CN-119708530-B - Supermolecular polymer porous material PTP3 and synthesis and application thereof

Abstract

The invention discloses a supermolecular polymer porous material PTP3, which is formed by crosslinking a terphenyl macrocycle with a large cavity as a base to form the supermolecular polymer porous material PTP3, and a complex polymer network structure is formed by a crosslinking mode, so that the terphenyl macrocycle TP3 with the large cavity is changed into the supermolecular polymer porous material PTP3 with larger specific surface area, and the binding capacity to dye molecules is improved. Because of the abundant cavities and the netlike structures of the polymer porous material, the two materials play a synergistic effect at the same time, so that the supermolecular polymer porous material PTP3 has a faster removal rate and smaller adsorbent dosage when absorbing and removing the multi-component dye in water. The invention provides a new thought for removing the dye in the aqueous solution.

Inventors

• YAO HONG
• SUN XIANGTING
• YU FEIYAN
• LI JIAHUI
• YANG MINKANG
• LIN QI
• WEI TAIBAO

Assignees

• 西北师范大学

Dates

Publication Date

20260508

Application Date

20250109

Claims (3)

1. 1. A supermolecular polymer porous material PTP3, which has the structural formula: R is H; The supermolecular polymer porous material PTP3 is prepared by the following method: (1) Synthesizing a compound TP, namely taking p-dibromobenzene and 2, 4-dimethoxyphenylboric acid as substrates, taking a1, 4-dioxane/water mixed solution as a solvent, adding sodium carbonate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 10-15 h at 100-105 ℃ under the protection of nitrogen, after the reaction is finished, spin-drying the 1, 4-dioxane at 60-70 ℃ and extracting with dichloroethane, concentrating the combined organic phases, and separating residues through column chromatography to obtain a white solid, namely the compound TP; (2) Synthesizing a compound TP3, namely, taking the compound TP and paraformaldehyde as substrates, taking 1, 2-dichloroethane as a solvent, slowly adding boron trifluoride diethyl ether, reacting for 1-3 hours at normal temperature, directly adding a reaction solution into a saturated sodium bicarbonate solution to quench after the reaction is finished, concentrating a combined organic phase by an extraction liquid, drying the concentrated organic phase by using anhydrous sodium sulfate, and carrying out column chromatography on residues to obtain a white solid, wherein the obtained product is the compound TP3; (3) The synthesis of the compound OH-TP3 comprises the steps of taking the compound TP3 as a substrate, taking methylene dichloride as a solvent, slowly adding boron tribromide, reacting for 45-50 hours at normal temperature, adding a reaction liquid into ice water by a suction pipe after the reaction is finished, separating out white solid, and carrying out suction filtration and flushing by methylene dichloride to obtain the compound OH-TP3; (4) The PTP3 is synthesized by taking a compound OH-TP3 as a substrate, taking 1, 2-dibromoethane as a cross-linking agent, taking acetonitrile as a solvent, adding triphenylphosphine, and reacting for 48 hours at 70-80 ℃ under the protection of nitrogen; in the step (1), the molar ratio of the p-dibromobenzene to the 2, 4-dimethoxy phenylboronic acid is 1:1-1:3; in the step (1), in the 1, 4-dioxane/water mixed solution, the volume ratio of the 1, 4-dioxane to the water is 3:1-5:1; In the step (1), the molar ratio of the p-dibromobenzene to the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 18:1-22:1, and the molar ratio of the p-dibromobenzene to the sodium carbonate is 1:1-1:3; In the step (2), the molar ratio of the compound TP to the paraformaldehyde is 1:1-1:2; In the step (3), the molar ratio of the compound TP3 to the boron tribromide is 1:45-1:50; In the step (4), the mol ratio of the compound OH-TP3 to the 1, 2-dibromoethane is 1:8-1:10, and the mol ratio of the compound OH-TP3 to the triphenylphosphine is 1:3-1:5.
2. 2. Use of a supramolecular polymeric porous material PTP3 according to claim 1 for the removal of dyes in water.
3. 3. The method for removing dye from water using a porous supramolecular polymer material PTP3 according to claim 2, wherein the porous supramolecular polymer material PTP3 is co-adsorbed with at least two of methyl green, rhodamine B, methyl orange, acid chrome blue K.

