereof. The preparation method comprises the following steps: reacting an amino acid amide monomer and a pyridine aldehyde monomer in an organic solvent to obtain the ionic porous organic polymer gel; wherein the amino acid amide monomer has a structural formula of , the pyridine aldehyde is a substance having a pyridine aldehyde structure; the amino acid amide monomer is monofunctional or difunctional, and the pyridine aldehyde monomer is difunctional or trifunctional.

[0070] Furthermore, the amino acid amide monomer, pyridine aldehyde monomer and reaction solvent are ultrasonically treated to fully dissolve the organic monomers, and then added into a syringe (5 mL), placed in a 90-120 ° C oven to react for 3 hours to 3 days. After the reaction is completed, the gel is pushed out of the syringe to obtain a complete ionic porous organic polymer.

[0071] In the above-mentioned method for preparing the ionic porous organic polymer gel, R1 is selected from H, C 1-8 Alkyl (preferably C 1-4 Alkyl), phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl (preferably C 1-8 Alkyl, more preferably C 1-4 Alkyl), C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group consisting of 2-10 amino acids with one amino group removed, , n=1-500. Preferably n=1-400. n=1-300. n=1-200. n=1-100. Further, R1 is selected from H, methyl, isopropyl, i-Bu, hydroxymethyl, benzyl, and R2 is selected from methyl, -CH2CF3, cyclopropyl, phenyl, p-methoxyphenyl, p-nitrophenyl, -CH2COOH, , . Most preferably, the amino acid amide monomer is selected from: glycine-N-methylamide hydrochloride, (S)-2-amino-N-methylpropionamide hydrochloride, (S)-2-amino-3-methyl-N-phenylbutanamide hydrochloride, (S)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, (R)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride, 2-amino-N-cyclopropylacetamide hydrochloride, N1-phenylglycinamide hydrochloride, 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride, L-leucine-4-nitroaniline hydrochloride, L-alanine-4-nitroaniline hydrochloride, , glycine hydrochloride.

[0072] In the above-mentioned method for preparing the ionic porous organic polymer gel, the raw material pyridine aldehyde monomer can be any substance having a pyridine-2-carboxaldehyde structure, and in order to prepare the polymer, the pyridine-2-carboxaldehyde needs to be difunctional or trifunctional. Preferably, the pyridine-2-carboxaldehyde monomer is selected from: [3,3'-bipyridine]-6,6'-dicarboxaldehyde or 1,3,5-tris(2-formylpyridin-5-yl)benzene.

[0073] In the above-mentioned method for preparing the ionic porous organic polymer gel, DMSO is preferably used as the organic solvent, because the reaction rate can be reduced in DMSO, and the interaction between the polymer and the solvent can be promoted, thereby forming a gel.

[0074] The amino acid amide hydrochloride and pyridine aldehyde raw material structures that can be used in the present invention are listed in Figure 1 The structures of amino acid amide monomers and pyridine aldehyde monomers that can be used are listed in Figure 2 The imidazolidinone compounds and ionic porous organic polymer structures prepared by the present invention are listed in Figure 3 .

[0075] The experimental scheme of the present invention will be described in detail below with reference to examples. The raw materials, reagents or instruments used without indicating the manufacturer can be purchased from the market or prepared by conventional raw materials using existing methods.

[0076] Example 1 Synthesis of five-membered ring-shaped positively charged ionic small molecules

[0077] Add glycine-N-formamide hydrochloride (1 mmol), pyridine-2-carboxaldehyde (2 mmol) and acetic acid (3 mL) into a 10 mL sample bottle, react at 80 °C for 12 hours, and evaporate the solvent to obtain the final product ( Fig.11 and 12 ).

