CN111085179A - Application of sulfur-containing polyimide resin as silver adsorbent - Google Patents
Application of sulfur-containing polyimide resin as silver adsorbent Download PDFInfo
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Abstract
The invention discloses an application of sulfur-containing polyimide resin as a silver adsorbent, wherein the sulfur-containing polyimide resin is a random sulfur-containing polyimide resin or a block sulfur-containing polyimide resin, the structural formula of the random sulfur-containing polyimide resin is shown as a formula I, and the structural formula of the block sulfur-containing polyimide resin is shown as a formula II. The sulfur-containing polyimide resin particles can also be prepared into a film type adsorbent, so that the use is convenient. The adsorption process of silver is simple, the operation is convenient, the adsorbent has specific adsorption to silver elements, and meanwhile, the adsorption process is not interfered by common elements such as potassium, sodium, calcium, magnesium, iron, zinc, copper, cadmium and the like. The adsorbent provided by the invention can be used in strong acidThe resin can be normally used in a high-temperature and high-pressure environment, and the resin material can be regenerated through a simple desorption process, so that the resin is economic and environment-friendly.
Description
Technical Field
The invention relates to an application of sulfur-containing polyimide resin as a silver adsorbent.
Background
Silver, as a precious metal, is a precious natural resource, has high physical and chemical stability, is easy to cut, and is often used as precious jewelry and currency. In modern industry, because of its good properties such as ductility, conductivity, corrosion resistance, oxidation resistance and catalytic activity, it is widely used in chemical industry, light industry, aviation, military industry, medicine and environmental protection.
However, silver is present in the earth's crust in very small amounts, and resources are extremely scarce relative to the increasing demand. At present, the precious metal metallurgical industry mainly adopts a hydrometallurgical process, the operation is simple, the production cost is low, but the problems of low precious metal concentration, multiple impurity metal types, high concentration and the like in a leaching solution exist.
The methods for enriching and separating noble metals mainly comprise a metal replacement method, an activated carbon adsorption method, a resin adsorption method and an extraction method, wherein the metal replacement method is gradually replaced by activated carbon due to higher cost. Activated carbon has the characteristics of economy and high efficiency, but with the development and progress of the process, a resin method with simple regeneration process and strong selectivity is gradually replacing the activated carbon method. The chelate resin has the advantages of large adsorption capacity, easy elution, less interference and good stability, can be combined with different extraction devices, is used for the enrichment and separation of noble metals, and is the first choice at present.
Most of the currently used noble metal adsorption chelating resins are prepared by high molecular reaction on polystyrene, polyacrylonitrile and other high molecular frameworks, and have general temperature resistance. Meanwhile, the enrichment and adsorption of noble metals are generally carried out by adopting a particle structure, and the post-treatment is more complex.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the sulfur-containing polyimide resin material with high temperature resistance, organic solvent resistance and strong acid resistance is prepared by utilizing a polyimide framework structure, is used for selectively adsorbing silver ions, and simultaneously provides two resin forms of particles and films. Furthermore, an elution technique is provided, thereby realizing the recycling of the resin material.
The technical scheme adopted by the invention is as follows:
an application of sulfur-containing polyimide resin as a silver adsorbent, wherein the sulfur-containing polyimide resin is a random sulfur-containing polyimide resin or a block sulfur-containing polyimide resin, the structural formula of the random sulfur-containing polyimide resin is shown as a formula I, the structural formula of the block sulfur-containing polyimide resin is shown as a formula II,
wherein m, n and x are integers of 1-1000 respectively.
The sulfur-containing polyimide resin is sulfur-containing polyimide resin particles or a sulfur-containing polyimide resin film, and the sulfur-containing polyimide resin film is prepared by film-forming of the sulfur-containing polyimide resin particles.
Further, the sulfur-containing polyimide resin film comprises a random sulfur-containing polyimide resin film or a block sulfur-containing polyimide resin film, and is prepared from random sulfur-containing polyimide resin particles or block sulfur-containing polyimide resin particles respectively.
Further, the Synthesis method of the sulfur-containing polyimide resin particles, i.e., the random-type sulfur-containing polyimide resin particles or the block-type sulfur-containing polyimide resin particles, has been disclosed in Chen, g., Pei, X, Wei, h, Xu, l.and Fang, X (2015), Synthesis and purification of sulfonated block-synthesized from 4,4' -sulfonic-bis (naphthalene anhydride) for proto-on exchange membranes, j.appl.polymer.sci., 132,41501.
