CN113024713B - Allyl monomer-based hydrophilic heavy metal ion chelating copolymer resin and synthetic method thereof - Google Patents
Allyl monomer-based hydrophilic heavy metal ion chelating copolymer resin and synthetic method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of modified resin synthesis, and particularly relates to a hydrophilic heavy metal ion chelating copolymer resin based on an allyl monomer and a synthesis method thereof. The basic structural units of the resin of the present invention are as follows:
wherein R1 is Me or H; r2 is Me, or H, or t-Bu. The hydrophilic heavy metal ion chelating copolymer resin can be complexed with metal ions such as copper, cobalt, nickel, mercury, lead, palladium and the like, and is used for the fields of metal ion removal, metal ion enrichment of noble metal ores, metal ion catalysis of loaded metal ions and the like in the fields of precision electronic industry, medical treatment, nuclear power, pharmacy, traditional Chinese medicine and the like.
Description
Technical Field
The invention belongs to the technical field of modified resin synthesis, and particularly relates to a hydrophilic heavy metal ion chelating copolymer resin based on an allyl monomer and a synthesis method thereof.
Background
With the acceleration of urbanization and industrialization, heavy metal ion pollution is more and more concerned by people. The heavy metal ions have carcinogenic and neurotoxic effects on organisms, cannot be biodegraded, can be enriched along a biological chain, and is low in pathogenic amount, so that the method for efficiently removing the heavy metal ions can obviously improve the utilization rate of human beings on water resources, and reduce the incidence rate of diseases and death. The traditional method for removing heavy metal ions comprises the following steps: chemical precipitation, adsorption, membrane separation, electrolysis, and the like. The chemical precipitation method is economical and practical, but cannot remove low-concentration metal ions; the investment of the membrane separation method equipment is high, and the membrane needs to be replaced frequently; the electrolysis process is too energy-consuming. The adsorption method has incomparable advantages in cost and efficiency compared with other methods, and is the most common treatment method.
In the traditional adsorbing material, the chelating resin is the most common material for adsorbing heavy metal ions, and has the advantages of high adsorption speed, high capacity and good selectivity. Common chelating functional groups are: aminophosphonic acids, iminoacetic acids, Schiff bases, 8-hydroxyquinolines, amidoximes, and the like, wherein the IDA group is N (CH)2COOH)2Are the most widely used chelating groups. Purolite S-930 (Libinge et al, Imidiacetic acid type chelate resin application research progress and prospect, materials guide 2015,29(15), P59-64), Amberlite IRC-748 (Seggianetic, Recovery of organic from flash by organic acidic chemistry fastening 2006,81(1),9-14), Amberlite IRC-718, and Chelex-100(3), and Diaion CR20 (Linetic, Ion-exchange equilibrium of Cu (II) and Zn (II) Chemical aqueous solutions with Chelex 100and Amberlite IRC resins, Journal Engineering 2005,112, 218 TP-207), Leom-acetic acid type chelate resin application research progress and prospect, materials guide 2015,29(15), P59-64, Amberlite IRC-748, and Chelex-100(3)
Commercial resins such as Removal of Cd (II) and Pb (II) complexes with a glycolic acid from a water solution on a differential exchange, Canadian Journal of Chemistry 2010,88(6), 540-. These chelating resins are useful for a variety of metal ions such as: cu, Ni, Co, Pb, etc. all have good adsorption effect. Wherein the adsorption capacities of Lewatit TP-207, Amberlite IRC-718 and Amberlite IRC-748 on copper ions are respectively as follows: 0.91, 1.12 and 1.17 mmol/g.