[0078] Embodiment 2-6

[0079] The preparation process and the ratio of reactants are the same as those in Example 1, except that the amino monomer in step 1) is changed from glycine-N-formamide hydrochloride to (S)-2-amino-N-methylpropionamide hydrochloride (Example 2, Fig.13 and 14 ), 2-amino-N-cyclopropylacetamide hydrochloride (Example 3, Fig.15 and 16 ), 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride (Example 4, Fig.17 and 18 ), (S)-2-amino-3-methyl-N-phenylbutanamide hydrochloride (Example 5, Fig.19 and 20 ), Glycine Hydrochloride (Example 6, Fig.21 and 22 ) reacts with pyridine-2-carboxaldehyde to produce the corresponding product.

[0080] Example 7 Preparation of five-membered ring-shaped positively charged porous organic polymer gel

[0081] 1) In a 10 mL sample bottle, add glycine-N-formamide hydrochloride (0.1 mmol), 1,3,5-tri(2-formylpyridin-5-yl)benzene (0.066 mmol) and DMSO (1 mL) and sonicate for 10 minutes to fully dissolve the monomer, then transfer it to a 5 mL syringe and place it in a 90 °C oven for reaction for 1 day. After the reaction is completed, push the gel out of the syringe to obtain a complete black gel (MeG1-Tpy);

[0082] 2) Soak the wet gel obtained in step 1) in N,N-dimethylformamide for 2 days, replace the solvent every 12 hours, take it out after two days, soak it in ethanol for 2 days, replace the solvent every 12 hours, and then dry it with supercritical carbon dioxide to obtain a dry gel (MeG1-Tpy).

[0083] Embodiment 8-9

[0084] The preparation process is the same as that of Example 7, except that the monomer concentration in step 1) is changed (i.e., the molar volume ratio of glycine-N-formamide hydrochloride to DMSO in Example 7 is changed) to 0.2 mol / L (Example 8) and 0.3 mol / L (Example 9), respectively; and gels can be obtained in both cases.

[0085] Examples 10-13

[0086] The preparation process is the same as that of Example 7, except that the amino monomer in step 1) is changed from glycine-N-formamide hydrochloride to (S)-2-amino-N-methylpropionamide hydrochloride (Example 10, polymer MeA1-Tpy), N1-phenylglycineamide hydrochloride (Example 11, polymer PhG1-Tpy), (Example 12, polymer PhG2-Tpy) reacts with 1,3,5-tri(2-formylpyridin-5-yl)benzene to form a polymer; the aldehyde monomer in step 1) is changed from 1,3,5-tri(2-formylpyridin-5-yl)benzene to [3,3'-bipyridine]-6,6'-dicarboxaldehyde and The reaction generated a polymer (Example 13, polymer PhG2-Bpy), and the results showed that the corresponding gel structure (such as Figure 4 as shown).

[0087] Example 14 Preparation of anion conducting material from ion-type porous organic polymer gel after solvent exchange

[0088] The wet gel of MeG1-Tpy (Example 7) with a monomer concentration of 0.1 mol / L is immersed in a 1 mol / L sodium hydroxide solution and taken out after immersion for 24 hours to obtain an anion conductive material.

[0089] Structural characterization

[0090] 1) Infrared spectra of polymers corresponding to different amino acid amide monomers

[0091] After drying, the wet gels of the products of the reaction of different amino acid amide monomers with pyridine aldehyde were subjected to infrared testing. Figure 5 As shown: The 2865 cm-1 ions do not exist in the spectrum of MeG1-Tpy. -1 The peak at 2925 cm corresponds to the NH vibration in the monomer MeG1, indicating that glycine-N-formamide hydrochloride is completely consumed. -1 The peak at 1698 cm-1 in MeG1-Tpy is attributed to the CH vibration of the methylene group, which confirms that the amino acid derivative has been successfully incorporated into the polymer. -1 The peak corresponding to the C=O vibration of the aldehyde group disappeared and the peak at 1683 cm -1 A new peak appeared at , indicating that the aldehyde group was successfully converted into imine, so the infrared spectrum showed that the reaction occurred.

