CN103788264A - Grafted acylamino hydroximic acid polymer and preparation method thereof - Google Patents
Grafted acylamino hydroximic acid polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a grafted acylamino hydroximic acid polymer and a preparation method thereof. The grafted acylamino hydroximic acid polymer is prepared from polyacrylic acid or chloromethylated polystyrene and N-acetamino alkylhydroximic acid through a substitution reaction, wherein the N-acetamino alkylhydroximic acid is obtained by making lactam react with acetylchloride through N-amidation and then performing a ring-opening reaction by using hydroxylamine under a slightly alkaline condition. The preparation method disclosed by the invention is simple in process, mild in reaction conditions and high in yield; the grafting rate of hydroximic acid in the prepared acylamino hydroximic acid polymer reaches above 97 percent; the grafted acylamino hydroximic acid polymer has better coordination properties to iron, copper, cobalt, nickel, lanthanum, cerium, yttrium, praseodymium, neodymium and the like in a solution, and can be used as a flocculating agent, or metal ion precipitator, or ion exchange resin.
Description
Technical field
The present invention relates to a kind of grafting amido hydroximic acid polymkeric substance and preparation method thereof, belong to polymkeric substance preparation field.
Background technology
Hydroximic acid compound forms unique coordination structure and excellent ligancy is widely used in the fields such as flotation, solvent extraction, chemical analysis, medicine and the waste water control in burning ore deposit because of itself and metal ion.Hydroximic acid resin is also applied to the field such as separation, enrichment of the metal ions such as iron, copper, rare earth.
At present, the synthetic of hydroximic acid polymkeric substance is that the method for carrying out polymer modification take polystyrene, polyacrylic ester, polyacrylonitrile, polyacrylamide, starch and their multipolymer etc. as skeleton prepares mostly.Patent CN1872885A discloses a kind of method of the water-soluble polymers containing hydroxamic acid group of preparing amount of polymers, this method is dispersed in the water-soluble acrylic polymer powder of amount of polymers in polar organic solvent, carry out heterogeneous esterification with alkylating reagent and hydroxylamine solution respectively and hydroxamic acid reacts, generate the water-soluble polymers containing hydroxamic acid group of amount of polymers.Wang Bi etc. have studied polyacrylamide and have prepared and contain hydroximic acid side group polymkeric substance collecting agent with azanol reaction under alkaline condition, (king is green by force for the chelating ability of this collecting agent and lead ion, Xu Guili, Hu Xingqi. chemical research and application .2008,20 (5): 561-564).Kumar etc. have studied the adsorption and enrichment of polyacrylamide base hydroxamic acid resin to rare earth elements such as La, Ce, Pr in seawater, enrichment factor can reach more than 100, and be not subject to interference (the Kumar S A of Na (I), Mg (II), Pandey S P, Shenoy N S, et al.Desalination, 2011,281:49-54).Lee etc. are take ethyl propenoate as monomer, divinylbenzene is linking agent, trimethylpentane is pore-creating agent, adopt the method for suspension polymerization to prepare the crosslinked divinylbenzene spheroid of polyethyl acrylate, again this resin is reacted under alkaline condition with oxammonium hydrochloride and makes hydroximic acid resin (T.S.Lee, D.W.Jeon, J.K.Kim, et al.Fibers and Polymers.2001,2 (1): 13～17.).Because the hydroxyl efficiency of oximation reaction of polymkeric substance is subject to the restriction of polymer backbone, reaction efficiency is lower.Patent CN103304713A discloses a kind of preparation method of poly-N-hexyl hydroximic acid acrylamide polymer, take the amino hexyl hydroximic acid of acrylic acid polymer and 6-as raw material, at the temperature of 100～160 ℃, react and syntheticly obtain poly-N-hexyl hydroximic acid acrylamide polymer in 1～4 hour.The method utilizes the amino of the carboxyl of acrylic acid polymer and the amino hexyl hydroximic acid of 6-to carry out substitution reaction to realize the grafting of superpolymer, obviously improve reaction efficiency, but the temperature of reaction of this method is still higher, under hydroximic acid high temperature, easily there is rearrangement reaction, decompose.