Specifically, the random type sulfur-containing polyimide resin particles or block type sulfur-containing polyimide resin particles can be prepared by the following method:
the random type sulfur-containing polyimide resin particles are prepared by the following method: under the protection of nitrogen, 2 ' -di (sulfonic group) -4, 4' -diaminodiphenyl ether, triethylamine and m-cresol are mixed, stirred to completely dissolve 2,2 ' -di (sulfonic group) -4, 4' -diaminodiphenyl ether, then 4,4' -diaminodiphenyl ether, thioether naphthalene dianhydride and benzoic acid are added, the mixture is stirred for 30 minutes at room temperature, then heated to 80 ℃ for reaction for 4 hours, then heated to 180 ℃ for reaction for 18 hours, cooled to 80 ℃ and poured into acetone to obtain a fibrous polymer, the fibrous polymer is washed by acetone, extracted by acetone for 20 hours in a Soxhlet extractor, and dried in a vacuum oven at 150 ℃ for 24 hours to obtain the irregular sulfur-containing polyimide resin particles. The ratio of the sum of the amounts of the 2,2 ' -di (sulfonic acid group) -4, 4' -diaminodiphenyl ether and 4,4' -diaminodiphenyl ether to the amount of thioether naphthalene dianhydride is 1:1, the ratio of the amounts of the 2,2 ' -bis (sulfonic) -4, 4' -diaminodiphenyl ether and 4,4' -diaminodiphenyl ether is 1: 0.001-1000, preferably 1:0.1 to 10, more preferably 1: 0.2 to 4; the mass ratio of the 2,2 ' -di (sulfonic group) -4, 4' -diaminodiphenyl ether to triethylamine is 1: 2-4, and the mass ratio of the 4,4' -diaminodiphenyl ether to benzoic acid is 1: 3-5
The reaction formula is shown as the following formula:
for the synthesis of 2,2 '-bis (sulfo) -4, 4' -diaminodiphenyl ether, see Fang, j.; guo, x.; harada, s.; watari, t.; tanaka, k.; kita, H.macromolecules,2002,35,9022.
Synthetic methods for thioether naphthalene dianhydride are described in rusanol, a.l. poly m Syn Adv poly m Sci,1994,111,115.
The random polymer is prepared by adopting a one-pot method, namely, a sulfur-containing diamine monomer, a sulfur-free diamine monomer and dianhydride are dissolved in a m-cresol solvent and are directly heated to prepare the random polymer.
The block type sulfur-containing polyimide resin particles can be prepared by the following method:
(1) under the protection of nitrogen, 2 '-di (sulfonic group) -4, 4' -diaminodiphenyl ether, triethylamine and m-cresol A are mixed, stirred to completely dissolve the 2,2 '-di (sulfonic group) -4, 4' -diaminodiphenyl ether, then thioether naphthalene dianhydride A and benzoic acid A are added, the mixture is stirred for 30 minutes at room temperature, then the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 18 hours, so that the amino-terminated polyimide oligomer is obtained;
(2) adding thioether naphthalene dianhydride B and m-cresol B under the protection of nitrogen, stirring and dissolving, then adding 4,4' -diaminodiphenyl ether and benzoic acid B, and reacting for 18h at 180 ℃ to obtain anhydride-terminated polyimide oligomer;
(3) and (2) when the mixture in the step (1) and the step (2) is cooled to 80 ℃, adding the mixture in the step (2) into the mixture in the step (1), reacting the reaction solution at 80 ℃ for 4h, reacting at 180 ℃ for 18h, cooling to 80 ℃, pouring into acetone to obtain a fibrous polymer, washing with acetone, extracting with acetone in a Soxhlet extractor for 20h, and drying in a vacuum oven at 150 ℃ for 24h to obtain the block-type sulfur-containing polyimide resin particles.
The thioether naphthalene dianhydride A in the step (1) and the thioether naphthalene dianhydride B in the step (2) are used for distinguishing the thioether naphthalene dianhydride in different steps, and the letter A, B has no chemical meaning.
Benzoic acid a, benzoic acid B, m-cresol a, m-cresol B are also starting materials for distinguishing between the different steps, the letter A, B not having a chemical meaning.
The ratio of the sum of the total substance amount of the thioether naphthalene dianhydride A and the thioether naphthalene dianhydride B to the sum of the substance amount of the 2,2 ' -di (sulfonic group) -4, 4' -diaminodiphenyl ether and the 4,4' -diaminodiphenyl ether is 1: 1;
the ratio of the amounts of thioether naphthalene dianhydride A and 2,2 '-bis (sulfonic) -4, 4' -diaminodiphenyl ether is 0.5-0.9999: 1, preferably 0.9-0.99: 1;
the mass ratio of the thioether naphthalene dianhydride B to the 4,4' -diaminodiphenyl ether is 1.0001-1.5: 1, preferably 1.01-1.1: 1;
the ratio of the amounts of the 2,2 ' -bis (sulfonic) -4, 4' -diaminodiphenyl ether and 4,4' -diaminodiphenyl ether is 1: 0.001-1000, preferably 1: 0.1-10, more preferably 1: 0.2 to 4.
The ratio of the amounts of 2,2 ' -bis (sulfo) -4, 4' -diaminodiphenyl ether, triethylamine and benzoic acid A is 1: 2-4: 1.2-2, and the ratio of the amounts of 4,4' -diaminodiphenyl ether and benzoic acid B is 1: 1.2-2.
The reaction formula is shown as the following formula:
the preparation method of the block copolymer adopts a two-pot method, sulfonated diamine monomer and partial dianhydride react in one pot to prepare sulfonated block with end capped by amino, diamine monomer without sulfur reacts with dianhydride in the other pot to prepare sulfonated block with end capped by anhydride, and then the two pots are combined into one pot to carry out imidization to prepare the block copolymer.
