Supramolecular polymer porous material ptp3 and synthesis and application thereof

Abstract

The application discloses a supramolecular polymer porous material PTP3, which is formed by cross-linking a triphenyl macrocycle with a large cavity to form a supramolecular polymer porous material PTP3, and the complex polymer network structure is formed by the cross-linking mode, so that the triphenyl macrocycle TP3 with a large cavity becomes the supramolecular polymer porous material PTP3 with a larger specific surface area, and the combination capacity for dye molecules is improved. Due to the rich cavity and network structure of the polymer porous material, the supramolecular polymer porous material PTP3 has a faster removal rate and a smaller adsorbent dosage when adsorbing and removing multi-component dyes in water. The application provides a new idea for a new supramolecular adsorbent for removing dyes in a water solution.

Description

Technical Field

[0001] This invention relates to a supramolecular polymer porous material PTP3, and also to the synthesis of supramolecular polymer porous material PTP3 and its application in removing dyes from water, belonging to the fields of chemical synthesis and wastewater treatment. Background Technology

[0002] Freshwater is one of the world's most important natural resources. However, in recent years, with the continuous advancement of modern technology, the global production and use of chemicals, such as dyes, pharmaceuticals, and pesticides, has increased. Most dyes are organic compounds with strong carcinogenic and mutagenic properties; their indiscriminate discharge can have adverse effects on water bodies, aquatic organisms, human health, and the environment. Common water purification technologies include electrochemical, photochemical, and sonochemical methods, while adsorption, as a simple and efficient water treatment technology, is also widely used in the field. Therefore, developing functional materials that can effectively remove organic dyes from water is of profound significance, especially supramolecular polymer materials with advantages such as good stability, strong recyclability, and high removal rates, which offer more advantages than traditional adsorbents.

[0003] Therefore, to improve the dye removal rate, this invention crosslinks a terphenyl macrocycle with large cavities to form a supramolecular polymer porous material PTP3. The terphenyl macrocycle has even larger cavities, capable of accommodating larger dye molecules, and the electron-rich cavities of the terphenyl macrocycle exhibit strong affinity for both cationic and electron-deficient neutral dyes. Thus, the supramolecular polymer based on the terphenyl macrocycle can enhance its dye adsorption capacity. Furthermore, this supramolecular polymer porous material PTP3 possesses both electron-rich large cavities and a network structure; the synergistic effect between these two aspects further enhances its binding capacity to target dyes. Therefore, this invention discloses the synthesis of a supramolecular polymer porous material PTP3 based on a terphenyl macrocycle and its synergistic adsorption of multi-component dye molecules. Summary of the Invention

[0004] The purpose of this invention is to provide a supramolecular polymer porous material PTP3 based on a terphenyl macrocycle;

[0005] Another object of the present invention is to provide a method for synthesizing the above-mentioned supramolecular polymer porous material PTP3;

[0006] Another objective of this invention is to provide an application of the supramolecular polymer porous material PTP3 for the adsorption and removal of dyes from water.

[0007] I. Supramolecular polymer porous materials and their synthesis

[0008] The structural formula of the supramolecular polymer porous material PTP3 is:

[0009] .

[0010] The present invention discloses a method for preparing the supramolecular polymer porous material PTP3, comprising the following steps:

[0011] (1) Synthesis of compound TP: Using p-dibromobenzene and 2,4-dimethoxyphenylboronic acid as substrates, and a 1,4-dioxane / water mixture as solvent, sodium carbonate and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added, and the reaction was carried out at 100-105℃ for 10-15 h under nitrogen protection. After the reaction was completed, 1,4-dioxane was evaporated to dryness at 60-70℃ and extracted with dichloroethane. The combined organic phases were concentrated, and the residue was separated by column chromatography to obtain a white solid, which is compound TP. The molar ratio of p-dibromobenzene to 2,4-dimethoxyphenylboronic acid was 1:1 to 1:3 (preferably 1:2); the volume ratio of 1,4-dioxane to water in the 1,4-dioxane / water mixture was 3:1 to 5:1 (preferably 4:1). The molar ratio of p-dibromobenzene to [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 18:1 to 22:1 (preferably 20:1); the molar ratio of p-dibromobenzene to sodium carbonate is 1:1 to 1:3 (preferably 1:2).

