CN102504061B - Super chelating ion exchange resin - Google Patents
Super chelating ion exchange resin Download PDFInfo
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- CN102504061B CN102504061B CN 201110322503 CN201110322503A CN102504061B CN 102504061 B CN102504061 B CN 102504061B CN 201110322503 CN201110322503 CN 201110322503 CN 201110322503 A CN201110322503 A CN 201110322503A CN 102504061 B CN102504061 B CN 102504061B
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- ion exchange
- general formula
- exchange resin
- ball
- organic solvent
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- OMHSYLNUQGUJLG-UHFFFAOYSA-N C(C1)C11C(C2)C2CC1 Chemical compound C(C1)C11C(C2)C2CC1 OMHSYLNUQGUJLG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a super chelating ion exchange resin which comprises three functional groups including a macroporous spherical polystyrene resin ball surface bonded quaternary ammonium group, the Schiff base group and the amidoxime group. The quaternary ammonium group has the anion exchange function, the Schiff base group shows the chromogenic and fluorogenic properties together with heavy metal ions including Zn<2+>, Pb<2+>, Cr<3+>or Cu<2+>, and the amidoxime group has the function of selectively adsorbing UO2<2+> of Au<3+> or Ag<+> in a chelating way, therefore, the super chelating ion exchange resin provided by the invention has the functions of in situ detection, chromogenic and fluorogenic analysis, efficient separation and state making, also has the function of easily recovering precious metal ions and heavy metal ions in various water systems and is easy to regenerate.
Description
Technical field
The present invention relates to a kind of functional high molecule material, particularly the polystyrene side chain connects the macromolecular material of quaternary ammonium group and Schiff's base and three kinds of function bases of amidoxim, as chelating ion exchange resin, belongs to field of functional materials.Be used for detection and the removal of water resources and drink heavy metal ion.
Technical background
Two large serial ion exchange resin, film or the filamentary material that is carried the functional group such as Schiff's base, amidoxim, amido, carboxyl, phosphonate group, sulfydryl, carbonyl by polystyrene and polyacrylic ester and produce is the normal functional materialss that use of the industries such as modern chemical industry, light industry wine brewing, Treatment of Industrial Water, mineral products metallurgy, and purpose is to remove or extract such as Ca
2+, Mg
2+, Hg
2+, Cd
2+, Zn
2+, Pb
2+, Cr
3+, Au
3+Or Cu
2+Deng metal ion.Traditional ion exchanging function material only has function or the effect of pre-concentration, separation, enrichment, recovery heavy metal ion, but do not possess detection, identification, analytic function to metal ion, especially can't indicate or in time show the saturated adsorption state of ion exchanging function material.The fluorescence chemical sensor detection technique of report and ion intelligent identification technology etc. can be realized the original position identification of many kinds of metal ions and detect in recent years, these technology have trace routine easy, detect sensitive, identification is responsive, analyzing and testing circulation ratio high as a result.But the chemical structure of present employed metal ion sensor and metal ion Intelligent Recognition material is complicated, and synthetic cost is high, and they also only have the analysis recognition function simultaneously, do not have separation, enrichment, recovery metal ion function or effect.Therefore, people are anxious expect search out a kind ofly have that in situ detection, concentration analysis, kind are separated concurrently, the novel material of metal ion in the enriching and recovering water system, and require its characteristic with real-time expression adsorbing metal ions state of saturation, be convenient to that practicality operation in industrial and mining enterprises' Domestic sewage treatment tank is disposed and seawater in extract metal ion.
Problem in view of art methods and material existence the invention provides a kind of super chelating ion exchange resin, and described super chelating ion exchange resin refers to polystyrene polymer side chain bonding quaternary ammonium group, Schiff's base and three kinds of functional groups of amidoxim.Described quaternary ammonium group has the anionresin function, is to extract UO in the aqueous solution
2 2+, UO
2(SO
4)
3 4-Or UO
2(CO
3)
3 4-The function base; Described Schiff's base has and Zn
2+, Cu
2+, Pd
2+Or Ni
2+Fluorescence developing character etc. heavy metal ion; Described amidoxim has selectivity chelating absorption UO
2 2+, UO
2(CO
3)
3 4-, Au
3+Or Ag
+Function, so super chelating ion exchange resin provided by the invention has in situ detection, fluorometric analysis, high efficiency separation, manifests adsorbed state, regeneration easily, function or the effect that can reclaim precious metal ion in each water system and heavy metal ion.