Summary of the invention
The object of the invention is to be to provide a kind of amido hydroximic acid polymkeric substance of high percentage of grafting, this polymkeric substance has good ligancy to the iron in solution, copper, cobalt, nickel, lanthanum, cerium, yttrium, praseodymium, neodymium etc., can be used as flocculation agent, or precipitation by metallic ion agent, or ion exchange resin.
Another object of the present invention is the method that is to provide the described amido hydroximic acid of the preparation polymkeric substance that a kind of process is simple, reaction conditions is gentle, yield is high.
A kind of grafting amido hydroximic acid polymkeric substance of the present invention, this grafting amido hydroximic acid polymkeric substance is prepared through substitution reaction by polyacrylic acid or chloromethylated polystyrene and the N-kharophen alkyl hydroximic acid with formula I structure, has formula II structural unit:
Wherein,
N is that 3～5, R is
or
group;
The percentage of grafting of N-kharophen alkyl hydroximic acid on polyacrylic acid or chloromethylated polystyrene is not less than 97%.
Described polyacrylic acid comprises that molecular weight is 200～6 × 10
6linear polyacrylic acid or the degree of crosslinking CP that is 2%～12%, described chloromethylated polystyrene degree of crosslinking is 2%～12%.
Described N-kharophen alkyl hydroximic acid is prepared by following methods: by C
4～C
6lactan and Acetyl Chloride 98Min. join in reactor with mol ratio 1:1.0～1.5, stir at 0～50 ℃, carry out N-amidate action, simultaneously, the alkaline compound of 1.0～3.0 times of molar weights of described lactan is slowly joined in described reactor, in and N-amidate action generate acid; After N-amidate action completes, in described reactor, add the azanol of 1～1.2 times of molar weight of described lactan and the alkaline compound of 1～3 times of molar weight of described lactan, carry out ring-opening reaction, after ring-opening reaction completes, in reactor, add acid to be adjusted to pH value for acid, to obtain final product.
The described preferred temperature of reaction of N-acylation reaction is 15～40 ℃; Most preferably be 25～35 ℃.
The described N-acylation reaction time is 1～4h.
The described ring-opening reaction time is 1～4h.
Described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate, Quilonum Retard, calcium oxide, tertiary butyl sodium alkoxide or tertiary butyl potassium alcoholate.
The process that described alkaline compound slowly adds is that alkaline compound is divided into some parts, and some parts of alkali of gained are added in reaction solution in batches.
The solvent that described N-acylation reaction adopts is methylene dichloride, chloroform or tetrahydrofuran (THF), and described solvent load is 2～5 times of lactan quality.
Described ring-opening reaction also adds water and/or methyl alcohol as solvent.
Described adjusting pH value is acid, and being preferably and regulating pH value is 4～6.
Described azanol adds with hydroxylammonium salt form, and described hydroxylammonium salt is oxammonium hydrochloride, oxammonium sulfate or carbonic acid azanol.
The present invention also provides a kind of preparation method of described grafting amido hydroximic acid polymkeric substance, this preparation method be by described N-kharophen alkyl hydroximic acid and polyacrylic acid or chloromethylated polystyrene under alkaline compound and condensing agent existence condition, carry out substitution reaction in 20～80 ℃, to obtain final product; Wherein, the chloromethyl in carboxyl or the chloromethylated polystyrene in polyacrylic acid: the kharophen in N-kharophen hydroximic acid: alkaline compound: the mol ratio of condensing agent is 1:1～2:1.5～4:0.5～1.
Described condensing agent is N, N-carbonyl dimidazoles (CDI), benzotriazole-N, N, N, N-tetramethyl-urea phosphofluoric acid ester (HBTU), O-(7-nitrogen benzotriazole)-N, N, N, N-tetramethyl-urea phosphofluoric acid ester (HATU), N, N-dicyclohexylcarbodiimide (HOBt), N, N-DIC (DIC) or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus (PyBOP).
Described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate, Quilonum Retard, calcium oxide, tertiary butyl sodium alkoxide or tertiary butyl potassium alcoholate.