The invention also provides a preparation method of the sulfur-containing polyimide resin film, which comprises the following steps: dissolving sulfur-containing polyimide resin particles in m-cresol to obtain a uniform viscous solution with the solid content of 10%, coating the solution on a clean glass plate to form a film by tape casting, drying the film in an oven at the temperature of 80 ℃ for 12h, then heating to the temperature of 120 ℃, continuing to dry for 12h, and naturally cooling to the room temperature. And (2) placing the glass plate into ethanol to naturally strip the glass plate, then placing the film into the ethanol to be soaked for 48 hours, taking out the film, fully washing the film by using deionized water, then soaking the film for 72 hours by using 2mol/L hydrochloric acid solution to completely protonate the film, finally taking out the film, fully washing the film by using the deionized water, and storing the film in water for later use to prepare the sulfur-containing polyimide resin film. The thickness of the sulfur-containing polyimide resin film is generally 0.05 to 2mm, preferably 1 mm.
Specifically, the random sulfur-containing polyimide resin particles are prepared into a random sulfur-containing polyimide resin film, and the block sulfur-containing polyimide resin particles are prepared into a block sulfur-containing polyimide resin film
The present invention provides the use of a sulfur-containing polyimide resin as a silver adsorbent, and further, a block-type sulfur-containing polyimide resin is preferable as a silver adsorbent. Further, as the silver adsorbent, block-type sulfur-containing polyimide resin particles or block-type sulfur-containing polyimide resin films are preferable.
Further, the application method of the silver adsorbent comprises the following steps: adding sulfur-containing polyimide resin particles or a sulfur-containing polyimide resin film into the solution to be treated containing silver ions, shaking for 10 to 2 hours by a shaking table or shaking for 10 to 30 minutes by vortex, and removing the resin particles or the resin film to obtain the treated solution.
The amount of the sulfur-containing polyimide resin particles or the sulfur-containing polyimide resin film added is generally 0.001 to 0.1g/mL, preferably 0.01 to 0.05g/mL, based on the volume of the solution to be treated.
And after the adsorption treatment is finished, separating the resin particles from the solution by using a centrifugal or standing method to obtain the treated solution.
After the adsorption treatment is finished, the resin film is directly taken out, the operation is simple and convenient, and the loss of the resin adsorbent is small.
The silver content of the solution before and after treatment can be measured by inductively coupled plasma mass spectrometry (ICP-MS), and the silver adsorption amount of the resin can be calculated.
In the adsorption application method, the pH value of the solution to be treated containing silver is less than or equal to 7, and the resin adsorbent can be used in a strong acid environment for a long time; the adsorption process can be carried out under the conditions of high temperature or high pressure, and can be normally used under the condition of 140 ℃ pressurization.
The sulfur-containing polyimide resin can be desorbed and regenerated after silver is adsorbed, and can be recycled.
The invention also provides a regeneration method of the sulfur-containing polyimide resin, which comprises the following process steps and conditions: putting the sulfur-containing polyimide resin particles or films adsorbed with silver into 1mol/L hydrochloric acid solution containing 10% of thiourea in mass fraction, desorbing by using ultrasonic oscillation or vortex oscillation for 10-60 minutes, centrifuging or filtering to obtain resin particles, or directly taking out the resin films, soaking and cleaning the obtained particles or films by using 3mol/L hydrochloric acid solution, and drying at 100 ℃ to obtain the regenerated sulfur-containing polyimide resin particles.
Compared with the prior art, the invention has the following advantages: the used sulfur-containing polyimide resin is resistant to strong acid, and can be used for adsorbing silver in an acid solution, such as strongly acidic industrial wastewater and the like. Meanwhile, the material is high temperature resistant, has good thermal stability under the condition of below 280 ℃ and normal pressure, can be normally used under the condition of high pressure of 140 ℃, and fills the blank of the organic polymer silver adsorption material in the high-temperature strong acid environment.
The number of the sulfur-containing functional groups on the surfaces of the sulfur-containing polyimide resin particles is adjustable, and the adsorption capacity of the material to metal is controllable.
The sulfur-containing polyimide resin has strong hydrophilicity and extremely hydrophilicity, can be uniformly dispersed in a sample solution to be adsorbed, and has good adsorption effect.
The sulfur-containing polyimide resin provided by the invention has the advantages of simple adsorption process on silver, convenience in operation, specific adsorption on silver elements, no interference of potassium, sodium, calcium, magnesium, iron, zinc, copper, cadmium and other elements in the adsorption process, simple and convenient regeneration process, cyclic use, long service life and environmental protection.
Drawings
FIG. 1 is an infrared spectrum of a random type sulfur-containing polyimide resin particle prepared in example 1. 1709cm-1And 1668cm-1Two obvious absorption peaks are respectively asymmetric stretching vibration and symmetric stretching vibration of carbonyl on an imide ring. 1368cm-1Is a C-N stretching vibration peak on an imide ring, 1193,1030cm-1And 1239,1085cm-1The four absorption peaks are symmetric and asymmetric stretching vibration of the sulfonic acid group respectively.
FIG. 2 is a nuclear magnetic resonance spectrum of the random type sulfur-containing polyimide resin particles prepared in example 1. 7.84,7.45, and 7.03ppm are respectively the hydrogen a, b, c on the 2,2 ' -bis (sulfo) -4, 4' -diaminodiphenyl ether benzene ring, 7.45 and7.24ppm are the hydrogen d on the 4,4' -diaminodiphenyl ether benzene ring, e.
FIG. 3 is a TEM image of a sulfur-containing polyimide resin film, wherein (a) is a random-type sulfur-containing polyimide resin film and (b) is a block-type sulfur-containing polyimide resin film.
