Trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer, preparation method thereof and application thereof

Abstract

The present invention discloses a trans-disubstituted calix[4]pyrrole supramolecular macrocycle porous organic polymer, a preparation method thereof, and an application thereof. The present invention belongs to the technical field of supramolecular materials and porous materials, and specifically discloses a series of preparation methods and applications of porous organic polymers based on calix[4]pyrrole supramolecular macrocycles connected by acetylenic bonds and imine bonds, respectively. The porous polymer in the present invention is obtained by Sonogashira coupling reaction or Schiff base reaction of trans-disubstituted calix[4]pyrrole and three-headed or four-headed rigid structural units. The material contains a calix[4]pyrrole supramolecular macrocycle, a cross-linked network structure, and a rich pore structure, so that it has the characteristics of both supramolecular macrocycles and organic porous materials, and can be used in the fields of selective adsorption and adsorption separation of gases, organic micropollutants, and radioactive pollutants.

Description

Technical Field

[0001] The present invention relates to the field of supramolecular materials and porous materials, specifically to a preparation method for a series of porous organic polymers based on calix[4]pyrrole supramolecular macrocycles, and their applications in the selective adsorption and adsorption separation of gases, organic micropollutants and radioactive pollutants. Background Art

[0002] Porous organic polymers are a class of porous polymers composed of light elements such as carbon, hydrogen, oxygen, and nitrogen. Compared with inorganic porous materials, porous organic polymers have the advantages of higher specific surface area, high porosity, high thermal stability, high chemical stability, and adjustable pore size. Therefore, they have developed rapidly in the past decade and are ideal candidate materials in the field of adsorption separation. The synthesis of supramolecular macrocyclic compounds and their molecular recognition have always been a hot research direction in supramolecular materials. Common supramolecular macrocycles include crown ethers, cyclodextrins, calixarenes, calix[4]pyrroles, and pillararenes. They all have their own unique stereostructures and cavity structures, and can selectively recognize and complex guest molecules. Among them, calix[4]pyrrole is the simplest calixpyrrole macrocyclic system, which is composed of four α-positions of pyrrole and four sp 3 Hybridized carbon atoms are connected to form non-planar non-aromatic macrocyclic compounds. The four pyrrole rings in the cone configuration can form a hydrophobic electron-rich cavity. At the same time, the NH on the pyrrole can effectively complex with anions through hydrogen bonds. Among them, the trans-disubstituted calix[4]pyrrole molecule presents a chair-like structure as a whole. The calix[4]pyrrole core adopts a 1,2-alternating conformation in the solid state. The size of the calix[4]pyrrole macrocyclic cavity is about Therefore, trans-disubstituted calix[4]pyrrole is sufficient to accommodate iodine molecules or small organic micropollutants.

[0003] Numerous reports have been published on the application of simple calix[4]pyrrole small molecule derivatives, linear calix[4]pyrrole-based polymers, and gels based on calix[4]pyrrole for compound separation and purification. The adsorption separation of gases and pollutants has broad application prospects in areas such as compound purification, energy storage, and environmental pollution control. However, the adsorption capacity and adsorption rate of current adsorbents need to be improved, and the design and preparation of new adsorbents are urgent issues that need to be addressed. Summary of the Invention

[0004] In order to solve the problems of the prior art, the purpose of the present invention is to overcome the shortcomings of the existing technology and provide a trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymer, its preparation method and application, which can provide two types of trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymers connected by acetylenic bonds and imine bonds respectively. This type of material contains calix[4]pyrrole supramolecular macrocycle, a cross-linked network structure and a rich pore structure, so that it has the characteristics of both supramolecular macrocycle and organic porous material, and can be used in the fields of selective adsorption and adsorption separation of gases, organic micropollutants and radioactive pollutants.

[0005] In order to achieve the above invention purpose, the present invention adopts the following inventive concept:

[0006] The focus of the present invention is to combine supramolecular macrocyclic chemistry with porous organic polymers based on material structure design. The present invention selects trans-disubstituted calix[4]pyrrole supramolecular macrocycles and introduces calix[4]pyrrole as a structural unit into the rigid skeleton of the porous organic polymer, so that it has both the host-guest interaction characteristics of calix[4]pyrrole supramolecular chemistry and the rich pore structure of the porous organic material. At the same time, the rigid porous skeleton structure is also conducive to the exposure of calix[4]pyrrole and other active sites in the structure to interact with guest molecules, thereby improving the material's adsorption capacity for gases and organic micropollutants. By changing the molecular size, type and number of substituents, stereostructure and electronic properties of the comonomer, porous organic polymers with different skeleton structures can be obtained. The comonomer is a three-headed or four-headed rigid structural unit, the three-headed rigid structural unit is selected from at least one of 1,3,5-trihydroxybenzene, 2,4,6-triphenyltriazine, triphenylamine and tripolyindene; the four-headed rigid structural unit is selected from at least one of tetraphenylethylene, 1,3,6,8-tetraphenylpyrene, tetraphenylmethane and 1,4-bis(triphenylmethyl)benzene.