Summary of the invention
Super chelating ion exchange resin provided by the invention has chemical structure shown in the general formula (I):
In its formula of (I)
Refer to crosslinked or uncrosslinked polystyrene resin ball, Q be selected from replace or unsubstituted phenyl ring, naphthalene nucleus, pyridine ring, quinoline ring, benzothiazole ring, benzoglyoxaline ring or benzoxazole ring in a kind of.
In general formula provided by the invention (I) super chelating ion exchange resin each water system in 1～14pH value scope, present different state of charge, complex ability to metal ion changes to some extent, especially to the complexing high adsorption capacity of heavy metal ion, and then produce the function of separation of heavy metal ions.
Behind general formula of the present invention (I) the super chelating ion exchange resin adsorbing metal ions, can use inexpensive hydrochloric acid, nitric acid, Sodium Sulphide or ammonium sulfide to make things convenient for its metal ion that adsorbs of desorption, and recovery metal ion, described general formula (I) super chelating ion exchange resin is also regenerated simultaneously, recycles safe and effective.
The raw materials of general formula of the present invention (I) super chelating ion exchange resin comprises: chloromethylated polystyrene macroporous resin ball (referred to as the chlorine ball), two (2-cyanoethyl) amine, 5-chloromethyl salicylaldehyde, anthranilic acid, para-amino benzoic acid, Ortho-Aminophenol, 2-amino-1-naphthoic acid, PA, 6-quinolylamine, 5-amino-8-hydroxyquinoline and ethyl acetate, diox, acetone and other organic solvent all belong to commodity, are easy to buy.The technology of preparing of described general formula (I) super chelating ion exchange resin is simple and easy to do, and each step yield is high, and the three wastes are few, and described super chelating ion exchange resin price is low.
In sum, general formula provided by the invention (I) super chelating ion exchange resin has functions such as the analysis of many kinds of metal ions fluorescence developing, impurity elimination separation, extracting and enrichings, so be the efficient material that industrial and mining enterprises process waste water and recovery many kinds of metal ions.
Super chelating ion exchange resin of the present invention makes as follows:
Step 1,
The chlorine ball is dispersed in swelling in the organic solvent, alkali reagent with two (2-cyanoethyl) amine reactions 20～150 hours, filters under the room temperature as acid binding agent, make general formula (II) weakly alkaline polystyrene functional resin balls (referred to as PS-BN), see that reaction formula is 1.:
Wherein reaction formula is described in 1.
Refer to crosslinked or uncrosslinked polystyrene resin ball, described organic solvent refers to 1,4-dioxane, acetone, 1,2-ethylene dichloride, ethanol, propyl alcohol, Virahol or ethyl acetate, the consumption of described organic solvent is 2～20 times of chlorine ball quality, described alkali reagent refers to salt of wormwood or yellow soda ash, and the mass ratio of described chlorine ball/pair (2-cyanoethyl) amine/alkali reagent is 1: 0.2～5: 0.2～2.
The 5-chloromethyl salicylaldehyde of 0.2～2 times of relative PS-BN quality is dissolved in the organic solvent, add again the prepared general formula of step 1 (II) PS-BN, stirring at room reaction 20～80 hours, filter, behind organic solvent washing, make general formula (III) the polystyrene functional resin balls (being called for short PS-BNS) that side chain connects salicylic aldehyde and quaternary ammonium group, see that reaction formula is 2.:
Wherein reaction formula is described in 2.
Refer to crosslinked or uncrosslinked polystyrene resin ball, described organic solvent refers to 1,4-dioxane, tetrahydrofuran (THF), acetone, 1,2-ethylene dichloride, chloroform, methylene dichloride, acetonitrile or ethyl acetate, the consumption of described organic solvent is 2～20 times of PS-BN quality.
Step 3,
In dehydrated alcohol, add Q-NH
2(Q refer to replace or unsubstituted phenyl ring, naphthalene nucleus, pyridine ring, quinoline ring, benzothiazole ring, benzoglyoxaline ring or benzoxazole ring in a kind of), after the stirring and dissolving, drop into again the prepared general formula of step 2 (III) PS-BNS, Glacial acetic acid is as catalyzer, 60～80 ℃ of temperature controls, reacted 2～80 hours, and made general formula (IV) PS-BNSA polystyrene functional resin balls, see that reaction formula is 3.:
Wherein reaction formula is described in 3.
Refer to crosslinked or uncrosslinked polystyrene resin ball, Q be selected from replace or unsubstituted phenyl ring, naphthalene nucleus, pyridine ring, quinoline ring, benzothiazole ring, benzoglyoxaline ring or benzoxazole ring in a kind of, PS-BNS and Q-NH
2Mass ratio be 0.2～2: 1, the consumption of described dehydrated alcohol is 2～20 times of PS-BNS quality.