Detailed Description
The following examples are given to illustrate the present invention, but it should be understood that the following examples are only for illustrative purposes and are not to be construed as limiting the scope of the present invention.
Example 1
The molar ratio of the sulfur-containing diamine monomer 2,2 ' -bis (sulfonic) -4, 4' -diaminodiphenyl ether (ODADS) to the sulfur-free diamine monomer 4,4' -diaminodiphenyl ether (ODA) is set to 6:4, and the mixture is subjected to a feeding reaction according to a preparation method of the random sulfur-containing polyimide to prepare the random sulfur-containing polyimide resin particles.
2,2 ' -bis (sulfo) -4, 4' -diaminodiphenyl ether ODADS (0.6524g,1.81mmol), triethylamine (0.5390g,5.33mmol) and 8mL of m-cresol were added to a three-necked flask equipped with nitrogen blanket, and after stirring to completely dissolve ODADS, 4' -diaminodiphenyl ether ODA (0.2417g,1.21mmol), thioether naphthalene dianhydride SBNTA (1.2866g,3.02mmol) and benzoic acid (0.5522g,4.53mmol) were added. The mixture was stirred at room temperature for 30 minutes, then heated to 80 ℃ for 4 hours and 180 ℃ for 18 hours. After the mixture was cooled to 80 ℃, it was poured into 500mL of acetone to obtain a fibrous polymer. After being washed once by acetone, the sulfonated polyimide is extracted by acetone in a Soxhlet extractor for 20 hours and dried in a vacuum oven at 150 ℃ for 24 hours to obtain the triethylamine salt type polymer of the sulfonated polyimide. The infrared spectrum and nuclear magnetic resonance spectrum of the product are shown in figures 1 and 2, respectively.
SPI-R(6/4):FT-IR(film):1709cm-1(vasymC＝O),1668cm-1(vsymC＝O),and 1368cm-1(vC-Nimide),1239,1193,1085,1030cm-1(sulfonic acid group stretching).
2.5g of the resin particles prepared above were added into 50mL of a 2mg/L silver ion solution, the mixture was shaken in a shaker for 30 minutes, and the resin particles were removed by centrifugation, and the concentration of silver ions in the treated solution was measured to be 0.274mg/L, and the removal rate of silver ions was 86.3%.
And (3) putting the resin particles adsorbed with the silver ions into 10mL of 1mol/L hydrochloric acid solution containing 10% by mass of thiourea, desorbing by using ultrasonic oscillation for 30 minutes, centrifuging, taking supernate, and detecting to obtain the desorption rate of the silver ions, wherein the desorption rate of the silver ions is 85.5%. And soaking and cleaning the centrifuged resin particles by using 3mol/L hydrochloric acid, and then drying at 100 ℃ to complete resin regeneration.
2.5g of the regenerated resin was added to 50mL of a 2mg/L silver ion solution, the mixture was shaken in a shaker for 30 minutes, and resin particles were removed by centrifugation, and the concentration of silver ions in the treated solution was measured to be 0.281mg/L, and the removal rate of silver ions was 85.95%. The silver adsorption capacity of the regenerated resin is not significantly different from that of the resin before regeneration.
After adsorption and regeneration according to the method, the removal rate of silver ions is 80.7 percent and still reaches more than 80 percent after 10 times of total adsorption and regeneration.
Example 2
The molar ratio of the sulfur-containing diamine monomer to the non-sulfur-containing diamine monomer is set to 6:4, the mixture is subjected to a feeding reaction, the reaction is carried out according to the preparation method of the block-type sulfur-containing polyimide resin, and the length of the hydrophilic block is controlled to prepare the block-type sulfur-containing polyimide resin particles.
A nitrogen-blanketed jar was charged with sulfonated diamine ODADS (0.6618g,1.84mmol), triethylamine (0.4467g,4.41mmol) and 8mL m-cresol, stirred to dissolve ODADS completely, and then thioether naphthalene dianhydride SBNTA (0.7640g,1.79mmol) and benzoic acid (0.3274g,2.68mmol) were added. The mixture was stirred at room temperature for 30 minutes, then heated to 80 ℃ for 4 hours and 180 ℃ for 18 hours to give an amine-terminated polyimide oligomer. In another nitrogen-protected two-neck flask, the remaining naphthalene dianhydride SBNTA (0.5420g,1.27mmol), 8mL of m-cresol were added, stirred to dissolve, and then unsulfonated diamine ODA (0.2454g,1.23mmol), benzoic acid (0.2324g,1.91mmol) were added and reacted at 180 ℃ for 18 h. When the mixture in the two reaction bottles is cooled to 80 ℃, the mixture in the second inclined three-necked bottle is transferred to the first inclined three-necked bottle, and then the reaction liquid is reacted for 4 hours at 80 ℃ and for 18 hours at 180 ℃. After the mixture in the reaction flask was cooled to 80 ℃, it was poured into 500mL of acetone to obtain a fibrous polymer. After being washed once by acetone, the sulfonated polyimide is extracted by acetone in a Soxhlet extractor for 20 hours and dried in a vacuum oven at 150 ℃ for 24 hours to obtain the triethylamine salt type polymer of the sulfonated polyimide.
SPI-B(6/4)-40:FT-IR(film):1704cm-1(vasymC＝O),1656cm-1(vsymC＝O),and1363cm-1(vC-Nimide),1229,1186,1081,1025cm-1(sulfonic acid group stretching).