Described substitution reaction temperature of reaction is preferably 40～60 ℃; Most preferably be 50 ℃.
The described substitution reaction time is 1～4h.
The solvent that described substitution reaction adopts is acetone or toluene.
The linear grafting amido hydroximic acid polymkeric substance making take linear polypropylene acid polymer as raw material in the present invention can be used as flocculation agent or precipitation by metallic ion agent; Can be used as ion exchange resin take CP or crosslinked chloromethylated polystyrene resin as the hydroximic acid resin that raw material makes.
Beneficial effect of the present invention: first the present invention obtains N-kharophen alkyl hydroximic acid by simple method, then N-kharophen alkyl hydroximic acid is grafted on to the grafting amido hydroximic acid polymkeric substance that obtains high percentage of grafting on polyacrylic acid or chloromethylated polystyrene resin.The present invention is by the strict temperature of reaction of controlling, and in conjunction with the use of weak base compound, farthest reduce decomposition and the rearrangement reaction of N-kharophen alkyl hydroximic acid in grafting substitution reaction process, can make polymkeric substance in obtaining higher yields, keep the hydroxyl oximate rate of superelevation, the grafting amido hydroximic acid polymkeric substance that the present invention makes has good ligancy to the iron in solution, copper, cobalt, nickel, lanthanum, cerium, yttrium, praseodymium, neodymium etc., can be used as flocculation agent, or precipitation by metallic ion agent, or ion exchange resin; The preparation process of this polymkeric substance is simple, reaction conditions gentleness, and product yield is high.
Accompanying drawing explanation
The infrared spectrogram of [Fig. 1] linear poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid polymkeric substance.
The infrared spectrogram of [Fig. 2] linear poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid polymkeric substance.
[Fig. 3] gathers the infrared spectrogram of 4-(N-ethanoyl acrylamide)-butyl hydroximic acid resin.
[Fig. 4] gathers 4-[(N-ethanoyl)-4-polyethylene benzamido group] infrared spectrogram of-butyl hydroximic acid resin.
[Fig. 5] gathers the infrared spectrogram of 6-(N-ethanoyl acrylamide)-hexyl hydroximic acid resin.
[Fig. 6] gathers 6-[(N-ethanoyl)-4-polyethylene benzamido group] infrared spectrogram of-hexyl hydroximic acid resin.
Embodiment
Following examples are to the further illustrating of content of the present invention, rather than limit the scope of the invention.
In embodiment, all umbers and percentage ratio all refer to quality except as otherwise herein provided.
Embodiment 1
The preparation of linear poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid polymkeric substance
(1) controlling temperature of reactor is 30 ℃, the 2-Pyrrolidone that is 99% by 17.02 parts of purity and 16.48 parts of purity are that 99% Acetyl Chloride 98Min. adds in reactor, add 45.28 parts of methylene dichloride to make solvent, under agitation divide the multiple batches of reactor that adds by 12.72 parts of sodium carbonate, react after 3 hours; And then 13.90 parts of oxammonium hydrochlorides and 42.40 parts of sodium carbonate are added in above-mentioned reactor, and add 47.40 parts of methyl alcohol to make solvent, further react 3 hours; Then being adjusted to pH value with 1mol/L sulfuric acid is 6 to separate out organic phase and be 4-kharophen butyl hydroximic acid.
(2) linear polyacrylic acid and 16 parts of CDI that the 4-kharophen butyl hydroximic acid that 32 parts of steps 1 made, 7.20 parts of molecular-weight average are 3000 add in reactor; add 92 parts of toluene to make solvent; under agitation add 32.4 parts of sodium carbonate; be heated to 50 ℃; react 4 hours, filter, obtain linear poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid solid; product yield is 97.8%, and calculating polyacrylic hydroxyl oximate rate according to results of elemental analyses is 97.6%.The infrared spectra of product is shown in Fig. 1, wherein 3201cm
-1for N-H and O-H stretching vibration; 2912cm
-1and 2845cm
-1for saturated C-H stretching vibration; 1637cm
-1for C=O stretching vibration, 1569cm
-1for the stretching vibration of acid amides.
