CN113429534B - Preparation method of high-stability strong-basicity porous ion exchange material - Google Patents
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- CN113429534B CN113429534B CN202110760618.8A CN202110760618A CN113429534B CN 113429534 B CN113429534 B CN 113429534B CN 202110760618 A CN202110760618 A CN 202110760618A CN 113429534 B CN113429534 B CN 113429534B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/14—Dicyandiamides; Dicyandiamidines; Guanidines; Biguanidines; Biuret; Semicarbazides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
Abstract
The invention discloses a high-stability strong-basicity porous ion exchange material and a preparation method thereof, belonging to the technical field of high-molecular ion exchange materials. The invention uses triaminoguanidine salt and 2, 5-dimethoxy-1, 4-benzene dicarbaldehyde as reaction monomers to synthesize the high-stability strong-basicity porous ion exchange material in a reaction container in one step. The preparation method is simple and convenient, and the reaction monomers are cheap and easy to obtain. The infrared spectroscopy demonstrated that the polymerization reaction had occurred efficiently. Thermogravimetric analysis shows that the material of the invention has high thermal stability. Through testing the nitrogen adsorption and desorption curves of the material of the invention, the BET specific surface area of the material reaches 645.8m by calculation2g‑1. The XRD spectrogram and the nitrogen adsorption and desorption curve after the strong acid and strong base treatment prove that the material has high chemical stability and can be used as a good matrix material in severe environment. The high-stability strong-basicity porous ion exchange material is expected to be industrially popularized and applied in the fields of catalytic synthesis, water treatment, pollutant adsorption and the like.
Description
Technical Field
The invention belongs to the technical field of high-molecular ion exchange materials, and particularly relates to a preparation method of a high-stability strong-basicity porous ion exchange material.
Background
The ion exchange material is applied to the fields of water treatment, electric power industry, separation and purification of biological and chemical agents, catalytic synthesis and the like. Among them, the anion exchange resins are particularly widely used.
The anion exchange resin particles are formed by a cross-linked framework with a three-dimensional space network structure and are connected with a plurality of functional groups which are active and can not move freely. Such functional groups are capable of dissociating ions and can be exchanged with other ions of the same charge surrounding them during use or regeneration. The method has the advantages of large processing capacity, wide application range, long service life, low operating cost and the like, so that the method is widely applied to industrial production.
The traditional method for preparing anion exchange resin is mainly to perform chloromethylation on the copolymer and then obtain the anion exchange resin through amination reaction. However, reagents such as chloromethyl ether and dichloromethyl ether used in the chloromethylation process have strong carcinogenicity, and thus the method is limited to some extent. Moreover, the use temperature of common commercially available strongly basic anion exchange resins, particularly hydroxide anion exchange resins, is limited to below 60 ℃ due to the low thermal stability of the anion exchange resin, limiting the range of applications of strongly basic anion exchange resins. In recent years, scientists have attempted to modify the attachment of quaternary ammonium groups to the resin backbone to improve the thermal stability of the quaternary ammonium groups. However, this method does not fundamentally improve the thermal stability of the material. The preparation of these high temperature resistant strong basic anion exchange resins still has the disadvantages of long synthesis route, complex process, severe operating conditions, monomer separation, low yield, difficult purification, high production cost and the like, and is difficult to popularize and apply. Meanwhile, ion position inclusion is formed among polymer chains of the traditional ion exchange resin due to winding, so that the ion exchange capacity of the traditional ion exchange resin is influenced; and its lack of permanent channels results in slower adsorption rates.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a high-stability strong-basicity porous ion exchange material.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-stability strong-basicity porous ion exchange material is prepared from triaminoguanidine salt and 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde through reaction on alcohol or 1, 4-dioxane as solvent in the presence of acid as catalyst.
The invention relates to a high-stability strong-basicity porous ion exchange material, which is prepared by the following reaction equation:
the structural formula of the ion exchange material is shown as follows:
the polymerization reaction employed is an acid-catalyzed schiff base formation reaction.