0.5g of the resin particles prepared above was added to 50mL of a 2mg/L silver ion solution, the solution was shaken in a vortex shaker for 30 minutes, and the resin particles were removed by centrifugation, and the concentration of silver ions in the treated solution was measured to be 0.133mg/L, and the removal rate of silver ions was 93.3%.
And (3) putting the resin particles adsorbed with the silver ions into 50mL of 1mol/L hydrochloric acid solution containing 10% thiourea, desorbing by using vortex oscillation for 60 minutes, centrifuging, taking supernate, and detecting to obtain the desorption rate of the silver ions, wherein the desorption rate of the silver ions is 89.1%. And soaking and cleaning the centrifuged resin particles by using 3mol/L hydrochloric acid, and then drying at 100 ℃ to complete resin regeneration.
0.5g of the regenerated resin is taken out and added into 50mL of silver ion solution with the concentration of 2mg/L, the solution is placed into a shaking table to be shaken for 30 minutes, resin particles are removed by centrifugation, the concentration of the silver ions in the solution after the treatment is measured to be 0.139mg/L, and the removal rate of the silver ions is 93.05 percent. The silver adsorption capacity of the regenerated resin is not significantly different from that of the resin before regeneration.
After adsorption and regeneration according to the method, the removal rate of silver ions is 88.7 percent and still reaches more than 88 percent after 10 times of total adsorption and regeneration.
Example 3
The feeding reaction was carried out with the molar ratio of the sulfur-containing diamine monomer to the sulfur-free diamine monomer set to 6:4, and the reaction was carried out in accordance with the method for producing a block-type sulfur-containing polyimide resin of example 2 while controlling the hydrophilic block length to obtain block-type sulfur-containing polyimide resin particles.
Iron ions, zinc ions, copper ions and cadmium ions are added into the silver ion solution to prepare a multi-element mixed solution containing 2mg/L of silver ions, 1mg/L of iron ions, 1mg/L of zinc ions, 1mg/L of copper ions and 1mg/L of cadmium ions respectively.
Taking 1.0g of the block type sulfur-containing polyimide resin particles prepared by the method, adding the block type sulfur-containing polyimide resin particles into 50mL of multi-element mixed solution containing 2mg/L of silver ions and 1mg/L of iron, zinc, copper and cadmium ions, placing the mixed solution into a shaking table to oscillate for 30 minutes, centrifuging the mixed solution to obtain supernatant, measuring that the concentration of the silver ions in the supernatant is 0.209mg/L, the removal rate of the silver ions is 89.6 percent, and the concentrations of the iron, zinc, copper and cadmium ions are basically unchanged, thereby proving that the resin particles basically have no adsorption on the iron, zinc, copper and cadmium ions.
Example 4
The feeding reaction was carried out with the molar ratio of the sulfur-containing diamine monomer to the sulfur-free diamine monomer set to 6:4, and the reaction was carried out in accordance with the method for producing a block-type sulfur-containing polyimide resin of example 2 while controlling the hydrophilic block length to obtain block-type sulfur-containing polyimide resin particles.
Potassium ions, sodium ions, calcium ions and magnesium ions are added into the silver ion solution to prepare a multi-element mixed solution containing 2mg/L of silver ions, potassium ions, sodium ions, calcium ions and magnesium ions respectively at 2 mg/L.
Taking 1.0g of the block type sulfur-containing polyimide resin particles prepared by the method, adding the block type sulfur-containing polyimide resin particles into 50mL of multi-element mixed solution containing 2mg/L of silver ions and 2mg/L of potassium, sodium, calcium and magnesium ions, placing the mixed solution into a shaking table to oscillate for 30 minutes, centrifuging the mixed solution to obtain supernatant, measuring that the concentration of the silver ions in the supernatant is 0.247mg/L, the removal rate of the silver ions is 87.6 percent, and the concentrations of the potassium, sodium, calcium and magnesium ions are basically unchanged, thereby proving that the resin particles basically have no adsorption on the potassium, sodium, calcium and magnesium ions.
Example 5
The feeding reaction was carried out with the molar ratio of the sulfur-containing diamine monomer to the sulfur-free diamine monomer set to 6:4, and the reaction was carried out in accordance with the method for producing a block-type sulfur-containing polyimide resin of example 2 while controlling the hydrophilic block length to obtain block-type sulfur-containing polyimide resin particles. Then preparing the block type sulfur-containing polyimide film according to the preparation method of the sulfur-containing polyimide film, and activating in a hydrochloric acid solution.
The block type sulfur-containing polyimide resin pellets were prepared in the same manner as in example 2.
The preparation method of the film comprises the following steps: dissolving block type sulfur-containing polyimide resin particles in m-cresol to obtain a uniform viscous solution with the solid content of 10%, coating the solution on a clean glass plate to form a film by tape casting, drying the film in an oven at the temperature of 80 ℃ for 12 hours, then heating to the temperature of 120 ℃, continuing to dry for 12 hours, and naturally cooling to the room temperature. And (2) placing the glass plate into ethanol to naturally strip the glass plate, then placing the film into the ethanol to be soaked for 48h, taking out the film, fully washing the film by using deionized water, then soaking the film for 72h by using 2mol/L hydrochloric acid solution to completely protonate the film, finally taking out the film, fully washing the film by using the deionized water, and storing the film in water for later use to prepare the block-containing type polyimide sulfide resin film. The thickness of the block type sulfur-containing polyimide resin film was 1 mm.