[0092] 2) N2 adsorption-desorption spectra of polymers corresponding to different amino acid amide monomers

[0093] Take a certain amount of sample in a sample tube, vacuum dry it at 120 °C, and then set the program to test the N2 adsorption-desorption curve of the sample to obtain the specific surface area (BET), such as Figure 6 As shown in the figure, the five polymers (a is the adsorption-desorption curve of MeG1-Tpy, b is the pore size distribution of MeG1-Tpy; c is the adsorption-desorption curve of MeA1-Tpy, d is the pore size distribution of MeA1-Tpy; e is the adsorption-desorption curve of PhG1-Tpy, f is the pore size distribution of PhG1-Tpy; g is the adsorption-desorption curve of PhG2-Tpy, h is the pore size distribution of PhG2-Tpy; i is the adsorption-desorption curve of PhG2-Bpy, j is the pore size distribution of PhG2-Bpy) all show typical type II adsorption curves, among which MeG1-Tpy has the largest specific surface area of ​​681 m 2 g -1 The pore size distribution shows that the ionic porous organic polymer contains micropores, mesopores and macropores, and the main size distribution is around 2 nm.

[0094] Electrochemical impedance spectroscopy

[0095] The MeG1-Tpy obtained in Example 7 was placed in a hollow polytetrafluoroethylene gasket with a height of 0.2 cm, an outer diameter of 1.5 cm, and an inner diameter of 1 cm. Silver sheets with a diameter of 1.5 cm were used at both ends to contact the sample. The gasket was then clamped with electrodes, and the sample was placed in a constant temperature and humidity chamber, the humidity was adjusted to 100% RH, and the electrochemical impedance spectrum was tested at 30-80 °C using an electrochemical workstation. The conductivity is calculated according to σ = l / (A*R), where σ is the conductivity (mS cm -1 ), l is the electrode distance (cm), A is the contact area between the electrode and the sample (cm 2 ), R is the impedance (Ω). Figure 7 As shown in Figure 2, MeG1-Tpy exhibits excellent anion conductivity under different temperature conditions of 100% RH. Under the test conditions of 80 °C and 100% RH, the anion conductivity reaches 164 mS cm -1 .

[0096] According to the same test conditions as above, the impedance of the polymers with different monomer concentrations in Examples 8 and 9 at a temperature range of 30-80°C and a relative humidity of 100% RH is measured as follows: Figure 8 As shown (a corresponds to Example 8, b corresponds to Example 9), Fig. 9(a corresponds to Example 10, b corresponds to Example 11, c corresponds to Example 12, and d corresponds to Example 13) It can be seen that: as the monomer concentration increases, the conductivity decreases. The presumed reason is that the increase in monomer concentration causes the microstructure of the iPOP gel to become tighter, thereby blocking the ion transmission channel and causing the ion conductivity to decrease.

[0097] Further, under the same test conditions, the conductivity of the polymers corresponding to the different amino acid amide monomers in Examples 7-13 at a temperature range of 30-80° C. and a relative humidity of 100% RH was measured as follows: Fig.10 As shown in (a) corresponding to Examples 7, 8, and 9, it was found that among the five polymers, when the amino acid derivative monomer was (S)-2-amino-N-methylpropionamide hydrochloride, the corresponding polymer MeA1-Tpy had the largest conductivity under the same conditions, which was 186 mS cm -1 .

Claims

1. A method for preparing an imidazolidinone compound, characterized in that: The method comprises the following steps: reacting amino acid amide hydrochloride with pyridine aldehyde in an organic solvent to obtain the imidazolidinone compound. ; Wherein, the amino acid amide hydrochloride structural formula is , R1 is selected from H, C 1-8 Alkyl, phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500; the pyridine aldehyde structural formula is , R3 is selected from H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Haloalkyl, amide, ester, phenyl.

2. The method for preparing an imidazolidinone compound according to claim 1, wherein: The amino acid amide hydrochloride is selected from the group consisting of glycine-N-methylamide hydrochloride, (S)-2-amino-N-methylpropionamide hydrochloride, (S)-2-amino-3-methyl-N-phenylbutyramide hydrochloride, (S)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, (R)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride, 2-amino- N-cyclopropylacetamide hydrochloride, N1-phenylglycinamide hydrochloride, 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride, L-leucine-4-nitroaniline hydrochloride, L-alanine-4-nitroaniline hydrochloride, glycylglycine hydrochloride; the pyridine aldehyde is selected from: pyridine-2-carboxaldehyde, 5-methylpyridine-2-carboxaldehyde, 5-methoxypyridine-2-carboxaldehyde, 5-chloropyridine-2-carboxaldehyde, 5-trifluoromethylpyridine-2-carboxaldehyde.

