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CN-121718023-B - Self-microporous degradable polymer material based on biomass and heterocalixarene, and preparation method and application thereof

CN121718023BCN 121718023 BCN121718023 BCN 121718023BCN-121718023-B

Abstract

The invention discloses a self-contained microporous degradable polymer material based on biomass and heterocalixarene, a preparation method and application thereof, wherein the method firstly takes cyanuric chloride and resorcinol as raw materials, adopts a one-pot method to synthesize oxygen atom bridged heterocalixarene macrocyclic molecules in one step under alkaline condition, and then introducing lignin derivatives into oxygen atom bridged heterocalixarene by utilizing aromatic nucleophilic substitution reaction on triazine ring in a macrocyclic molecule, so as to obtain condensation reaction of polyaldehyde-functionalized oxygen atom bridged heterocalixarene and polyfunctional mercaptan under acidic condition, and obtaining the target degradable polymer material. When in use, the material is directly put into aqueous solution of iodine simple substance, iodine anion and bivalent mercury ion for adsorption. The material has the removal rate of over 90 percent for low-concentration iodine simple substance, iodine negative ions and bivalent mercury ions, and the adsorbed material can be repeatedly used after being washed by acidic aqueous solution. The material can be degraded under alkaline conditions.

Inventors

  • LIU HANBIN
  • TAN FUWEN
  • DAI YUXUAN
  • ZENG ZHIYONG
  • ZHANG YUXUAN

Assignees

  • 湖南工程学院

Dates

Publication Date
20260508
Application Date
20260213

Claims (10)

  1. 1. A self-contained microporous degradable polymer material based on biomass and heterocalixarene is characterized in that the polymer material is a three-dimensional network polymer prepared by condensation reaction of multi-aldehyde-group functionalized oxygen atom bridged heterocalixarene and multi-functionality mercaptan, wherein the multi-aldehyde-group functionalized oxygen atom bridged heterocalixarene is prepared by nucleophilic substitution reaction of oxygen atom bridged heterocalixarene macrocyclic molecules and lignin-derived aldehyde-containing phenolic biomass raw materials.
  2. 2. The biomass and heterocalixarene-based self-microporous degradable polymeric material of claim 1 wherein the polyfunctional thiol is selected from one of 1, 4-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, 1, 8-octanedithiol, 1, 4-benzenedimethanethiol, bis (2-mercaptoethyl) ether, 3, 6-dioxo-1, 8-octanedithiol, diethylene glycol di (ethanethiol), dipentaerythritol hexa (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate).
  3. 3. The biomass and heterocalixarene-based self-microporous degradable polymeric material according to claim 1, wherein the oxygen atom bridged heterocalixarene macrocyclic molecule is oxacalixarene [2] triazine, which is synthesized from cyanuric chloride and resorcinol or its derivatives by one-pot reaction under alkaline conditions, the molar ratio of cyanuric chloride to resorcinol or its derivatives being 1:1-1.1.
  4. 4. The biomass and heterocalixarene-based self-microporous degradable polymer material according to claim 3, wherein the resorcinol derivative is resorcinol with nitro, ester or halogen substituents, and the catalyst is a basic catalyst selected from one of sodium hydroxide, potassium hydroxide, cesium carbonate or triethylamine.
  5. 5. The biomass and heterocalixarene-based self-microporous degradable polymer material according to claim 1, wherein the lignin-derived aldehyde-containing phenolic biomass material is at least one of 4-hydroxybenzaldehyde, vanillin or syringaldehyde in an amount of 1-4 times the amount of oxygen atom bridged heterocalixarene macrocyclic molecular species.
  6. 6. A method for the preparation of a biomass and heterocalixarene-based self-microporous degradable polymeric material according to any one of claims 1 to 5, comprising the steps of: s1, under the action of an alkaline catalyst, cyanuric chloride reacts with resorcinol or a derivative thereof through a one-pot method to synthesize oxygen atom bridged heterocalixarene; S2, carrying out nucleophilic substitution reaction on the oxygen atom bridged heterocalixarene obtained in the step S1 and an aldehyde group-containing phenolic biomass raw material derived from lignin under the action of a catalyst to obtain multi-aldehyde group functionalized oxygen atom bridged heterocalixarene; S3, carrying out condensation reaction on the multi-aldehyde-group functionalized oxygen atom bridged heterocalixarene and multi-functionality mercaptan under the condition of an acid catalyst to obtain the self-microporous degradable polymer material.
  7. 7. The preparation method of claim 6, wherein in the step S1, at least one of DMSO, DMF, tetrahydrofuran, 1, 4-dioxane, acetone or acetonitrile is adopted as the organic solvent, the solvent dosage is 20-50 times of the mass of cyanuric chloride, at least one of acetonitrile and acetone is adopted as the organic solvent in the step S2, the solvent dosage is 5-10 times of the mass of oxygen atom bridged heterocalixarene, and the catalyst is potassium carbonate or sodium hydroxide.
  8. 8. The preparation method of claim 6, wherein in the step S3, the acid catalyst is trifluoroacetic acid, the dosage of the acid catalyst is 0.5% -5% of the total mass of the reaction raw materials, dichloromethane is adopted as an organic solvent, the molar ratio of multi-aldehyde-functionalized oxygen atom bridged heterocalixarene to multi-functionality mercaptan is 1:1-4, the reaction temperature is 20-80 ℃, and the reaction time is 0.5-3 hours.
  9. 9. Use of the self-contained microporous degradable polymeric material of any one of claims 1 to 5 for adsorbing contaminants in a body of water.
  10. 10. The use according to claim 9, wherein the contaminant is at least one of elemental iodine, negative iodine ion or divalent mercury ion, the concentration of the contaminant is 50-100ppm when in use, the amount of the microporous degradable polymer material is 20-50mg/L, and the adsorption time is 30-60min.