Embodiment 2
The preparation of linear poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid polymkeric substance
(1) according to the method for embodiment 1 step (1), the 2-Pyrrolidone that is 99% by 17.02 parts of purity used changes the hexanolactam that 22.64 parts of purity are 99% into, and controlling temperature of reactor is 25 ℃, and other condition is constant, makes 6-kharophen hexyl hydroximic acid.
(2) the 6-kharophen hexyl hydroximic acid, the 7.20 parts of molecular-weight average that 37.6 parts of steps 1 are made are 2 × 10
6polyacrylic acid and 16 parts of CDI add in reactor; add 58 parts of acetone to make solvent; under agitation add 31.8 parts of sodium carbonate; be heated to 40 ℃; react 4 hours, filter, obtain poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid solid; product yield is 96.1%, and calculating polyacrylic hydroxyl oximate rate according to results of elemental analyses is 98.9%.The infrared spectra of product is shown in Fig. 2, wherein 3156cm
-1for N-H and O-H stretching vibration; 2934cm
-1and 2856cm
-1for saturated C-H stretching vibration; 1644cm
-1for C=O stretching vibration, 1582cm
-1for the stretching vibration of acid amides.
Embodiment 3
The preparation of poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid resin
The preparation process of 4-kharophen butyl hydroximic acid is identical with embodiment 1 step (1), just temperature of reaction is adjusted to 25 ℃.32 parts of 4-kharophen butyl hydroximic acids, 8.62 parts of macropore polyacrylic resin D113 and 16 parts of CDI are added in reactor; add 58 parts of acetone to make solvent; under agitation add 32.4 parts of sodium carbonate; be heated to 60 ℃; react 4 hours, filter, obtain poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid resin; product yield is 96.4%, and the hydroxyl oximate rate that calculates polyacrylic resin according to results of elemental analyses is 97.9%.The infrared spectrogram of product is shown in Fig. 3, wherein 3429cm
-1for N-H and O-H stretching vibration; 2960cm
-1and 2927cm
-1for saturated C-H stretching vibration; 1734cm
-1for C=O stretching vibration, 1635cm
-1for the stretching vibration of acid amides.
Embodiment 4
Poly-4-[(N-ethanoyl)-4-polyethylene benzamido group] preparation of-butyl hydroximic acid resin
The preparation process of 4-kharophen butyl hydroximic acid is identical with embodiment 1 step (1), just temperature of reaction is adjusted to 25 ℃.32 parts of 4-kharophen butyl hydroximic acids and 18.11 parts of chloromethylation styrene resins (cl content is 19.6%) are added in reactor with 10 parts of CDI; add 92 parts of toluene to make solvent; under agitation add 25.2 parts of sodium bicarbonates; be heated to 50 ℃; react 4 hours; filter; obtain poly-4-[(N-ethanoyl)-4-polyethylene benzamido group]-butyl hydroximic acid resin; product yield is 98.1%, and the hydroxyl oximate rate that calculates chloromethylation styrene resin according to results of elemental analyses is 98.7%.Product infrared spectrogram is shown in Fig. 4, wherein 3441cm
-1for N-H and O-H stretching vibration; 3023cm
-1and 2924cm
-1for saturated C-H stretching vibration; 1627cm
-1for amino stretching vibration.
The preparation of poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid resin
The preparation process of 6-kharophen hexyl hydroximic acid is identical with embodiment 2 steps (1), just temperature of reaction is adjusted to 35 ℃.37.6 parts of 6-kharophen hexyl hydroximic acids are added in reactor with 8.62 parts of macropore polyacrylic resin D113 and 16 parts of CDI; add 58 parts of acetone to make solvent; under agitation add 42.4 parts of sodium carbonate; be heated to 50 ℃; react 4 hours, filter, obtain poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid resin; product yield is 97.7%, and the hydroxyl oximate rate that calculates polyacrylic resin according to results of elemental analyses is 97.2%.The infrared spectrogram of product is shown in Fig. 5, wherein 3426cm
-1for N-H and O-H stretching vibration; 2988cm
-1and 2927cm
-1for saturated C-H stretching vibration; 1727cm
-1for C=O stretching vibration, 1645cm
-1for the stretching vibration of acid amides.