[0007] The synthesis of the comonomers can refer to the reported literature: Synthesis reference of A-2: Catal. Sci. Technol., 2015, 5, 2585-2589, Synthesis reference of A-3: Polym. Chem., 2021, 12, 3551-3555, Synthesis reference of A-4: J. Fluoresc., 2014, 24, 197-202, Synthesis reference of A-5: Org. Lett., 2010, 12, 22, 5192-5195 and the synthesis reference of B-1: Small, 2019, 15, 1804519, the synthesis of C-2 can refer to the reference: Org. Mater., 2021, 3, 277-282, the synthesis of C-3 can refer to the reference: Chin. J. Catal., 2021, 42, 2010-2019, the synthesis of C-4 can refer to the reference: Dyes andPigments,2021,193,109534, the synthesis of C-5 can refer to the literature: J.Mater.Chem.C,2015,3,10066-10069, the synthesis of D-1 can refer to the literature: Angew.Chem.Int.Ed.,2020,59,20090-20098, the synthesis of D-3 can refer to the literature: J.Am.Chem.Soc.,2018,140,13,4494-4498.

[0008]

[0009] According to the above invention concept, the present invention adopts the following technical solutions:

[0010] A trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymer, which adopts a trans-disubstituted calix[4]pyrrole supramolecular macrocyclic; calix[4]pyrrole is introduced as a structural unit into the rigid skeleton of the porous organic polymer to form a comonomer, so that the comonomer contains both the calix[4]pyrrole supramolecular chemical host and guest and the pore structure of the porous organic material; at the same time, the rigid porous skeleton structure exposes the calix[4]pyrrole and other active sites in the structure to form sites for interacting with guest molecules and adsorbing gas molecules and organic micro-pollutant molecules; by changing the molecular size, substituent type and number, and stereostructure of the comonomer, porous organic polymers with different skeleton structures can be obtained; the comonomer selects a three-head rigid structural unit or a four-head rigid structural unit.

[0011] Preferably, the trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer of the present invention has one of the following molecular structures:

[0012]

[0013] Among them, the triangle Represents a three-headed rigid structural unit, which adopts at least one of 1,3,5-trihydroxybenzene, 2,4,6-triphenyltriazine, triphenylamine and tripolyindene; square ◆ represents a four-headed rigid structural unit, which adopts at least one of tetraphenylethylene, 1,3,6,8-tetraphenylpyrene, tetraphenylmethane and 1,4-bis(triphenylmethyl)benzene; in the structural formula: X is a carbon or nitrogen atom; Y is an acetylenic bond or an aldehyde group; alkyl chain is an alkyl chain of different lengths and shapes.

[0014] Further preferably, in the trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymer according to the present invention, the polymer (I) and the polymer (III) connected by acetylenic bonds are prepared by Sonogashira coupling of trans-bis(4-iodophenyl)calix[4]pyrrole in the following structural formula with a triacetylenic rigid structural unit A or a tetraacetylenic rigid structural unit B; the polymer (II) and the polymer (IV) connected by imine bonds are prepared by Schiff base reaction of trans-bis(4-aminophenyl)calix[4]pyrrole in the following structural formula with a trialdehyde rigid structural unit C or a tetraaldehyde rigid structural unit D;

[0015]

[0016] As a preferred technical solution, the trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymer of the present invention adopts trans-bis(4-iodophenyl)calix[4]pyrrole, and trans-bis(4-iodophenyl)calix[4]pyrrole and three-headed rigid structural unit A are dissolved in anhydrous toluene and triethylamine according to a molar ratio of 3:(2-3), and tetrakis(triphenylphosphine)palladium and cuprous iodide are used as catalysts to carry out Sonogashira coupling reaction under nitrogen protection. The obtained crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran and acetone, and then extracted with dichloromethane Soxhlet. The remaining solid is polymer (I).

[0017] As another preferred technical solution, the trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymer of the present invention adopts trans-bis(4-iodophenyl)calix[4]pyrrole, and trans-bis(4-iodophenyl)calix[4]pyrrole and four-headed rigid structural unit B are dissolved in anhydrous toluene and triethylamine according to a molar ratio of 2:(1-2), and tetrakis(triphenylphosphine)palladium and cuprous iodide are used as catalysts to carry out Sonogashira coupling reaction under nitrogen protection. The obtained crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran and acetone, and then extracted with dichloromethane Soxhlet, and the remaining solid is polymer (III).