[0012] (2) Synthesis of compound TP3: Using compound TP and paraformaldehyde as substrates, and 1,2-dichloroethane as solvent, boron trifluoride diethyl ether was slowly added and the reaction was carried out at room temperature for 1-3 hours. After the reaction was completed, the reaction solution was directly quenched in a saturated sodium bicarbonate solution. The combined organic phases were concentrated by extraction and drying with anhydrous sodium sulfate. The residue was subjected to column chromatography to obtain a white solid, which was compound TP3. The molar ratio of compound TP to paraformaldehyde was 1:1 to 1:2.

[0013] (3) Synthesis of compound OH-TP3: Using compound TP3 as substrate and dichloromethane as solvent, boron tribromide was slowly added and reacted at room temperature for 45-50 h. After the reaction was completed, the reaction solution was added to ice water with a pipette, and a white solid was precipitated. The solid was filtered and washed with dichloromethane to obtain compound OH-TP3.

[0014] The molar ratio of compound TP3 to boron tribromide is 1:45 to 1:50 (preferably 1:48).

[0015] (4) Synthesis of compound PTP3: Using compound OH-TP3 as a substrate, 1,2-dibromoethane as a crosslinking agent, acetonitrile as a solvent, and triphenylphosphine, the reaction was carried out at 70-80℃ for 48 h under nitrogen protection. After the reaction was completed, an orange-red solid precipitated. The solid was filtered and washed with water and methanol. The product obtained was compound PTP3. The molar ratio of compound OH-TP3 to 1,2-dibromoethane was 1:8 to 1:10 (preferably 1:9); the molar ratio of compound OH-TP3 to triphenylphosphine was 1:3 to 1:5 (preferably 1:4).

[0016] The supramolecular polymer porous material prepared above is labeled as PTP3, and its synthetic route is as follows:

[0017] .

[0018] The infrared spectra and high-temperature gel permeation chromatograms of compounds OH-TP3 and PTP3 are shown below. Figure 1 and Figure 2 By comparing the FT-IR spectra of PTP3 and its raw material OH-TP3 ( Figure 1 It can be seen that: at 1300 and 699cm respectively −1 The presence of characteristic stretching vibration peaks of Ph−O−C and C−Br nearby indicates that the crosslinking reaction proceeded successfully, and compound PTP3 was successfully synthesized. Furthermore, the molecular weight of PTP3 was determined to be approximately 10 by high-temperature gel permeation chromatography. 6 The molecular weight of PTP3 was approximately 1000 times greater than that of its raw material OH-TP3, demonstrating the successful polymerization of PTP3.

[0019] The nitrogen adsorption-desorption curve of compound OH-TP3 is shown in the figure. Figure 3 The nitrogen adsorption-desorption curve of compound PTP3 is shown in the figure. Figure 4 The specific surface areas of the raw material OH-TP3 and the polymer PTP3 were measured by N2 adsorption-desorption experiments at 77 K, which were 20.4100 and 46142.4821 m², respectively. 2 ·g −1 The specific surface area of ​​polymer PTP3 is about twice that of the raw material, which shows that the polymer network structure increases the specific surface area of ​​polymer PTP3.

[0020] II. Application of PTP3, a supramolecular polymer porous material, in the removal of dyes from water.