Embodiment 6
Poly-6-[(N-ethanoyl)-4-polyethylene benzamido group] preparation of-hexyl hydroximic acid resin
The preparation process of 6-kharophen hexyl hydroximic acid is identical with embodiment 2 steps (1), just temperature of reaction is adjusted to 25 ℃.37.6 parts of 6-kharophen hexyl hydroximic acids and 18.11 parts of chloromethylation styrene resins (cl content is 19.6%) are added in reactor with 12 parts of DIC; add 92 parts of toluene to make solvent; under agitation add 42.4 parts of sodium carbonate; be heated to 40 ℃; react 4 hours, filter, obtain poly-6-[(N-ethanoyl)-4-polyethylene benzamido group]-hexyl hydroximic acid resin; product yield is 97.9%, and the hydroxyl oximate rate that calculates polyacrylic resin according to results of elemental analyses is 97.6%.The infrared spectrogram of product is shown in Fig. 6, wherein 3448cm
-1for N-H and O-H stretching vibration; 3025cm
-1and 2925cm
-1for saturated C-H stretching vibration; 1627cm
-1for amino stretching vibration.
Embodiment 7
The sedimentation function of linear poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid
Get respectively the Co that 100 parts of concentration are 10mmol/L (II), Cu (II), Fe (III) metal ion solution, with sulphur acid for adjusting pH value be 5.5, respectively add 1 part of linearity to gather 4-(N-ethanoyl acrylamide)-butyl hydroximic acid as precipitation agent, at 25 ℃, stir 30 minutes, filtering separation filtrate and precipitation, measure the concentration of metal ion in filtrate, calculate Co in solution (II), Cu (II), the clearance of Fe (III) is respectively 89.22%, 95.30% and 90.85%, illustrate that linear poly-4-(N-ethanoyl acrylamide)-butyl hydroximic acid is to Co (II), Cu (II), Fe (III) has good precipitation and removes ability.
The flocculating settling characteristics of linear poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid
To gather after the saponification of 6-(N-ethanoyl acrylamide)-hexyl hydroximic acid sodium hydroxide; join solid content and be in 25% alumina laterite slurry; it is poly-that 6-(N-ethanoyl acrylamide)-hexyl hydroximic acid consumption is 5mg/L; within 15 minutes, substantially complete settling process; red mud height of deposition is 22.8% of the former height of ore pulp, illustrates that poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid has good settling property to red mud.
Embodiment 9
The absorption property of polyamidoamines hydroximic acid resin to metal ion
The Fe (III) that compound concentration is 1g/L respectively, Cu (II), Ni (II), La (III), Y (III) metal ion solution, poly-4-(N-ethanoyl the acrylamide)-butyl hydroximic acid resin that respectively adds respectively embodiment 3～6 to prepare by the consumption of 4g/L, poly-6-(N-ethanoyl acrylamide)-hexyl hydroximic acid resin, poly-4-[(N-ethanoyl)-4-polyethylene benzamido group]-butyl hydroximic acid resin and poly-6-[(N-ethanoyl)-4-polyethylene benzamido group]-hexyl hydroximic acid resin, controlling adsorption temp is 25 ℃, adsorption time is 3 hours, the loading capacity that records resin is as shown in table 1.
The loading capacity (unit: mmol/g) of table 1 polyamidoamines hydroximic acid resin to metal ion
Claims (10)
1. a grafting amido hydroximic acid polymkeric substance, is characterized in that, is prepared through substitution reaction by polyacrylic acid or chloromethylated polystyrene and the N-kharophen alkyl hydroximic acid with formula I structure, has formula II structural unit:
Wherein,
N is that 3～5, R is
or
group;
The percentage of grafting of N-kharophen alkyl hydroximic acid on polyacrylic acid or chloromethylated polystyrene is not less than 97%.