Description

Supermolecular polymer porous material PTP3 and synthesis and application thereof Technical Field The invention relates to a supermolecular polymer porous material PTP3, and also relates to synthesis of the supermolecular polymer porous material PTP3 and application of removing dye in water, belonging to the fields of chemical synthesis and wastewater treatment. Background Fresh water is one of the most important natural resources in the world. However, with the recent progress of modern technology, chemicals such as dyes, medicines, pesticides, etc. are being increased in global production and use. The dye is mostly an organic compound, has strong carcinogenic and mutagenic properties, and can cause adverse effects on water, aquatic organisms, human health and environment when being discharged at will. Common water purification technologies include electrochemistry, photochemistry, sonochemistry, etc., and adsorption is a simple and efficient water treatment technology, and is also widely used in the water treatment field. Therefore, the development of the functional material capable of effectively removing the organic dye in the water body has profound significance, and particularly has the advantages of good stability, strong circularity, high removal rate and the like, and has more advantages than the traditional adsorbent. Therefore, in order to improve the removal rate of the dye, the invention crosslinks the terphenyl macrocycle with a large cavity as a basis to form the supermolecular polymer porous material PTP3, the terphenyl macrocycle has a larger cavity and can accommodate larger dye molecules, and the electron-rich cavity of the terphenyl macrocycle has strong affinity to cations and electron-deficient neutral dyes, so that the supermolecular polymer based on the terphenyl macrocycle can improve the adsorption capacity of the supermolecular polymer to the dye. The supermolecular polymer porous material PTP3 has a large cavity rich in electrons and a network structure, and the combination capability of the supermolecular polymer porous material PTP3 to a target object can be further improved by utilizing the synergistic effect of the large cavity and the network structure. Therefore, the invention discloses synthesis of a supermolecular polymer porous material PTP3 based on a terphenyl macrocycle and cooperative adsorption of the supermolecular polymer porous material PTP3 on multicomponent dye molecules. Disclosure of Invention The invention aims to provide a supermolecular polymer porous material PTP3 based on a terphenyl macrocycle; another object of the present invention is to provide a method for synthesizing the above-mentioned supramolecular polymeric porous material PTP 3; It is also an object of the present invention to provide the use of the supramolecular polymeric porous material PTP3 for adsorption removal of dyes from water. 1. Supermolecular polymer porous material and its synthesis The structural formula of the supermolecular polymer porous material PTP3 is as follows: 。 The preparation method of the supermolecular polymer porous material PTP3 comprises the following steps: (1) The synthesis of the compound TP comprises the steps of taking p-dibromobenzene and 2, 4-dimethoxyphenylboric acid as substrates, taking a1, 4-dioxane/water mixed solution as a solvent, adding sodium carbonate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 10-15 hours at 100-105 ℃ under the protection of nitrogen, spinning the 1, 4-dioxane at 60-70 ℃ after the reaction is finished and extracting with dichloroethane, concentrating the combined organic phases, and separating residues through column chromatography to obtain white solids, namely the compound TP. The molar ratio of the p-dibromobenzene to the 2, 4-dimethoxyphenylboronic acid is 1:1-1:3 (preferably 1:2), and the volume ratio of the 1, 4-dioxane to the water in the 1, 4-dioxane/water mixed solution is 3:1-5:1 (preferably 4:1). The molar ratio of the p-dibromobenzene to the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is 18:1-22:1 (preferably 20:1), and the molar ratio of the p-dibromobenzene to the sodium carbonate is 1:1-1:3 (preferably 1:2). (2) The synthesis of the compound TP3 comprises the steps of taking the compound TP and paraformaldehyde as substrates, taking 1, 2-dichloroethane as a solvent, slowly adding boron trifluoride diethyl etherate, reacting for 1-3 hours at normal temperature, directly adding the reaction solution into saturated sodium bicarbonate solution for quenching after the reaction is finished, concentrating the combined organic phases through extraction and separation, drying the organic phases through anhydrous sodium sulfate, and carrying out column chromatography on residues to obtain white solid, wherein the obtained product is the compound TP3. Wherein the molar ratio of the compound TP to the paraformaldehyde is 1:1-1:2. (3) The method comprises the steps of s