In addition, the block type sulfur-containing polyimide resin particles were changed to the random type sulfur-containing polyimide resin particles prepared in example 1, to prepare a random type sulfur-containing polyimide resin film. TEM images of the two films were measured, as shown in FIG. 3.
In FIG. 3, (a) shows a random sulfur-containing polyimide resin film, and (b) shows a block-type sulfur-containing polyimide resin film. The measurement method is as follows: putting the sulfur-containing polyimide resin film in 0.5mol/L AgNO3The aqueous solution was taken overnight, washed with water and dried at room temperature for 12 hours. The treated film was embedded in epoxy resin, cut into a 70nm thick thin sheet with a microtome, and then observed under a transmission electron microscope. In TEM, dark portions represent hydrophilic phase segments and bright portions represent hydrophobic phase segments. In the random copolymer (a), the ion cluster is smaller: (<10nm, on average 4-5nm), whereas in the block copolymer (b) the ion clusters are significantly larger ((b)>40nm), indicating that a microphase separation of the hydrophilic phase (containing sulfonic acid groups) and the hydrophobic phase (containing no sulfonic acid groups) was formed, but no distinct gray band was found.
1.5g of the block type sulfur-containing polyimide film prepared above was added to 50mL of a solution containing 2mg/L of silver ions, the solution was shaken in a shaker for 30 minutes, and the film was taken out, whereby the concentration of silver ions in the solution was 0.189mg/L and the removal rate of silver ions was 90.6%.
And (3) putting the film adsorbed with the silver ions into 15mL of 1mol/L hydrochloric acid solution containing 10% thiourea, desorbing by using ultrasonic oscillation for 30 minutes, centrifuging, taking supernate, and detecting to obtain the desorption rate of the silver ions, wherein the desorption rate of the silver ions is 89.2%. And soaking and cleaning the centrifuged film by using 3mol/L hydrochloric acid to complete film regeneration.
1.5g of the regenerated film was added to 50mL of a 2mg/L silver ion solution, the mixture was shaken in a shaker for 30 minutes, and the film was taken out, and the concentration of silver ions in the treated solution was measured to be 0.196mg/L, and the removal rate of silver ions was measured to be 90.2%. The silver adsorption capacity of the regenerated resin is not significantly different from that of the resin before regeneration.
After adsorption and regeneration according to the method, the removal rate of silver ions is 85.5 percent and still reaches more than 85 percent after 10 times of total adsorption and regeneration.
Example 6
The molar ratio of the sulfur-containing diamine monomer 2,2 ' -bis (sulfonic) -4, 4' -diaminodiphenyl ether (ODADS) to the sulfur-free diamine monomer 4,4' -diaminodiphenyl ether (ODA) was set to 8:2, and a charge reaction was carried out according to the method for producing a block-type sulfur-containing polyimide to obtain block-type sulfur-containing polyimide resin particles.
A nitrogen-blanketed jar was charged with sulfonated diamine ODADS (0.9318g,2.45mmol), triethylamine (0.5956g,5.88mmol) and 20mL m-cresol, stirred to dissolve ODADS completely, and then thioether naphthalene dianhydride SBNTA (1.0158g,2.38mmol) and benzoic acid (0.4365g,3.57mmol) were added. The mixture was stirred at room temperature for 30 minutes, then heated to 80 ℃ for 4 hours and 180 ℃ for 18 hours to give an amine-terminated polyimide oligomer. In another nitrogen-protected two-neck flask, the remaining naphthalene dianhydride SBNTA (0.2902g,0.68mmol), 5mL of m-cresol were added, stirred to dissolve, and then unsulfonated diamine ODA (0.1217g,0.61mmol), benzoic acid (0.1155g,0.95mmol) were added and reacted at 180 ℃ for 18 h. When the mixture in the two reaction bottles is cooled to 80 ℃, the mixture in the second inclined three-necked bottle is transferred to the first inclined three-necked bottle, and then the reaction liquid is reacted for 4 hours at 80 ℃ and for 18 hours at 180 ℃. After the mixture in the reaction flask was cooled to 80 ℃, it was poured into 500mL of acetone to obtain a fibrous polymer. After being washed once by acetone, the sulfonated polyimide is extracted by acetone in a Soxhlet extractor for 20 hours and dried in a vacuum oven at 150 ℃ for 24 hours to obtain the triethylamine salt type polymer of the sulfonated polyimide.
0.5g of the block-type sulfur-containing polyimide resin particles thus obtained was added to 50mL of a 2mg/L silver ion solution, the solution was shaken in a vortex shaker for 30 minutes, and the resin particles were removed by centrifugation, and the concentration of silver ions in the treated solution was measured to be 0.143mg/L, and the removal rate of silver ions was measured to be 92.8%.
And (3) putting the resin particles adsorbed with the silver ions into 50mL of 1mol/L hydrochloric acid solution containing 10% thiourea, desorbing by using vortex oscillation for 60 minutes, centrifuging, taking supernate, and detecting to obtain the desorption rate of the silver ions, wherein the desorption rate of the silver ions is 88.2%. And soaking and cleaning the centrifuged resin particles by using 3mol/L hydrochloric acid, and then drying at 100 ℃ to complete resin regeneration.