The invention relates to a high-specific surface area, high-stability and strong-basicity porous ion exchange material which is prepared by the following steps:
(1) adding triaminoguanidine salt and aldehyde ligand into a reaction container, and then sequentially adding a reaction solvent and a catalyst into the container;
(2) carrying out ultrasonic treatment on the reaction liquid in the step (1) for 5-20 min to ensure that the solution is uniformly mixed, then carrying out freezing-vacuumizing-unfreezing operation in a nitrogen or argon atmosphere and under liquid nitrogen (77K), circulating for 2-5 times, and sealing the reaction container under a vacuum condition;
(3) reacting the sealed reaction container in the step (2) for 2-7 days at the temperature of 80-150 ℃;
(4) and (3) cooling the reaction container (with brown yellow precipitate at the bottom) to room temperature, opening, and carrying out vacuum filtration to obtain a red solid. Washing the red solid with DMF, water and absolute methanol for multiple times; and then Soxhlet extracting for several days by using methanol, and drying the extracted product for 4-40 hours at 80-200 ℃ in vacuum to obtain an orange solid.
(5) And (3) carrying out ion exchange on the solid obtained in the step (4) by using a 1-5M KOH solution (or other strong base solutions) for 1-10 days to obtain the high-stability strong-base porous ion exchange material.
Preferably, the molar ratio of triaminoguanidine salt: aldehyde group ligand ═ 2: 3.
preferably, the washing method comprises the following steps: after the obtained product is filtered, the product is washed 3-5 times by dimethylformamide (20-90 ℃), water (20-100 ℃) and methanol (20-50 ℃) in sequence.
Preferably, the purification method comprises the following steps: and (3) sequentially performing Soxhlet extraction on the washed substance with tetrahydrofuran, dichloromethane and methanol for 3-5 times.
Preferably, the triaminoguanidine salt is triaminoguanidine hydrochloride.
Tests show that the material obtained by the invention has good stability and porous property, can be stabilized at the temperature of nearly 200 ℃, has strong alkaline ions in pore channels, and has the BET specific surface area of 645.8m2(ii) in terms of/g. The material of the invention can be applied in a plurality of fields such as adsorption, separation, catalysis and the like.
Compared with the prior ion exchange resin, the invention has the beneficial effects that:
(1) compared with common commercial strong-base anion exchange resin, the material has high thermal stability and chemical stability. The use temperature of common commercial strong-base anion exchange resin, particularly hydroxide type anion exchange resin, is limited below 60 ℃, which limits the application range of the strong-base anion exchange resin. The material obtained by the invention can be used in a high-temperature environment of nearly 200 ℃, and meanwhile, the high acid-base stability enables the material to be used under various extreme conditions without affecting the performance of the product, so that the material can be recycled.
(3) Compared with common commercial strong-base anion exchange resin, the material disclosed by the invention is a porous material, has the advantages of high specific surface area, rapid pore channel mass transfer, high ion capacity and the like, and has better industrial application potential in the fields of catalysis, adsorption, separation, ion exchange and the like.
(2) It is worth mentioning that the invention adopts cheap monomers, is convenient to obtain, has simple reaction operation, can be obtained in one step, and has obvious economic advantages and industrial application potential.