Chinese patent CN1210099C discloses an amidoxime chelate resin which has a good adsorption effect on gallium and has an adsorption capacity as high as 3.06 g/L. Chinese patent CN1231508C discloses a method for preparing a chelating material by grafting non-woven fabric, which takes the non-woven fabric and chloromethyl styrene or methacrylic glyceride as a base material, grafts chelating groups such as iminodiacetic acid, diethanolamine, amino acid and the like on the base material by a chemical method to prepare the metal chelating material, has good adsorption effect on metal ion copper, and can reduce the concentration of copper ions to 0.09 ppm. Chinese patent CN101811030B discloses a method for removing metal ions by synergistic treatment of a plurality of chelating resins. The patent utilizes benzylamino methylene phosphate resin, mercapto resin, amino resin and iminodiacetic acid resin to synergistically adsorb various metal ions contained in the traditional Chinese medicine, wherein the removal rate is 100%, and the removal rate has a good effect on ions such as lead, cadmium, copper and mercury. Chinese patent CN103143393A discloses a macroporous chelating resin complex metal salt as a catalyst for catalyzing aromatic ring chlorination reaction, and a high para-position selectivity product can be obtained by regulating the ortho-position proportion of a chlorination product by utilizing the size of a resin pore channel. U.S. Pat. No. 4,3214413 discloses a process for preparing a chelating monomer and a chelating resin. Taking a phenylenediethylene monoepoxy compound as a substrate, bonding the chelation-reducing group with the phenylenediethylene monoepoxy compound through an epoxy ring-opening reaction to obtain a polymerizable chelating monomer, and preparing the chelating resin through a polymerization reaction. World patent WO2017201758a1 discloses a method for preparing a battery negative electrode by complexing metal ions with a chelating resin. By adding the chelating resin into the negative electrode of the battery and taking the complexed metal ions as an electrolyte cation storage pool, the metal ions are slowly released to enter the electrolyte to supplement the inactivated metal ions, so that the cycle life of the battery is prolonged. U.S. Pat. No. 4, 20060065604, 1 discloses a resin containing a chelate group of Trocaric acid. The chelate resin prepared by directly bonding the troxacid on the polymer skeleton and generating the troxacid through chemical conversion has good adsorption effect on copper and nickel, and can selectively adsorb the copper and the nickel in the presence of interfering ions such as calcium, magnesium and the like. Chinese patent CN101870747 discloses a resin containing imido-bis (methylene phosphonic acid) chelating group, chinese patent CN1231508C discloses a resin containing iminodiacetic acid chelating group, these two resins have good adsorption effect on some heavy metal ions, but two chelating groups are flexible structures, two chelating groups can freely rock, which is not beneficial to forming stable complex with heavy metal ions, and the skeleton forming the resin is a hydrophobic skeleton cross-linked by polystyrene and divinylbenzene, which is not beneficial to the diffusion of water-soluble metal ions in the resin, and affects the actual adsorption effect.
The review of literature finds that the pyridine dicarboxylic acid monomer has a good adsorption effect on metal ions, but research is focused on the material performance (for example, Schmidt, B.Bioorg Med Chem Lett,2004,4203-6), the research on the application of the framework in the field of heavy metal ion removal is very little, only one of the researches uses 2,6-pyridine dihydrazone or 2,6-pyridine diformaldehyde as a complexing group (Chessa, Gavino, Reactive Polymers,1990, 219-.
Disclosure of Invention
The invention aims to provide a chelating resin with stable performance, high adsorption efficiency and good selectivity and a synthesis method thereof. 2,6-pyridine dicarboxylic acid is used as a complexing group, and the hydrophilicity of the whole polymer is enhanced through copolymerization with acrylic acid, so that a novel metal ion removal polymer is obtained.
In order to realize the aim, the invention firstly synthesizes a rigid tridentate ligand (4-hydroxypyridine-2, 6-dicarboxylic acid), obtains polymerizable chelating monomer through methyl esterification, hydroxyl allylation or p-vinyl benzylation, then copolymerizes the polymerizable chelating monomer with tert-butyl acrylate, and then prepares hydrophilic tridentate chelating resin through one-step or two-step hydrolysis reaction; or hydrolyzing the chelating monomer to obtain a pyridine 2, 6-dicarboxylic acid polymerizable monomer, and directly polymerizing the polymerizable monomer with acrylic acid to obtain the hydrophilic tridentate chelating resin.
Wherein, the basic structural unit of the resin of the invention is as follows:
wherein R1 is Me or H; r2 is Me, or H, or t-Bu; x and y are monomer molar ratio, and the ratio of the two is 0.01 to 0.99 or 0.99 to 0.01. Preferably, the molar ratio of the two types of polymeric monomers, namely the pyridine 2, 6-dicarboxylate derivatives to the acrylic derivatives, is in the range of: 100: 1-1: 100.
The beneficial effects of the invention compared with the prior art comprise:
(1) the rigid tridentate monomer has a simple synthesis process and can be produced in a kilogram level;
(2) the synthesized copolymer has a definite structure, and the water solubility or water absorption performance of the copolymer can be controlled by the acrylic acid monomer, so that the copolymer is favorable for adsorbing heavy metal ions;
(3) the complexing monomer with a rigid structure has strong adsorption capacity on heavy metal ions, and can be used for purifying industrial wastewater containing heavy metals such as copper, lead, mercury, nickel and the like and selectively purifying industrial wastewater containing high-concentration alkaline metal ions.