[0018] As another preferred technical solution, the trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer of the present invention adopts trans-bis(4-aminophenyl)calix[4]pyrrole, and trans-bis(4-aminophenyl)calix[4]pyrrole and three-headed rigid structural unit C are dispersed in the ionic liquid 1-butyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide ([BMIm][NTf2]) according to a molar ratio of 3:(2-3), and a Schiff base reaction is carried out. The obtained crude product is washed with acetone and ethanol, and the remaining solid is polymer (II).

[0019] As another preferred technical solution, the trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer described in the present invention is characterized in that: trans-bis(4-aminophenyl)calix[4]pyrrole is used, trans-bis(4-aminophenyl)calix[4]pyrrole and a four-headed rigid structural unit D are dispersed in the ionic liquid 1-butyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide ([BMIm][NTf2]) in a molar ratio of 2:(1-2), and a Schiff base reaction is carried out. The obtained crude product is washed with acetone and ethanol, and the remaining solid is polymer (IV).

[0020] Preferably, the structural formulas of the 18 polymer materials in the present invention are as follows:

[0021] (1) Trans-bis(4-iodophenyl)calix[4]pyrrole and the tri-alkynyl rigid structural unit A undergo Sonogashira copolymerization to obtain the acetylenic bond-linked polymer I with the following structure:

[0022]

[0023] (2) Trans-bis(4-iodophenyl)calix[4]pyrrole undergoes Sonogashira copolymerization with the tetra-alkynyl rigid structural unit B to obtain the structure of the alkyne-linked polymer III:

[0024]

[0025] (3) Trans-bis(4-aminophenyl)calix[4]pyrrole reacts with the trialdehyde rigid structural unit C to form the structural formula of polymer II connected by imine bond:

[0026]

[0027] (4) Trans-bis(4-aminophenyl)calix[4]pyrrole reacts with the tetraaldehyde rigid structural unit D to form the imine bond-linked polymer IV.

[0028]

[0029] Tests and characterizations show that the polymer obtained by the present invention has high thermal stability and chemical stability, and also has porous properties.

[0030] A method for preparing a trans-disubstituted calix[4]pyrrole supramolecular macrocyclic porous organic polymer according to the present invention adopts any of the following methods:

[0031] First method:

[0032] Trans-bis(4-iodophenyl)calix[4]pyrrole is used, and trans-bis(4-iodophenyl)calix[4] and a three-headed rigid structural unit A or a four-headed rigid structural unit B are dissolved in anhydrous toluene and triethylamine. Tetrakis(triphenylphosphine)palladium and cuprous iodide are used as catalysts. After cyclic freezing and deoxygenation for at least three times, a Sonogashira coupling reaction is carried out at a temperature not lower than 90° C. under nitrogen protection for at least 3 days. The reaction mixture is then cooled to room temperature, the solvent is removed by filtration, and the resulting crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran, and acetone, and then subjected to Soxhlet extraction with dichloromethane for at least 24 hours and dried to obtain a polymer (I) or a polymer (III).

[0033] Dissolving trans-bis(4-iodophenyl)calix[4]pyrrole and three-headed rigid structural unit A in anhydrous toluene and triethylamine at a molar ratio of 3:(2-3); or dissolving trans-bis(4-iodophenyl)calix[4]pyrrole and four-headed rigid structural unit B in anhydrous toluene and triethylamine at a molar ratio of 2:(1-2);

[0034] Second method:

[0035] Trans-bis(4-aminophenyl)calix[4]pyrrole is used, and trans-bis(4-aminophenyl)calix[4]pyrrole and a three-headed rigid structural unit C or a four-headed rigid structural unit D are dispersed in an ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIm][NTf2]), and the mixture is allowed to stand at room temperature for at least 3 minutes to react with a Schiff base. The resulting crude product is washed with acetone and ethanol to obtain a polymer (II) or a polymer (IV);

[0036] Trans-bis(4-aminophenyl)calix[4]pyrrole and three-headed rigid structural unit C are dispersed in an ionic liquid at a molar ratio of 3:(2-3); or trans-bis(4-aminophenyl)calix[4]pyrrole and four-headed rigid structural unit D are dispersed in an ionic liquid at a molar ratio of 2:(1-2);

[0037] In any of the above methods, the three-head rigid structural element adopts any of the following structural formulas:

[0038]

[0039] In any of the above methods, the four-head rigid structural element adopts any of the following structural formulas:

[0040]

[0041] In the structural formula, Y in the three-headed rigid structural unit A is an acetylenic bond group, Y in the three-headed rigid structural unit C is an aldehyde group, Y in the four-headed rigid structural unit B is an acetylenic bond group, and Y in the four-headed rigid structural unit D is an aldehyde group; X is a carbon or nitrogen atom; and alkyl chain is an alkyl chain of different lengths and shapes.