0.5g of the regenerated resin was taken out, added into 50mL of a 2mg/L silver ion solution, put into a shaker and shaken for 30 minutes, and centrifuged to remove resin particles, and the concentration of silver ions in the solution after the treatment was measured to be 0.149mg/L, and the removal rate of silver ions was measured to be 92.5%. The silver adsorption capacity of the regenerated resin is not significantly different from that of the resin before regeneration.
Example 7
The molar ratio of the sulfur-containing diamine monomer 2,2 ' -bis (sulfonic) -4, 4' -diaminodiphenyl ether (ODADS) to the sulfur-free diamine monomer 4,4' -diaminodiphenyl ether (ODA) was set to 2:8, and a charge reaction was carried out according to the method for producing a block-type sulfur-containing polyimide resin pellet.
A nitrogen-blanketed jar was charged with sulfonated diamine ODADS (0.2194g,0.61mmol), triethylamine (0.1481g,1.46mmol) and 4mL m-cresol, stirred to dissolve ODADS completely, and then thioether naphthalene dianhydride SBNTA (0.2433g,0.57mmol) and benzoic acid (0.1085g,0.89mmol) were added. The mixture was stirred at room temperature for 30 minutes, then heated to 80 ℃ for 4 hours and 180 ℃ for 18 hours to give an amine-terminated polyimide oligomer. In another nitrogen-protected two-neck flask, the residual naphthalene dianhydride SBNTA (1.0586g,2.5mmol) and 16mL of m-cresol were added, stirred to dissolve, and then unsulfonated diamine ODA (0.4908g,2.46mmol) and benzoic acid (0.4648g,3.82mmol) were added, and reacted at 180 ℃ for 18 h. When the mixture in the two reaction bottles is cooled to 80 ℃, the mixture in the second inclined three-necked bottle is transferred to the first inclined three-necked bottle, and then the reaction liquid is reacted for 4 hours at 80 ℃ and for 18 hours at 180 ℃. After the mixture in the reaction flask was cooled to 80 ℃, it was poured into 500mL of acetone to obtain a fibrous polymer. After being washed once by acetone, the sulfonated polyimide is extracted by acetone in a Soxhlet extractor for 20 hours and dried in a vacuum oven at 150 ℃ for 24 hours to obtain the triethylamine salt type polymer of the sulfonated polyimide.
0.5g of the resin particles prepared above was added to 50mL of a 2mg/L silver ion solution, the mixture was shaken in a shaker for 30 minutes, and the resin particles were removed by centrifugation, and the concentration of silver ions in the treated solution was measured to be 0.151mg/L, and the removal rate of silver ions was measured to be 92.4%.
And (3) putting the resin particles adsorbed with the silver ions into 10mL of 1mol/L hydrochloric acid solution containing 10% by mass of thiourea, desorbing by using ultrasonic oscillation for 30 minutes, centrifuging, taking supernate, and detecting to obtain the desorption rate of the silver ions, wherein the desorption rate of the silver ions is 89.6%. And soaking and cleaning the centrifuged resin particles by using 3mol/L hydrochloric acid, and then drying at 100 ℃ to complete resin regeneration.
0.5g of the regenerated resin is taken out and added into 50mL of silver ion solution with the concentration of 2mg/L, the solution is placed into a shaking table to be shaken for 30 minutes, resin particles are removed by centrifugation, the concentration of the silver ions in the solution after the treatment is measured to be 0.155mg/L, and the removal rate of the silver ions is measured to be 92.2%. The silver adsorption capacity of the regenerated resin is not significantly different from that of the resin before regeneration.
Example 8
The block-type sulfur-containing polyimide resin particles were obtained by carrying out the charging reaction with the molar ratio of the sulfur-containing diamine monomer to the non-sulfur-containing diamine monomer set to 6:4 and carrying out the reaction in accordance with the method for producing the block-type sulfur-containing polyimide of example 2.
0.5g of the resin particles obtained above was added to 50mL of an acidic silver ion solution having a concentration of 2mg/L and a pH of 1, the mixture was shaken in a shaker for 30 minutes, and the resin particles were removed by centrifugation, and the concentration of silver ions in the solution after the treatment was measured to be 0.152mg/L, and the removal rate of silver ions was 92.4%. In comparison with the data of example 1, it can be seen that the adsorption performance of the sulfur-containing polyimide resin particles in the acidic solution is not affected.
Example 9
The block-type sulfur-containing polyimide resin particles were obtained by carrying out the charging reaction with the molar ratio of the sulfur-containing diamine monomer to the non-sulfur-containing diamine monomer set to 6:4 and carrying out the reaction in accordance with the method for producing the block-type sulfur-containing polyimide of example 2.
0.5g of the resin particles prepared above was added to 50mL of a 2mg/L silver ion solution, shaken in a shaker at a water bath temperature of 95 ℃ for 30 minutes, and centrifuged to remove the resin particles, and the concentration of silver ions in the treated solution was determined to be 0.135mg/L, and the removal rate of silver ions was 93.2%. In comparison with the data of example 1, it can be seen that the adsorption performance of the sulfur-containing polyimide resin particles is not affected under a high-temperature environment.