Drawings
FIG. 1 is a reaction equation for synthesizing 4-hydroxypyridine-2, 6-dicarboxylic acid according to the present invention;
FIG. 2 is a reaction equation for synthesizing compound III from compound II according to the present invention;
FIG. 3 is a reaction equation for synthesizing compound IV from compound III according to the present invention;
FIG. 4 is a first flow chart of the preparation of the hydrophilic tridentate chelating resin according to the present invention;
FIG. 5 is a second flow chart of the preparation of the hydrophilic tridentate chelating resin according to the present invention.
Detailed Description
The invention is further described below with reference to the following figures and specific examples.
4-hydroxypyridine-2, 6-dicarboxylic acid was prepared according to the reaction scheme of FIG. 1 (see How th etc., A new effective Method for the Preparation of 2,6-pyridine Dimethyl from Dimethyl 2,60-pyridine phenolic compounds 1999,29(21), 3719-3731).
Referring to FIG. 1, 67.63g (2.94mol) of metallic sodium is dissolved in 1200mL of absolute ethanol to prepare a sodium ethoxide solution, 400.00g (2.74mol) of diethyl oxalate is slowly dropped with stirring, 80.00g (1.38mol) of acetone is then slowly dropped with stirring, the temperature of the solution is slowly raised during dropping, the temperature of the solution is kept constant for 1h at 65 ℃ after dropping is finished, ethanol is evaporated under reduced pressure, the solution is cooled to room temperature, 200g of ice and 400mL of concentrated hydrochloric acid are added, stirring is carried out for 1h, filtering is carried out, a filter cake is washed by 100mL of ice water, and vacuum drying is carried out to obtain 313.8g of yellow solid with the yield of 88.20%.
313.8g of the yellow solid are reacted with 600mL of concentrated hydrochloric acid at 100 ℃ for 20h, cooled, 100g of ice are added, stirred for 5min, filtered, the filter cake is washed with 100mL of ice water and the filter cake is dried under vacuum to give 208.00g of compound I as a dark gray solid with a yield of 93.00%.
208.00g of compound I is added with 1118mL of 10% ammonia water, the temperature is raised to 100 ℃, 62mL of 28% ammonia water is added every 1h, the reaction is carried out for 5h, most of the ammonia water is pumped out under reduced pressure, the solution is cooled to room temperature, 50.00g of ice and 170mL of concentrated hydrochloric acid are added, the filtration is carried out, 50mL of ice water is used for washing a filter cake, and the compound II is dried in vacuum to obtain 198.90g of compound II off-white solid with the yield of 96.13%.
1H NMR(400MHz,DMSO)δ7.56(s,2H)。
Referring to fig. 2, 107.00g of compound II was added to 700mL of methanol, cooled to 0 ℃, 64mL of thionyl chloride was slowly added dropwise, stirred for 12h, refluxed for 2h, methanol was drained, 200mL of ice water was added, a saturated sodium carbonate solution was added dropwise under ice bath to a pH >8, a large amount of gray solid was precipitated, filtered, 50mL of water washed the filter cake, and vacuum dried to obtain 90.00g of compound III with a yield of 72.90%.
1H NMR(400MHz,CDCl3)δ7.45(s,2H),4.00(s,6H)。
Referring to fig. 3, 21.49g of compound III, 28.13g of potassium carbonate added 200mL of dmf, nitrogen replaced three times, 26.44mL of allyl bromide added dropwise with stirring, reacted at 50 ℃ for 12h, cooled to room temperature, filtered, the filter cake washed with 50mL of ethyl acetate, the filtrate was spin-dried, dissolved in 300mL of dichloromethane, washed with 30mL of 2 saturated brine (twice), dried over anhydrous sodium sulfate of the organic phase, filtered, the filtrate was spin-dried, and recrystallized 2 times with ethanol to give 19.35g of compound IV, yield 75.60%.
1H NMR(400MHz,CDCl3)δ7.82(s,2H),6.04(ddd,J＝21.8,10.8,5.8Hz, 1H),5.46(d,J＝17.3Hz,1H),5.38(d,J＝10.5Hz,1H),4.77–4.67(m,2H),4.01 (s,6H)。
Referring to FIG. 4, 10g of tridentate chelating monomer compound IV, 23mL of tert-butyl acrylate and 0.066g of AIBN are added into a 150mL Schlenk tube, nitrogen is pumped out three times, 25mL of DMF is added under the nitrogen atmosphere, nitrogen is pumped out 10 times, the mixture reacts for 10 hours at 70 ℃, the temperature is increased to 80 ℃ for 10 hours, the mixture is cooled to the normal temperature, DMF is dried in a spinning mode, 300mL of methanol is used for dissolving light yellow solid, a mixed solution (1:1) of methanol and water is dripped into the solution, light brown solid is separated out, the separation experiment is repeated once, and vacuum drying is carried out to obtain 3.6g of white solid compound V.