[0021] 1. Performance of supramolecular polymer porous material PTP3 in removing dyes from water

[0022] The supramolecular polymer porous material PTP3 is insoluble in common solutions such as dimethyl sulfoxide, water, dichloromethane, petroleum ether, methanol, and ethanol, and therefore can be used to remove dyes from water. We selected typical anionic and cationic dyes, methyl green (MG), rhodamine B (RhB), methyl orange (MO), and acid chrome blue K (AK), with the following structural formulas: Figure 5 Subsequently, adsorption experiments were conducted on anionic and cationic dyes. Studies on the performance of supramolecular polymer porous material PTP3 in removing dyes from water showed that PTP3 has a synergistic effect in the adsorption and removal of multi-component dyes, and can remove dyes more quickly than single-component dyes. Figure 6 ).

[0023] Inspired by the synergistic effect of supramolecular polymer porous material PTP3 in the adsorption and removal of multi-component dyes, we verified this synergistic effect from another perspective. We tested the adsorbent dosage for typical cationic dyes methyl green, rhodamine B, and their mixtures. Using the controlled variable method, the results showed that 0.3 mg of supramolecular polymer porous material PTP3 was required to adsorb the same amount of methyl green; 0.3 mg of supramolecular polymer porous material PTP3 was also required to adsorb the same amount of rhodamine B; while only 0.2 mg of supramolecular polymer porous material PTP3 was needed to adsorb the same amount of methyl green and rhodamine B mixture. Figure 7 From the perspective of adsorbent dosage, we have once again demonstrated that the supramolecular polymer porous material PTP3 has a synergistic effect on the adsorption and removal of multi-component dyes.

[0024] 2. Recycling of supramolecular polymer porous material PTP3

[0025] The reusability and recyclability of adsorbents are also important factors in evaluating their adsorption capacity. Using Rhodamine B as a model pollutant, used supramolecular polymer porous material PTP3 was soaked in a hydrochloric acid / ethanol mixture as a solvent, followed by centrifugation, washing, and freeze-drying to achieve desorption. The desorption process is simple and... Figure 8 As shown, the UV-Vis spectrum of the supramolecular polymer porous material PTP3 for Rhodamine B was almost identical in each cycle, and the removal rate did not change significantly after five cycles, indicating that the supramolecular polymer porous material PTP3 has good reusability and recyclability. Furthermore, Figure 8 The UV-Vis spectrum of the supramolecular polymer porous material PTP3 after five cycles showed no significant change compared to the original adsorbent, further demonstrating the stability of the supramolecular polymer porous material PTP3 in repeated use experiments.

[0026] In summary, this invention uses a terphenyl macrocycle with rich electrons and large cavities as a base to crosslink and form a supramolecular polymer porous material PTP3. Through crosslinking, a complex polymer network structure is formed, transforming the already large-cavity terphenyl macrocycle TP3 into a supramolecular polymer porous material with an even larger specific surface area, thereby improving its binding capacity for dye molecules. Due to the abundant cavities and network structure of this polymer porous material, both work synergistically, resulting in a faster removal rate and a smaller adsorbent dosage when adsorbing and removing multi-component dyes from water. This invention provides a novel approach for the removal of dyes from aqueous solutions using new supramolecular adsorbents. Attached Figure Description

[0027] Figure 1 Infrared spectra of supramolecular polymer porous material PTP3 and compound OH-TP3;

[0028] Figure 2 Gel permeation chromatogram of supramolecular polymer porous material PTP3 and compound OH-TP3;

[0029] Figure 3 The nitrogen adsorption-desorption curve of compound TP3 is shown.

[0030] Figure 4 This is a nitrogen adsorption-desorption curve of PTP3, the supramolecular polymer porous material of this invention;

[0031] Figure 5 This is a schematic diagram of the dye structure adsorbed by the supramolecular polymer porous material PTP3 of the present invention;

[0032] Figure 6 This is a comparison chart showing the rate at which the supramolecular polymer porous material PTP3 adsorbs dyes according to the present invention.