Drawings
FIG. 1: the infrared spectrogram of the high-stability strong-basicity porous ion exchange material synthesized by the invention (curve 1 in the figure) is soaked and stirred with 12M sodium hydroxide for one week (curve 2 in the figure) and soaked and stirred with 12M hydrochloric acid for one week (curve 3 in the figure);
FIG. 2: the carbon solid nuclear magnetic map of the high-stability strong base porous ion exchange material synthesized by the invention;
FIG. 3: thermogram of the high-stability strong base porous ion exchange material synthesized by the invention;
FIG. 4: the powder diffraction spectrogram of the high-stability strong base porous ion exchange material synthesized by the method (curve 1 in the figure) is soaked and stirred with 12M sodium hydroxide for one week (curve 2 in the figure) and soaked and stirred with 12M hydrochloric acid for one week (curve 3 in the figure);
FIG. 5: the nitrogen adsorption-desorption isotherm of the high-stability strong base porous ion exchange material synthesized by the invention;
FIG. 6: the high-stability strong base porous ion exchange material synthesized by the invention is treated by 12M hydrochloric acid to obtain a nitrogen adsorption-desorption isotherm for one week;
FIG. 7: the high-stability strong base porous ion exchange material synthesized by the invention is treated by 12M sodium hydroxide to form a nitrogen adsorption-desorption isotherm for one week;
FIG. 8: the pore diameter distribution diagram of the high-stability strong base porous ion exchange material synthesized by the invention;
Detailed Description
The present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1
First, 14.8mg (0.1mmol) of triaminoguanidine hydrochloride and 29.1mg (0.15mmol) of 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde were added to a 10mL ampoule; then, 0.2mL of trimethylbenzene, 0.2mL of water, 0.3mL of ethanol and 0.2mL of glacial acetic acid are sequentially added into the ampoule; carrying out ultrasonic treatment on the mixed solution for 10 min; freezing, vacuumizing and unfreezing under argon atmosphere and liquid nitrogen, and sealing the ampoule under vacuum after circulating for three times; the sealed ampoule was placed in a 120 ℃ oven for 3 days. The mixture was vacuum filtered to give a red solid, which was washed several times with dimethylformamide, water, and methanol in that order. Then the solid powder is subjected to Soxhlet extraction, the obtained product is subjected to vacuum drying at 120 ℃ for 12 hours, then is subjected to ion exchange for 4 days by using KOH or other alkaline solutions, and the product is obtained after washing.
FIG. 1 shows the comparison of the infrared spectra of the highly stable strong basic porous ion exchange material of the present invention and 12M acid-base for one week, 1620cm-1The peak at the position is a characteristic absorption peak of-C-N-generated by Schiff base reaction, and no reaction monomer-NH is contained in the figure2and-CHO characteristic absorption peaks, demonstrating that the polymerization reaction is very complete. And the infrared spectrogram has no change after acid-base treatment for one week, which proves that the product has high acid-base stability.
FIG. 2 shows a nuclear magnetic diagram of a carbon solid of the highly stable strongly basic porous ion exchange material of the present invention, wherein the-CHO carbon peak in 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde is 190ppm, however, no carbon peak appears at 190ppm in the material of the present invention, which proves that the polymerization reaction is complete.
FIG. 3 is a thermogravimetric graph of the highly stable strong base porous ion exchange material of the present invention, wherein thermogravimetric analysis shows that the material of the present invention has a thermal decomposition temperature of about 200 ℃ and high stability.
FIG. 4 shows that the diffraction patterns of the highly stable strongly basic porous ion exchange material and the powder treated with 12M acid and base for one week have distinct diffraction peaks, and the diffraction peaks do not change significantly after the acid and base treatment for one week.
FIG. 8 is a diagram showing the distribution of pore size of the highly stable strong base porous ion exchange material of the present invention, wherein the main pore size of the material of the present invention is at 0.661 nm.
Example 2
The reaction solvent in example 1 was changed to 1, 4-dioxane in example 2, and the rest was not
Alternatively, the same materials as described in example 1 were obtained, and the properties of the product obtained in example 1 were substantially the same.
In conclusion, the invention synthesizes the high-stability strong-basicity porous ion exchange material by taking triaminoguanidine salt and 2, 5-dimethoxy-1, 4-benzene dicarbaldehyde as reaction monomers under the catalysis of acid. Thermogravimetric analysis shows that the material of the invention has good thermal stability. According to a nitrogen adsorption and desorption curve, the BET specific surface area of the material reaches 645.8m2(ii) in terms of/g. The product which is soaked in acid and alkali and stirred for one week is tested by a powder diffractometer, and the material disclosed by the invention is found to have extremely high acid and alkali stability.