Referring to FIG. 5, 5g of white solid compound V, 200mL of dioxane was added, 10mL of concentrated hydrochloric acid was added, the reaction was carried out at 80 ℃ for 16h, the upper layer of dioxane was poured out, the solid was dissolved by spinning, the solid was washed with ethyl acetate, and dried under vacuum to give 4.1g of chelate resin VI.
With continued reference to FIG. 5, 4.1g of chelate resin VIII was added with 150mL of a methanol-water mixture (7:1), 4g of NaOH was added, reflux reaction was carried out for 18h, cooling was carried out to room temperature, the upper layer liquid was decanted off, a white solid was obtained by spin-drying, washed with ethyl acetate, and dried under vacuum to obtain 3.5g of chelate resin VII.
Chelate resin complex copper ion experiment
Preparing 200ppm copper chloride aqueous solution for later use. Adding 80mg of chelating resin VII into 5mL of 200ppm copper ion solution, stirring at room temperature for 12h at the stirring speed of 300rpm, filtering, and measuring the copper ion content of the filtrate to be 1.3ppm by ICP-OES, wherein the copper ion removal rate is 99.35%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A hydrophilic heavy metal ion chelating copolymer resin based on propylene-based monomers, which is characterized in that the structural formula of the resin is as follows:
wherein R1 is Me or H; r2 is Me, or H, or t-Bu; x and y are monomer molar ratio, and the ratio of the two is 0.01 to 0.99 or 0.99 to 0.01.
2. The method of claim 1, wherein the chelating resin is a polymer formed by radical copolymerization of a pyridine-2, 6-dicarboxylate derivative monomer and an acrylic derivative monomer, and the complexing atoms are N and O, wherein the pyridine-2, 6-dicarboxylate derivative monomer has the following structure:
3. the method for preparing a hydrophilic heavy metal ion chelate copolymer resin according to claim 2, wherein the molar ratio of the two types of the polymeric monomers, i.e., the pyridine 2, 6-dicarboxylate derivative monomer and the acrylic derivative monomer, is in the range of: 100: 1-1: 100.
4. The method for preparing the hydrophilic heavy metal ion chelate copolymer resin according to claim 2, which specifically comprises:
firstly synthesizing a rigid tridentate ligand 4-hydroxypyridine-2, 6-dicarboxylic acid, obtaining a polymerizable chelating monomer through methyl esterification and hydroxyl allylation, then copolymerizing with tert-butyl acrylate, and then performing one-step or two-step hydrolysis reaction to obtain the hydrophilic tridentate chelating resin.
5. The method for preparing a hydrophilic chelating resin for a hydrophilic heavy metal ion chelating copolymer resin according to claim 2, comprising:
firstly, synthesizing a rigid tridentate ligand 4-hydroxypyridine-2, 6-dicarboxylic acid, and obtaining a polymerizable chelating monomer through methyl esterification and hydroxyl allylation;
the pyridine 2, 6-dicarboxylic acid polymerizable monomer is obtained by hydrolyzing the chelating monomer, and the hydrophilic tridentate chelating resin is obtained by directly polymerizing the polymerizable monomer with acrylic acid.
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| EP1944034A1 (en) * | 2005-09-30 | 2008-07-16 | Kurume University | Adsorbent for advanced glycation endproducts |
| CN104774283A (en) * | 2015-04-27 | 2015-07-15 | 南京大学 | Acrylic acid pyridine chelating resin as well as preparation method and application thereof |
| CN108976325A (en) * | 2018-08-06 | 2018-12-11 | 海南师范大学 | A kind of amidoxime group pyridine chelating resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1944034A1 (en) * | 2005-09-30 | 2008-07-16 | Kurume University | Adsorbent for advanced glycation endproducts |
| CN104774283A (en) * | 2015-04-27 | 2015-07-15 | 南京大学 | Acrylic acid pyridine chelating resin as well as preparation method and application thereof |
| CN108976325A (en) * | 2018-08-06 | 2018-12-11 | 海南师范大学 | A kind of amidoxime group pyridine chelating resin and preparation method thereof |
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| "Water-soluble poly(N-isopropylacrylamide) nanoparticles grafted to trivalent lanthanide complexes as highly sensitive ratiometric nanothermometers";Sobrinho, Josiane Aparecida等;《Royal Society of Chemistry》;20201231;第8068-8075页 * |
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