[0033] Figure 7 This is a comparison chart of adsorbent dosage for the supramolecular polymer porous material PTP3 of the present invention;

[0034] Figure 8 This diagram illustrates the recycling of PTP3, the supramolecular polymer porous material of this invention. Detailed Implementation

[0035] The following specific examples further illustrate the synthesis of the supramolecular polymer porous material PTP3 of the present invention and its application in adsorbing dyes in water.

[0036] Example 1: Synthesis of supramolecular polymer porous material PTP3

[0037] (1) Synthesis of compound TP: p-Dibromobenzene (2.36 g, 10 mmol) and 2,4-dimethoxyphenylboronic acid (3.64 g, 20 mmol) were dissolved in 25 mL of solvent (water:1,4-dioxane = 1:4, V:V) and the catalyst [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.366 g, 0.5 mmol) was added. Then, sodium carbonate (2.12 g, 20 mmol) was added while stirring, and the reaction was carried out at 101 °C for 12 h under anaerobic conditions. After the reaction was completed, 1,4-dioxane was evaporated to dryness at 65 °C, and then water was added for lysis and extracted with dichloromethane until no product was found in the upper aqueous phase. Then, anhydrous sodium sulfate was added to the obtained organic phase for drying and vacuum concentration. The white solid obtained by column chromatography was compound TP (2.73 g). Yield: 78%; Melting point: 165~170 ℃.

[0038] (2) Synthesis of compound TP3: Compound TP (1 g, 2.85 mmol) and paraformaldehyde (107 mg, 3.567 mmol) were dissolved in 100 mL of 1,2-dichloroethane. The mixture was stirred at room temperature, and boron trifluoride diethyl ether (500 µL) was slowly added. The reaction was carried out for 2 h until the reactants were completely reacted. After the reaction was complete, the reaction solution was directly added to a saturated sodium bicarbonate solution to quench the reaction. The solution was then separated and dried over anhydrous sodium sulfate. The resulting solution was concentrated under vacuum. The white solid obtained by column chromatography was compound TP3 (0.72 g). Yield: 70%; Melting point: 254~260℃.

[0039] (3) Synthesis of compound OH-TP3: Compound TP3 (0.272 g, 0.25 mmol) was dissolved in 50 mL of dichloromethane, stirred at room temperature, and 1.13 mL (12 mmol) of boron tribromide was slowly added. After the reaction was sealed for 48 h, the resulting reaction solution was added to an appropriate amount of ice water bath with a pipette to obtain a white solid. Then, the solution was filtered and washed with dichloromethane to obtain compound OH-TP3.

[0040] (4) Synthesis of compound PTP3: Compound OH-TP3 (0.36 g, 0.4 mmol), 1,2-dibromoethane (0.35 mL, 3.6 mmol), and triphenylphosphine (0.43 g, 1.6 mmol) were dissolved in a double-necked flask containing 60 mL of acetonitrile and reacted at 75 °C for 48 h under a N2 atmosphere. After the reaction was completed, the precipitate was collected by suction filtration, washed with water and methanol, dried, and weighed to obtain 60 mg of orange-red solid, which was compound PTP3.

[0041] Example 2: Adsorption and removal of dyes from water using supramolecular polymer porous material PTP3