[0042] An application of the trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer of the present invention is applied to the selective adsorption and separation of small molecule gases, organic micropollutants, and radioactive pollutants.

[0043] Tests and characterizations have shown that the polymer obtained by the present invention can be used for adsorption of iodine and organic micropollutants in vapor state or in aqueous solution.

[0044] Compared with the prior art, the present invention has the following obvious outstanding substantial features and significant advantages:

[0045] 1. The porous organic polymer of the present invention has high thermal stability, and the decomposition temperature is not less than 250°C;

[0046] 2. The method for preparing the porous organic polymer of the present invention has a high yield and is suitable for industrial application;

[0047] 3. The material of the present invention contains a supramolecular macrocycle of calix[4]pyrrole, a cross-linked network structure and a rich pore structure, which makes it have the characteristics of both supramolecular macrocycle and organic porous material. As an adsorption material, it has a high adsorption capacity and a fast adsorption rate, and can be used in the fields of selective adsorption and adsorption separation of gases, organic micropollutants and radioactive pollutants. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 1 and 2 are solid-state NMR images of polymers 8 and 9 according to preferred embodiments of the present invention.

[0049] Figure 2 IR analysis diagrams of polymer 8 and polymer 9 according to preferred embodiments of the present invention.

[0050] Figure 3 These are thermogravimetric analysis diagrams of polymers 8 and 9 according to preferred embodiments of the present invention.

[0051] Figure 4 This is a graph showing the adsorption efficiency of polymer 8 and polymer 9 according to preferred embodiments of the present invention for iodine vapor at 75°C.

[0052] Figure 5 This is an ultraviolet spectrum of iodine adsorption by polymer 8 in aqueous solution according to a preferred embodiment of the present invention.

[0053] Figure 6 This is an ultraviolet spectrum of iodine adsorption by polymer 9 in aqueous solution according to a preferred embodiment of the present invention.

[0054] Figure 7 This is the UV absorption graph of polymer 8 according to a preferred embodiment of the present invention on 1-naphthylamine in aqueous solution.

[0055] Figure 8 This is an ultraviolet spectrum of the adsorption of 1-naphthylamine by polymer 9 according to a preferred embodiment of the present invention in aqueous solution.

[0056] Figure 9 The polymers 8 and 9 of the preferred embodiment of the present invention were heated to 2 mL / min. -1 and 10 mL / min -1 UV absorption graph of mobile phase iodine solution at flow rate. DETAILED DESCRIPTION

[0057] The technical solutions of the present invention are further illustrated below by way of examples, so as to provide a better understanding of the present invention.

[0058] (1) Preparation of trans-calix[4]pyrrole monomer

[0059] The synthesis of trans-bis(4-iodophenyl)calix[4]pyrrole can be found in the literature: J.Am.Chem.Soc.2012,134,10733-10736.

[0060] Synthesis of trans-bis(4-aminophenyl)calix[4]pyrrole:

[0061]

[0062] Trans-bis(4-iodophenyl)calix[4]pyrrole (530 mg, 0.66 mmol), cesium carbonate (861 mg, 2.64 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (95.2 mg, 0.20 mmol), palladium acetate (15.0 mg, 0.066 mmol), and tert-butyl carbamate (295.6 mg, 2.64 mmol) were dissolved in 200 mL of 1,4-dioxane. The mixture was heated to 100°C under nitrogen for 4 hours. After cooling to room temperature, the mixture was filtered and the filtrate was concentrated to obtain a crude product. The crude product was separated by column chromatography using ethyl acetate and petroleum ether (1:20, v:v) to obtain 464 mg of a white solid (90% yield).

[0063]

[0064] The above white solid (391 mg, 0.5 mmol) was dissolved in 50 mL of dichloromethane, and 2.0 mL of trifluoroacetic acid was added. The mixture was stirred at room temperature for 24 hours. The mixture was washed twice with 10% sodium bicarbonate solution and saturated brine, and concentrated to obtain a crude product. The crude product was recrystallized from dichloromethane and petroleum ether to obtain 261 mg of trans-bis(4-aminophenyl)calix[4]pyrrole (yield 90%).