Description

Self-microporous degradable polymer material based on biomass and heterocalixarene, and preparation method and application thereof Technical Field The invention relates to the field of advanced manufacturing materials and environmental treatment, in particular to a biomass and heterocalixarene-based self-contained microporous degradable polymer material, and a preparation method and application thereof. Background The pollutants such as iodine simple substance, iodine ions, mercury ions and the like in the industrial wastewater have great treatment difficulty due to environmental persistence, bioaccumulation and high toxicity. The existing treatment technology such as a coagulating sedimentation method mainly realizes pollutant removal through flocculation sedimentation, has a certain effect when treating wastewater with higher concentration, but obviously reduces the treatment efficiency of low-concentration pollutants with ppm level, and has the problems of large dosage of medicament, large sludge generation amount, poor selectivity and the like. Adsorption is another common technique, the effectiveness of which is highly dependent on the properties of the adsorbent material itself. The porous adsorption materials such as active carbon, molecular sieve and partial synthetic resin which are widely used at present mainly depend on physical adsorption, the adsorption mechanism of the porous adsorption materials generally lacks specificity, so that the selectivity of target pollutants is not high, meanwhile, the adsorption capacity of the porous adsorption materials is limited by the specific surface area and the pore channel structure, the adsorption balance is usually faster when the pollutants with low concentration are treated, but the saturated adsorption quantity is limited, and the deep purification is difficult to realize. In addition, after adsorption saturation, the regeneration process of the material is generally tedious and the efficiency is reduced, the adsorption performance is obviously reduced after multiple cycles, and finally, if the waste material is improperly treated, the environmental risk exists. Calixarene macrocyclic molecules, in particular to oxygen atom bridged heterocalixarene which is a derivative thereof, and has an inherent cavity structure and rich heteroatom (such as N, O) sites in the structure, so that the calixarene macrocyclic molecules endow the calixarene with unique molecular recognition and chelation capability for various guest molecules, and are ideal adsorption platforms in theory. However, when it is directly applied to water treatment as a separate small molecule adsorbent, there still remain the following problems: (1) The stability and separation problems are that the small molecular state is easy to run off in the water phase, the solid-liquid separation is difficult to realize, the operation is difficult, and new soluble organic pollutants can be introduced; (2) The adsorption capacity and the synergistic effect are limited, wherein adsorption sites of single molecules are limited, and a porous network structure with long-range order cannot be formed, so that the improvement of the density of the adsorption sites and the synergistic effect among the sites are limited; (3) The structure and the function are difficult to regulate, the chemical stability of small molecules and the density of functional groups are usually fixed, and different application scenes are difficult to adapt through physical form adjustment. Therefore, there is an urgent need to develop a functional material, which not only inherits the excellent recognition and chelating ability of calixarene molecules, but also has the characteristics of high specific surface area, easy recovery and good physicochemical stability of porous materials, so as to realize efficient and selective adsorption and recycling recovery of low-concentration pollutants. Disclosure of Invention Aiming at the technical problems, the invention provides a biomass and heterocalixarene-based self-contained microporous degradable polymer material, and a preparation method and application thereof. The invention adopts the technical scheme that: The self-contained microporous degradable polymer material based on biomass and heterocalixarene is a three-dimensional network polymer prepared by condensation reaction of multi-aldehyde-group functionalized oxygen atom bridged heterocalixarene and multi-functionality mercaptan, wherein the multi-aldehyde-group functionalized oxygen atom bridged heterocalixarene is prepared by nucleophilic substitution reaction of oxygen atom bridged heterocalixarene macrocyclic molecules and lignin-derived aldehyde-containing phenolic biomass raw materials. Further, the polyfunctional mercaptan is one selected from 1, 4-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, 1, 8-octanedithiol, 1, 4-benzenedimethylthiol, bis (2-mercaptoethyl) ether, 3, 6-dioxo-1, 8-octanedithi