[0042] 1 mg of supramolecular polymer porous material PTP3 was added to four centrifuge tubes, along with 3 mL of aqueous solutions of methyl green, rhodamine B, methyl orange, and acid chrome blue K, respectively. The centrifuge tubes were then fixed and stirred on a magnetic stirrer. The absorbance of the dyes was measured by UV spectrophotometry at regular time intervals. It was visually apparent that the color of the dye solution gradually faded over time; the UV spectrum also showed a decreasing trend in the absorbance of the dye molecules over time. Next, 1.5 mL of aqueous solutions of the two dyes were added to the centrifuge tubes containing 1 mg of supramolecular polymer porous material PTP3. The absorbance of the dyes was again measured by UV spectrophotometry at regular time intervals. The results were consistent with those for single-component dye adsorption and removal, and the supramolecular polymer porous material PTP3 showed a faster rate of adsorption and removal of multi-component dyes. To further investigate the adsorption and removal performance of the supramolecular polymer porous material PTP3 on multi-component dyes, we selected methyl green and rhodamine B as pollution models. Comparative analysis of the adsorption of methyl green, rhodamine B, and a mixture of methyl green and rhodamine B by PTP3 showed that 0.2 mg of PTP3 was sufficient to remove the mixture of methyl green and rhodamine B from aqueous solution, while 0.3 mg was required for either methyl green or rhodamine B alone. Based on these results, we believe that the cavity and network structure of the supramolecular polymer porous material PTP3 achieve a synergistic effect in the adsorption and removal of mixed dye solutions, promoting the adsorption and removal of dye molecules.

Claims

1. A supramolecular polymer porous material PTP3, the structural formula of which is: R is H; The supramolecular polymer porous material PTP3 is prepared by the following method: (1) Synthesis of compound TP: p-Dibromobenzene and 2,4-dimethoxyphenylboronic acid were used as substrates, and a mixture of 1,4-dioxane / water was used as solvent. Sodium carbonate and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added and reacted at 100-105℃ for 10-15 h under nitrogen protection. After the reaction was completed, 1,4-dioxane was evaporated to dryness at 60-70℃ and extracted with dichloroethane. The combined organic phases were concentrated, and the residue was separated by column chromatography to obtain a white solid, which was compound TP. (2) Synthesis of compound TP3: Using compound TP and paraformaldehyde as substrates, 1,2-dichloroethane as solvent, boron trifluoride diethyl ether was slowly added and the reaction was carried out at room temperature for 1-3 h. After the reaction was completed, the reaction solution was directly added to saturated sodium bicarbonate solution for quenching. The combined organic phases were concentrated by extraction and drying with anhydrous sodium sulfate. The residue was subjected to column chromatography to obtain a white solid, and the product obtained was compound TP3. (3) Synthesis of compound OH-TP3: Using compound TP3 as substrate and dichloromethane as solvent, boron tribromide was slowly added and reacted at room temperature for 45-50 h; after the reaction was completed, the reaction solution was added to ice water with a pipette, and a white solid was precipitated. The solid was filtered and washed with dichloromethane to obtain compound OH-TP3. (4) Synthesis of PTP3: Using compound OH-TP3 as substrate, 1,2-dibromoethane as crosslinking agent, acetonitrile as solvent, triphenylphosphine was added and reacted at 70~80℃ for 48h under nitrogen protection; after the reaction was completed, an orange-red solid was precipitated, filtered and washed with water and methanol, and the product obtained was PTP3. In step (1), the molar ratio of p-dibromobenzene and 2,4-dimethoxyphenylboronic acid is 1:1 to 1:3; In step (1), the volume ratio of 1,4-dioxane to water in the 1,4-dioxane / water mixture is 3:1 to 5:

1. In step (1), the molar ratio of p-dibromobenzene to [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 18:1 to 22:1; the molar ratio of p-dibromobenzene to sodium carbonate is 1:1 to 1:

3. In step (2), the molar ratio of compound TP to paraformaldehyde is 1:1 to 1:2; In step (3), the molar ratio of compound TP3 to boron tribromide is 1:45~1:50; In step (4), the molar ratio of compound OH-TP3 to 1,2-dibromoethane is 1:8 to 1:10; the molar ratio of compound OH-TP3 to triphenylphosphine is 1:3 to 1:

5.

2. The application of the supramolecular polymer porous material PTP3 according to claim 1 in the removal of dyes from water.

3. The application of the supramolecular polymer porous material PTP3 according to claim 2 in the removal of dyes from water, characterized in that: The supramolecular polymer porous material PTP3 synergistically adsorbs at least two of methyl green, rhodamine B, methyl orange, and acid chrome blue K.

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