[0065] Synthesis of rigid structural units A and B of (di)trialkynyl and tetraalkynyl groups

[0066] The synthesis of rigid structural elements A and B of trialkynyl and tetraalkynyl groups has been reported in the literature. The synthesis reference of A-2 is: Catal. Sci. Technol., 2015, 5, 2585-2589, the synthesis reference of A-3 is: Polym. Chem., 2021, 12, 3551-3555, the synthesis reference of A-4 is: J. Fluoresc., 2014, 24, 197-202, the synthesis reference of A-5 is: Org. Lett., 2010, 12, 22, 5192-5195, and the synthesis reference of B-1 is: Small, 2019, 15, 1804519. The general synthesis steps of rigid structural elements A and B of trialkynyl and tetraalkynyl groups are as follows:

[0067] Under nitrogen, tribromo A or tetrabromo B (1 equiv.), bistriphenylphosphine palladium dichloride (0.1 equiv.), triphenylphosphine (0.2 equiv.), and cuprous iodide (0.2 equiv.) were dissolved in tetrahydrofuran and triethylamine (1:1, v:v). Trimethylethynylsilane (4.5 equiv. for trisubstituted A and 6 equiv. for tetrasubstituted B) was then added via syringe and allowed to react at room temperature for 5 hours. Extraction was performed with dichloromethane and dilute hydrochloric acid. The organic phase was separated, washed with saturated ammonium chloride, and dried over anhydrous sodium sulfate. The crude product obtained by concentration was directly dissolved in tetrahydrofuran and methanol, and potassium carbonate (10 equiv.) was added. The reaction was allowed to react at room temperature for 3 hours. Extraction was performed with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Column chromatography was then performed to separate the rigid structural motifs A and B, respectively, for the trialkynyl and tetraalkynyl groups.

[0068] (III) Synthesis of rigid structural units C and D of trialdehyde and tetraaldehyde groups:

[0069] The synthesis of the rigid structural elements C and D of trialdehyde and tetraaldehyde groups can be referred to the literature: The synthesis of C-2 can be referred to the literature: Org.Mater., 2021, 3, 277-282, the synthesis of C-3 can be referred to the literature: Chin.J.Catal., 2021, 42, 2010-2019, the synthesis of C-4 can be referred to the literature: Dyes and Pigments, 2021, 193, 109534, the synthesis of C-5 can be referred to the literature: J.Mater.Chem.C, 2015, 3, 10066-10069, the synthesis of D-1 can be referred to the literature: Angew.Chem.Int.Ed., 2020, 59, 20090-20098, the synthesis of D-3 can be referred to the literature: J.Am.Chem.Soc., 2018, 140, 13, 4494-4498. The general synthesis steps of the rigid structural units C and D of trialdehyde and tetraaldehyde are as follows:

[0070] Under anhydrous and oxygen-free conditions, tribromo C or tetrabromo D (1 equiv.) was dissolved in tetrahydrofuran and cooled to -78°C. n-Butyl lithium (2.6 equiv. for trisubstituted C and 4.8 equiv. for tetrasubstituted D) was added dropwise, and the temperature was slowly raised to -30°C for half an hour. The temperature was then further lowered to -78°C, and an excess of N,N-dimethylformamide (40 equiv.) in tetrahydrofuran was added and stirred for 3 hours. The reaction was warmed to 0°C for 30 minutes, quenched with dilute hydrochloric acid, and extracted with chloroform. The organic phase was dried over anhydrous sodium sulfate and concentrated to yield a crude yellow product. Column chromatography was then performed to separate the rigid structural motifs C and D, respectively, with trialdehyde and tetraaldehyde motifs.

[0071] The above solution is further described below with reference to specific implementation examples. The preferred embodiments of the present invention are described in detail as follows:

[0072] Example 1

[0073] In this example, the synthesis of polymer 8 is as follows:

[0074] Trans-bis(4-iodophenyl)calix[4]pyrrole (96.5 mg, 0.12 mmol), tetraheaded rigid structural unit B-3 (50 mg, 0.12 mmol), tetrakis(triphenylphosphine)palladium (29 mg, 0.0252 mmol), and cuprous iodide (8.9 mg, 0.0468 mmol) were added to a mixed solvent of dry toluene (16 mL) and triethylamine (16 mL). After three cycles of refrigeration and deoxygenation, the mixture was reacted at 90°C for 3 days. The mixture was cooled to room temperature, filtered to remove the solvent, and washed sequentially with dichloromethane, dilute hydrochloric acid, tetrahydrofuran, and acetone. The mixture was then extracted with dichloromethane in a Soxhlet extractor for 24 hours and dried to obtain 83.4 mg of a yellow solid (yield 98%).