FIG. 5 shows the nitrogen adsorption-desorption isotherm of the highly stable strong base porous ion exchange material of the present invention, which was calculated to obtain a BET specific surface area of 645.8m2/g。
FIG. 6 shows the nitrogen adsorption-desorption isotherm of the highly stable strong base porous ion exchange material synthesized by the present invention after being treated with 12M hydrochloric acid for one week, and the BET specific surface area of the material is calculated to be 454.4M2/g。
FIG. 7 shows the nitrogen adsorption-desorption isotherm of the highly stable strongly basic porous ion exchange material synthesized by the present invention after being treated with 12M sodium hydroxide for one week, and the BET specific surface area of the material obtained by calculation is 310.5M2/g。
From the above, it will be apparent to those skilled in the art that other various changes and modifications may be made based on the technical solution and concept of the present invention, and all such changes and modifications are within the scope of the appended claims.
Claims (7)
1. A high-stability strong-basicity porous ion exchange material is characterized in that: the structural formula is as follows:
2. the method for preparing highly stable strongly basic porous ion exchange material according to claim 1, comprising the steps of: adding triaminoguanidine salt, 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde, a reaction solvent and a catalyst into an ampoule, ultrasonically mixing the mixed solution uniformly, then performing freezing-vacuumizing-unfreezing operation in nitrogen or argon atmosphere and liquid nitrogen, circulating for three times, sealing the ampoule under a vacuum condition, placing the sealed ampoule in an oven for heating reaction, reacting for 2-7 days at 80-150 ℃, and filtering, washing, ion exchanging and vacuum drying the obtained product to obtain a target product.
3. The method for preparing highly stable strongly basic porous ion exchange material according to claim 2, wherein the washing method comprises: and after the obtained product is subjected to suction filtration, sequentially washing the product with dimethylformamide at the temperature of 20-90 ℃, water at the temperature of 20-100 ℃ and methanol at the temperature of 20-50 ℃ for 3-5 times respectively.
4. The method for preparing a highly stable strongly basic porous ion exchange material according to claim 2, wherein the molar ratio of triaminoguanidine salt: 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde ═ 1: (1-10).
5. The method for preparing highly stable strongly basic porous ion exchange material according to claim 2, wherein the ion exchange method is: ion exchange is carried out for 1-10 days by using 1-5M KOH solution or NaOH solution.
6. The method of preparing a highly stable, strongly basic, porous ion exchange material according to claim 2, wherein the reaction solvent comprises: one or more of water, ethanol, trimethylbenzene, 1, 4-dioxane and N-methylpyrrolidone.
7. The method of preparing a highly stable, strongly basic, porous ion exchange material according to claim 2, wherein the catalyst comprises: one or more of glacial acetic acid, hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid.
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| CN107126937A (en) * | 2017-05-09 | 2017-09-05 | 安徽皖东化工有限公司 | A kind of preparation technology of high-adsorption-capacity strong-base anion-exchange resin |
| CN108855012A (en) * | 2018-07-19 | 2018-11-23 | 吉林大学 | A kind of polyarylether class covalent organic framework material and preparation method thereof |
| CN108970584A (en) * | 2018-07-16 | 2018-12-11 | 南开大学 | A kind of preparation method for the covalent organic nano piece of cation removing radioactivity anionic pollutant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107126937A (en) * | 2017-05-09 | 2017-09-05 | 安徽皖东化工有限公司 | A kind of preparation technology of high-adsorption-capacity strong-base anion-exchange resin |
| CN108970584A (en) * | 2018-07-16 | 2018-12-11 | 南开大学 | A kind of preparation method for the covalent organic nano piece of cation removing radioactivity anionic pollutant |
| CN108855012A (en) * | 2018-07-19 | 2018-11-23 | 吉林大学 | A kind of polyarylether class covalent organic framework material and preparation method thereof |
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