2. grafting amido hydroximic acid polymkeric substance as claimed in claim 1, is characterized in that, described polyacrylic acid comprises that molecular weight is 200～6 × 10
6linear polyacrylic acid or the degree of crosslinking CP that is 2%～12%, described chloromethylated polystyrene degree of crosslinking is 2%～12%.
3. grafting amido hydroximic acid polymkeric substance as claimed in claim 1, is characterized in that, described N-kharophen alkyl hydroximic acid is prepared by following methods: by C
4～C
6lactan and Acetyl Chloride 98Min. join in reactor with mol ratio 1:1.0～1.5, stir at 0～50 ℃, carry out N-amidate action, simultaneously, the alkaline compound of 1.0～3.0 times of molar weights of described lactan is slowly joined in described reactor, in and N-amidate action generate acid; After N-amidate action completes, in described reactor, add the azanol of 1～1.2 times of molar weight of described lactan and the alkaline compound of 1～3 times of molar weight of described lactan, carry out ring-opening reaction, after ring-opening reaction completes, in reactor, add acid to be adjusted to pH value for acid, to obtain final product.
4. grafting amido hydroximic acid polymkeric substance as claimed in claim 3, is characterized in that, the described N-acylation reaction time is 1～4h.
5. grafting amido hydroximic acid polymkeric substance as claimed in claim 3, is characterized in that, the described ring-opening reaction time is 1～4h.
6. grafting amido hydroximic acid polymkeric substance as claimed in claim 3, it is characterized in that, described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate, Quilonum Retard, calcium oxide, tertiary butyl sodium alkoxide or tertiary butyl potassium alcoholate.
7. the preparation method of the grafting amido hydroximic acid polymkeric substance as described in claim 1～6 any one, it is characterized in that, by described N-kharophen alkyl hydroximic acid and polyacrylic acid or chloromethylated polystyrene under alkaline compound and condensing agent existence condition, carry out substitution reaction in 20～80 ℃, to obtain final product; Wherein, the chloromethyl in carboxyl or the chloromethylated polystyrene in polyacrylic acid: the kharophen in N-kharophen hydroximic acid: alkaline compound: the mol ratio of condensing agent is 1:1～2:1.5～4:0.5～1.
8. preparation method as claimed in claim 7, it is characterized in that, described condensing agent is N, N-carbonyl dimidazoles, benzotriazole-N, N, N, N-tetramethyl-urea phosphofluoric acid ester, O-(7-nitrogen benzotriazole)-N, N, N, N-tetramethyl-urea phosphofluoric acid ester, N, N-dicyclohexylcarbodiimide, N, N-DIC or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus.
9. preparation method as claimed in claim 7, is characterized in that, described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate, Quilonum Retard, calcium oxide, tertiary butyl sodium alkoxide or tertiary butyl potassium alcoholate.
10. preparation method as claimed in claim 7, is characterized in that, the described substitution reaction time is 1～4h.
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| CN109530094A (en) * | 2019-01-17 | 2019-03-29 | 湖南中医药大学 | Amide groups hydroxycarboxylic acid/hydroximic acid compound and its application in mineral floating |
| CN112250779A (en) * | 2020-10-27 | 2021-01-22 | 深圳市裕同包装科技股份有限公司 | Photochromic microspheres, preparation method and application |
| CN115819652A (en) * | 2022-12-06 | 2023-03-21 | 中南大学 | 2-amino pentanedioxyhydroxamic acid modified polyacrylic acid chelating resin and preparation method and application thereof |
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| CN109530094A (en) * | 2019-01-17 | 2019-03-29 | 湖南中医药大学 | Amide groups hydroxycarboxylic acid/hydroximic acid compound and its application in mineral floating |
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| CN115819652A (en) * | 2022-12-06 | 2023-03-21 | 中南大学 | 2-amino pentanedioxyhydroxamic acid modified polyacrylic acid chelating resin and preparation method and application thereof |
| CN115819652B (en) * | 2022-12-06 | 2023-09-05 | 中南大学 | 2-aminopentanedioxime acid modified polyacrylic acid chelate resin and preparation method and application thereof |
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