[0075] Example 2

[0076] This embodiment is basically the same as the first embodiment, with the following special features:

[0077] In this example, the synthesis of polymer 9 is as follows:

[0078] Trans-bis(4-iodophenyl)calix[4]pyrrole (241.2 mg, 0.3 mmol), tetraheaded rigid structural unit B-4 (70.69 mg, 0.1 mmol), tetrakis(triphenylphosphine)palladium (24 mg, 0.021 mmol), and cuprous iodide (8 mg, 0.042 mmol) were added to a mixed solvent of dry toluene (16 mL) and triethylamine (16 mL). After three cycles of refrigeration and deoxygenation, the mixture was reacted at 90°C for 3 days. The mixture was cooled to room temperature, filtered to remove the solvent, and washed sequentially with dichloromethane, dilute hydrochloric acid, tetrahydrofuran, and acetone. The mixture was then extracted with dichloromethane in a Soxhlet extractor for 24 hours and dried to obtain 232.8 mg of a yellow solid (yield 99.9%).

[0079] Example 3

[0080] This embodiment is basically the same as the above embodiment, with the following special features:

[0081] In this example, the synthesis of polymer 17 was as follows:

[0082] Trans-bis(4-aminophenyl)calix[4]pyrrole (58.2 mg, 0.1 mmol), four-headed rigid structural unit D-3 (21.6 mg, 0.05 mmol) and 1-butyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide (100 μL) were allowed to stand at room temperature for 3 minutes, filtered, and washed with acetone and ethanol to obtain 45.7 mg of yellow crystals (yield 60%).

[0083] The synthesis of other polymers was prepared by referring to the synthesis steps of polymer 8, polymer 9 and polymer 17.

[0084] The structure of the polymer was confirmed to contain calix[4]pyrrole and comonomer by solid-state nuclear magnetic resonance and infrared spectroscopy, and thermogravimetric analysis showed that the polymer had high thermal stability (decomposition temperature > 250°C).

[0085] The above examples have been used to prepare polymers. The general synthesis steps of polymers are:

[0086] Trans-bis(4-iodophenyl)calix[4]pyrrole in the following structural formula is dissolved in anhydrous toluene and triethylamine at a molar ratio of 3:2 with a three-headed rigid structural unit A or at a molar ratio of 2:1 with a four-headed rigid structural unit B, and a Sonogashira coupling reaction is carried out under nitrogen protection using tetrakis(triphenylphosphine)palladium and cuprous iodide as catalysts. The resulting crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran, and acetone and extracted with dichloromethane Soxhlet to obtain polymers (I) and (III);

[0087] Trans-bis(4-aminophenyl)calix[4]pyrrole is dispersed in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIm][NTf2]) in a molar ratio of 3:2 with a three-headed rigid structural unit C or in a molar ratio of 2:1 with a four-headed rigid structural unit D to carry out a Schiff base reaction. The crude product is washed with acetone and ethanol to obtain polymers (II) and (IV).

[0088] Figure 1 1 and 2 are solid-state NMR images of polymers 8 and 9 of the above examples. Figure 2 IR analysis charts of polymer 8 and polymer 9 of the above examples. Figure 3 The thermogravimetric analysis diagrams of polymers 8 and 9 of the above examples are shown. The polymers were confirmed to contain calix[4]pyrrole and comonomer structures by solid-state nuclear magnetic resonance and infrared spectroscopy, such as Figure 3 As shown, thermogravimetric analysis shows that the polymer has high thermal stability, with a decomposition temperature greater than 250°C. At 250°C, the weight loss does not exceed 5%; at 300°C, the weight loss does not exceed 10%.

[0089] Example 4

[0090] In this example, the application of polymer in adsorption

[0091] The test method for polymer application in adsorption of vapor iodine is to calculate the adsorption amount by differential weight method:

[0092] A polymer (10 mg) was placed in a 5 mL beaker. 3 g of elemental iodine was weighed and placed in a 500 mL wide-mouth glass bottle, which was then placed inside the beaker. The bottle was then placed in an oven at 348.15 K. The oven was removed every 30 minutes to cool to room temperature, and the polymer mass in the beaker was weighed. After 210 minutes, the polymer mass remained essentially unchanged, and the maximum adsorption capacity of polymer 8 was 2.82 g g. -1 The maximum adsorption capacity of polymer 9 is 3.18 gg -1 See also Figure 4 .

[0093] Example 5

[0094] This embodiment is basically the same as the above embodiment, with the following special features:

[0095] In this embodiment, the polymer is used to test the adsorption of iodine in aqueous solution, and the adsorption efficiency is determined by the concentration method:

[0096] The polymer (2.5 mg) was added to a saturated iodine aqueous solution (2.5 mL, 1.2 mM) and stirred at room temperature. After a certain period of time, the solution was removed and filtered, and the residual iodine concentration in the solution was recorded by UV spectroscopy. After 6 minutes, the residual iodine concentration did not change. The maximum adsorption efficiency of polymer 8 was 95%, and the maximum adsorption efficiency of polymer 9 was 97.6%. Figure 5 and Figure 6 .