Claims (10)
1. An application of sulfur-containing polyimide resin as a silver adsorbent, wherein the sulfur-containing polyimide resin is a random sulfur-containing polyimide resin or a block sulfur-containing polyimide resin, the structural formula of the random sulfur-containing polyimide resin is shown as a formula I, the structural formula of the block sulfur-containing polyimide resin is shown as a formula II,
wherein m, n and x are integers of 1-1000 respectively.
2. The use according to claim 1, wherein the sulfur-containing polyimide resin is sulfur-containing polyimide resin particles or a sulfur-containing polyimide resin film, and the sulfur-containing polyimide resin film is formed by film formation of the sulfur-containing polyimide resin particles.
3. The use according to claim 2, wherein the sulfur-containing polyimide resin particles are random sulfur-containing polyimide resin particles or block sulfur-containing polyimide resin particles, and the sulfur-containing polyimide resin film comprises a random sulfur-containing polyimide resin film or a block sulfur-containing polyimide resin film prepared from the random sulfur-containing polyimide resin particles or the block sulfur-containing polyimide resin particles, respectively.
4. The use according to claim 3, wherein the random sulfur-containing polyimide resin particles are prepared by the following method: under the protection of nitrogen, 2 ' -di (sulfonic group) -4, 4' -diaminodiphenyl ether, triethylamine and m-cresol are mixed, stirred to completely dissolve 2,2 ' -di (sulfonic group) -4, 4' -diaminodiphenyl ether, then 4,4' -diaminodiphenyl ether, thioether naphthalene dianhydride and benzoic acid are added, the mixture is stirred for 30 minutes at room temperature, then heated to 80 ℃ for reaction for 4 hours, then heated to 180 ℃ for reaction for 18 hours, cooled to 80 ℃ and poured into acetone to obtain a fibrous polymer, the fibrous polymer is washed by acetone, extracted by acetone for 20 hours in a Soxhlet extractor, and dried in a vacuum oven at 150 ℃ for 24 hours to obtain the irregular sulfur-containing polyimide resin particles.
5. The use according to claim 3, wherein the block-type sulfur-containing polyimide resin particles are prepared by the following method:
(1) under the protection of nitrogen, 2 '-di (sulfonic group) -4, 4' -diaminodiphenyl ether, triethylamine and m-cresol A are mixed, stirred to completely dissolve the 2,2 '-di (sulfonic group) -4, 4' -diaminodiphenyl ether, then thioether naphthalene dianhydride A and benzoic acid A are added, the mixture is stirred for 30 minutes at room temperature, then the temperature is increased to 80 ℃ for reaction for 4 hours, and then the temperature is increased to 180 ℃ for reaction for 18 hours, so that the amino-terminated polyimide oligomer is obtained;
(2) adding thioether naphthalene dianhydride B and m-cresol B under the protection of nitrogen, stirring and dissolving, then adding 4,4' -diaminodiphenyl ether and benzoic acid B, and reacting for 18h at 180 ℃ to obtain anhydride-terminated polyimide oligomer;
(3) and (2) when the mixture in the step (1) and the step (2) is cooled to 80 ℃, adding the mixture in the step (2) into the mixture in the step (1), reacting the reaction solution at 80 ℃ for 4h, reacting at 180 ℃ for 18h, cooling to 80 ℃, pouring into acetone to obtain a fibrous polymer, washing with acetone, extracting with acetone in a Soxhlet extractor for 20h, and drying in a vacuum oven at 150 ℃ for 24h to obtain the block-type sulfur-containing polyimide resin particles.
6. The use according to claim 2, wherein the sulfur-containing polyimide resin film is prepared by the following method: dissolving sulfur-containing polyimide resin particles in m-cresol to obtain a uniform viscous solution with the solid content of 10%, coating the solution on a clean glass plate to form a film by tape casting, drying the film in an oven at the temperature of 80 ℃ for 12 hours, heating the film to the temperature of 120 ℃ to continue drying for 12 hours, naturally cooling the film to room temperature, putting the glass plate into ethanol to naturally peel the glass plate, then putting the film into the ethanol to soak for 48 hours, taking the film out, fully washing the film with deionized water, then soaking the film with 2mol/L hydrochloric acid solution for 72 hours to completely protonate the film, finally taking the film out to obtain the sulfur-containing polyimide resin film, and fully washing the film with the deionized water and then storing the film in water for later use.
7. Use according to claim 1 or 2, characterized in that the block-type sulfur-containing polyimide resin is used as silver adsorbent.
8. The use according to claim 1, characterized in that the method of application is: adding sulfur-containing polyimide resin particles or a sulfur-containing polyimide resin film into the solution to be treated containing silver ions, shaking for 10 to 2 hours by a shaking table or shaking for 10 to 30 minutes by vortex, and removing the resin particles or the resin film to obtain the treated solution.
9. The use of claim 8, wherein the sulfur-containing polyimide resin is subjected to desorption regeneration after silver adsorption and is recycled.
10. The use according to claim 9, wherein the sulfur-containing polyimide resin is regenerated by a method comprising: putting the sulfur-containing polyimide resin particles or films adsorbed with silver into 1mol/L hydrochloric acid solution containing 10% of thiourea in mass fraction, desorbing by using ultrasonic oscillation or vortex oscillation for 10-60 minutes, centrifuging or filtering to obtain resin particles, or directly taking out the resin films, soaking and cleaning the obtained particles or films by using 3mol/L hydrochloric acid solution, and drying at 100 ℃ to obtain the regenerated sulfur-containing polyimide resin particles.
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