3. The method for preparing an imidazolidinone compound according to claim 1 or 2, characterized in that: Satisfy at least one of the following: The molar ratio of the amino acid amide hydrochloride to pyridine aldehyde is 1: 1-10; The organic solvent is selected from acetic acid, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and n-butanol; The molar volume ratio of the amino acid amide hydrochloride to the organic solvent is 1 mmol: 1-15 mL; The reaction temperature is 25-80°C; The reaction time is 10 min-24 h.

4. Formula ( ) or its stereoisomers: Mode( ) in, R1 is selected from H, C 1-8 Alkyl, phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500; R3 is selected from H, halogen, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Haloalkyl, amide, ester, phenyl.

5. A method for preparing an ionic porous organic polymer gel, characterized in that: The method comprises the following steps: reacting an amino acid amide monomer and a pyridine aldehyde monomer in an organic solvent to obtain the ionic porous organic polymer gel; wherein the amino acid amide monomer has a structural formula of , R1 is selected from H, C 1-8 Alkyl, phenyl substituted C 1-4 Alkyl, hydroxy substituted C 1-4 Alkyl, carboxyl substituted C 1-4 Alkyl, -C 1-4 Alkyl-CONH2, methylthio substituted C 1-4 Alkyl, thiol substituted C 1-4 Alkyl; R2 is selected from C 1-12 Alkyl, C 1-4 Haloalkyl, C 3-6 Cycloalkyl, phenyl, C 1-4 Alkoxy substituted phenyl, nitro substituted phenyl, carboxyl substituted C 1-4 alkyl, , , a single amino acid group with one amino group removed, a polypeptide group formed by 2-10 amino acids with one amino group removed, n=1-500; the pyridine aldehyde monomer is selected from [3,3'-bipyridine]-6,6'-dicarboxaldehyde or 1,3,5-tri(2-formylpyridin-5-yl)benzene.

6. The method for preparing the ionic porous organic polymer gel according to claim 5, characterized in that: The amino acid amide monomer is selected from: glycine-N-methylamide hydrochloride, (S)-2-amino-N-methylpropionamide hydrochloride, (S)-2-amino-3-methyl-N-phenylbutanamide hydrochloride, (S)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, (R)-2-amino-N-methyl-3-phenylpropionamide hydrochloride, 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride, 2-amino-N-cyclopropylacetamide hydrochloride, N1-phenylglycinamide hydrochloride, 2-amino-N-(4-methoxyphenyl)acetamide hydrochloride, L-leucine-4-nitroaniline hydrochloride, L-alanine-4-nitroaniline hydrochloride, , glycine hydrochloride.

7. The method for preparing the ionic porous organic polymer gel according to claim 5 or 6, characterized in that: Satisfy at least one of the following: The molar ratio of the amino acid amide monomer to the pyridine aldehyde monomer is 1-4:2; The organic solvent is dimethyl sulfoxide; The molar volume ratio of the amino acid amide monomer to the organic solvent is 0.1 - 0.3 mmol: 1 mL; The reaction temperature is 90-120°C; The reaction time is 3 hours to 3 days.

8. An ionic porous organic polymer gel, characterized in that: The ionic porous organic polymer gel is prepared by the preparation method of any one of claims 5 to 7.

9. Use of the ionic porous organic polymer gel according to claim 8 or a xerogel prepared therefrom in anion conduction, heavy metal adsorption or gas separation.

10. An anion conducting material, characterized in that: The ionic porous organic polymer gel according to claim 8 or the dry gel prepared therefrom is prepared by subjecting the gel to solvent exchange in a solution containing hydroxide.

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