[0097] Example 6

[0098] This embodiment is basically the same as the above embodiment, with the following special features:

[0099] In this example, the polymer was used to test the adsorption of 1-naphthylamine in aqueous solution, and the adsorption efficiency was determined by the concentration method:

[0100] The polymer (2.5 mg) was added to a 1-naphthylamine solution (2.5 mL, 0.1 mM) and stirred at room temperature. After a certain period of time, the solution was removed and filtered, and the concentration of residual 1-naphthylamine in the solution was recorded by UV spectroscopy. After 120 minutes, the residual 1-naphthylamine concentration remained essentially unchanged. The maximum adsorption efficiency of polymer 8 was 98.02%, and the maximum adsorption efficiency of polymer 9 was 97.94%. Figure 7 and Figure 8 .

[0101] Example 7

[0102] This embodiment is basically the same as the above embodiment, with the following special features:

[0103] In this example, the polymer was used to test the adsorption of iodine in a flowing aqueous solution, and the adsorption efficiency was determined by the concentration method:

[0104] The polymer (10 mg) was filled into a 4 mm cross-sectional area 2 Saturated iodine aqueous solution (1.2 mM, 10 mL) was injected into the column at a rate of 1 to 10 mL min -1 The flow rate was eluted, and the eluate was collected. The adsorption efficiency of the polymer on the saturated iodine aqueous solution at different flow rates was obtained by the UV spectrum intensity. Among them, polymer 8 and polymer 9 had a flow rate of 2 mL min -1 The adsorption efficiencies of saturated iodine aqueous solution were 99.9% and 98.6% respectively, with a flow rate of 10 mL min-1 The adsorption efficiency of saturated iodine aqueous solution was 92.5% and 95.2% respectively. Figure 9 .

[0105] The above embodiments of the present invention are specifically a series of porous organic polymers based on a supramolecular macrocycle of calix[4]pyrrole connected by acetylenic bonds and imine bonds, and their preparation methods and applications. The porous polymers in the present invention are obtained by Sonogashira coupling reaction or Schiff base reaction of trans-disubstituted calix[4]pyrrole and a three-headed or four-headed rigid structural unit. This type of material contains a supramolecular macrocycle of calix[4]pyrrole, a cross-linked network structure and a rich pore structure, so that it has the characteristics of both supramolecular macrocycle and organic porous material, and can be used in the fields of selective adsorption and adsorption separation of gases, organic micropollutants and radioactive pollutants.

[0106] The above describes the embodiments of the present invention in conjunction with the accompanying drawings, but the present invention is not limited to the above embodiments. Various changes can be made according to the purpose of the invention. Any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principles of the technical solution of the present invention should be equivalent replacement methods. As long as they comply with the purpose of the invention and do not deviate from the technical principles and inventive concepts of the present invention, they belong to the scope of protection of the present invention.

Claims

1. A trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer, characterized by: A trans-disubstituted calix[4]pyrrole supramolecular macrocycle is used; calix[4]pyrrole is introduced as a structural unit into the rigid skeleton of a porous organic polymer to form a comonomer, so that the comonomer simultaneously contains the calix[4]pyrrole supramolecular chemical host and guest and the pore structure of the porous organic material. At the same time, the rigid porous skeleton structure exposes the calix[4]pyrrole and other active sites in the structure to form sites for interacting with guest molecules and adsorbing gas molecules and organic micropollutant molecules; The trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer has one of the following molecular structural formulas: In the structural formula, X is a carbon or nitrogen atom; Y represents a connection site; and alkyl chain is an alkyl chain.

2. The trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 1, characterized in that: The polymers (I) and (III) connected by alkyne bonds are prepared by Sonogashira coupling of trans-bis(4-iodophenyl)calix[4]pyrrole with a three-headed alkyne rigid structural unit A or a four-headed alkyne rigid structural unit B in the following structural formula; the polymers (II) and (IV) connected by imine bonds are prepared by Schiff base reaction of trans-bis(4-aminophenyl)calix[4]pyrrole with a three-headed aldehyde rigid structural unit C or a four-headed aldehyde rigid structural unit D in the following structural formula; in and As defined in claim 1.

3. The trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 2, characterized in that: Trans-bis(4-iodophenyl)calix[4]pyrrole is used, and trans-bis(4-iodophenyl)calix[4]pyrrole and a three-headed alkynyl rigid structural unit A are dissolved in anhydrous toluene and triethylamine in a molar ratio of 3:(2-3). Tetrakis(triphenylphosphine)palladium and cuprous iodide are used as catalysts. A Sonogashira coupling reaction is carried out under nitrogen protection. The obtained crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran and acetone, and then extracted with dichloromethane Soxhlet. The remaining solid is polymer (I).

4. The trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 2, characterized in that: Trans-bis(4-iodophenyl)calix[4]pyrrole is used, and trans-bis(4-iodophenyl)calix[4]pyrrole and a tetra-headed alkynyl rigid structural unit B are dissolved in anhydrous toluene and triethylamine in a molar ratio of 2:(1-2). Tetrakis(triphenylphosphine)palladium and cuprous iodide are used as catalysts to carry out a Sonogashira coupling reaction under nitrogen protection. The obtained crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran and acetone, and then extracted with dichloromethane Soxhlet. The remaining solid is polymer (III).

5. The trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 2, characterized in that: Trans-bis(4-aminophenyl)calix[4]pyrrole is used, and trans-bis(4-aminophenyl)calix[4]pyrrole and a three-headed aldehyde rigid structural unit C are dispersed in the ionic liquid 1-butyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide according to a molar ratio of 3:(2-3), and a Schiff base reaction is carried out. The obtained crude product is washed with acetone and ethanol, and the remaining solid is polymer (II).

6. The trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 2, characterized in that: Trans-bis(4-aminophenyl)calix[4]pyrrole is used, and trans-bis(4-aminophenyl)calix[4]pyrrole and a tetra-headed aldehyde rigid structural unit D are dispersed in the ionic liquid 1-butyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide according to a molar ratio of 2:(1-2), and a Schiff base reaction is carried out. The obtained crude product is washed with acetone and ethanol, and the remaining solid is polymer (IV).

7. A method for preparing a trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 1, characterized in that: Use any of the following methods: First method: Trans-bis(4-iodophenyl)calix[4]pyrrole is used, and trans-bis(4-iodophenyl)calix[4]pyrrole and a three-headed alkynyl rigid structural unit A or a four-headed alkynyl rigid structural unit B are dissolved in anhydrous toluene and triethylamine. Tetrakis(triphenylphosphine)palladium and cuprous iodide are used as catalysts. After cyclic freezing and deoxygenation for at least three times, a Sonogashira coupling reaction is carried out at a temperature not lower than 90° C. under nitrogen protection for at least 3 days. The reaction mixture is then cooled to room temperature, the solvent is removed by filtration, and the resulting crude product is washed with dichloromethane, dilute hydrochloric acid, tetrahydrofuran, and acetone, and then subjected to Soxhlet extraction with dichloromethane for at least 24 hours and dried to obtain a polymer (I) or a polymer (III). Dissolving trans-bis(4-iodophenyl)calix[4]pyrrole and a three-headed alkynyl rigid structural unit A in anhydrous toluene and triethylamine at a molar ratio of 3:(2-3); or dissolving trans-bis(4-iodophenyl)calix[4]pyrrole and a four-headed alkynyl rigid structural unit B in anhydrous toluene and triethylamine at a molar ratio of 2:(1-2); Second method: Trans-bis(4-aminophenyl)calix[4]pyrrole is used, and trans-bis(4-aminophenyl)calix[4]pyrrole and a three-headed aldehyde-based rigid structural unit C or a four-headed aldehyde-based rigid structural unit D are dispersed in the ionic liquid 1-butyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide, and the mixture is allowed to stand at room temperature for at least 3 minutes to carry out a Schiff base reaction. The resulting crude product is washed with acetone and ethanol to obtain a polymer (II) or a polymer (IV); Trans-bis(4-aminophenyl)calix[4]pyrrole and a three-headed aldehyde rigid structural unit C are dispersed in an ionic liquid at a molar ratio of 3:(2-3); or trans-bis(4-aminophenyl)calix[4]pyrrole and a four-headed aldehyde rigid structural unit D are dispersed in an ionic liquid at a molar ratio of 2:(1-2); In any of the above methods, the three-headed alkynyl rigid structural unit A or the three-headed aldehyde rigid structural unit C adopts any of the following structural formulas: In any of the above methods, the four-headed alkyne rigid structural unit B or the four-headed aldehyde rigid structural unit D adopts any of the following structural formulas: In the structural formula, Y in the three-headed alkynyl rigid structural unit A is an acetylenic bond group, Y in the three-headed aldehyde rigid structural unit C is an aldehyde group, Y in the four-headed alkynyl rigid structural unit B is an acetylenic bond group, and Y in the four-headed aldehyde rigid structural unit D is an aldehyde group; X is a carbon or nitrogen atom; alkyl chain is an alkyl chain.

8. An application of the trans-disubstituted calix[4]pyrrole-based supramolecular macrocyclic porous organic polymer according to claim 1, characterized in that: Used for selective adsorption and separation of small molecule gases, organic micropollutants, and radioactive pollutants.

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