In ethanol or methyl alcohol, add oxammonium hydrochloride, stir lower soda-lime adjusting pH value to 6.0～8.5 of using, filter and remove solids, add general formula (IV) PS-BNSA polystyrene functional resin balls in the gained filtrate, 75～85 ℃ of temperature controls, stirring reaction 2～80 hours is through filtration, deionized water wash three times, drying process, make general formula (I) super chelating ion exchange resin ball, see that reaction formula is 4.:
Wherein reaction formula is described in 3.
Refer to crosslinked or uncrosslinked polystyrene resin ball, Q be selected from replace or unsubstituted phenyl ring, naphthalene nucleus, pyridine ring, quinoline ring, benzothiazole ring, benzoglyoxaline ring or benzoxazole ring in a kind of, described soda-lime is composite and get according to mass ratio 1: 3 by yellow soda ash or salt of wormwood and calcium oxide (being also referred to as unslaked lime), the mass ratio of described PS-BNSA/ oxammonium hydrochloride/soda-lime is 1: 0.2～5: 0.2～5, and the consumption of described ethanol or methyl alcohol is 2～10 times of PS-BNSA quality.
Following embodiment further specifies general formula provided by the invention (I) super chelating ion exchange resin and preparation method thereof, and its purpose is to understand better content of the present invention.Therefore, unlisted general formula (I) super chelating ion exchange resin and preparation method thereof should not be considered as limiting the scope of the invention among the embodiment.
Description of drawings
Fig. 1 is that pH is to PS-BNSAH-1～5 super chelating ion exchange resins absorption Zn
2+Impact.
Specific embodiment
The preparation of embodiment 1 PS-BNSAH-1 super chelating ion exchange resin
The preparation of step 1 PS-BN-1
Taking by weighing commercially available degree of crosslinking is that 4 chlorinity are 14.7% polystyrene porous small ball 100 grams and 180 grams 1, the 4-dioxane splashes into two (2-cyanoethyl) amine of 200 grams continuously under the room temperature, stirring reaction is after 60 hours, add yellow soda ash 80 grams, continue to stir 1 hour.From reaction system, filter out bead, deionized water wash 3 times, oven dry makes 143.6 gram PS-BN-1.Ultimate analysis: nitrogen content 10.35%.
The preparation of step 2 PS-BNS-1
Take by weighing 5-chloromethyl salicylaldehyde 80 grams and be dissolved in 400 milliliters of ethyl acetate, in the PS-BN-1 input reaction system with the step 1 gained, stirring at room reaction 48 hours.Filter and take out bead, with hot cold ethyl acetate washing, vacuum drying, make 198.9 gram PS-BNS-1.Ultimate analysis: cl content 5.78%, nitrogen content 7.48%.
The preparation of step 3 PS-BNSA-1
Add 400 milliliters of dehydrated alcohols and 80 gram anthranilic acids in the reaction flask, after the stirring and dissolving, add the PS-BNS-1 that step 2 makes, 2 milliliters of Glacial acetic acid are catalyzer, heat up 65～75 ℃, react 48 hours.Filter, the deionized water wash of heat 3 times, oven dry makes the orange red PS-BNSA-1 polystyrene functional resin balls of 238.5 grams.Ultimate analysis: cl content 4.37%, nitrogen content 8.58%.
The preparation of step 4 PS-BNSAH-1
Add 400 milliliters of ethanol and 130 gram oxammonium hydrochlorides in the reaction flask, stir lower soda-lime 116 grams that progressively add, adjust the pH value after 7.0, filter and remove solids, add the PS-BNSA-1 that step 2 makes in the filtrate, 65～75 ℃ of temperature controls reacted 48 hours.Filter, deionized water wash 3 times, oven dry makes the orange red PS-BNSAH-1 super chelating ion exchange resin ball of 258.4 grams.Ultimate analysis: cl content 3.68%, nitrogen content 11.76%.
The preparation of embodiment 2 PS-BNSAH-2 super chelating ion exchange resins
Method and operation steps according to embodiment 1, it is PA that anthranilic acid in embodiment 1 step 3 is changed, namely make yellow PS-BNSAH-2 super chelating ion exchange resin, the analysis showed that the cl content 4.47% of PS-BNSAH-2 super chelating ion exchange resin, nitrogen content 15.63%.
The preparation of embodiment 3 PS-BNSAH-3 super chelating ion exchange resins
Method and operation steps according to embodiment 1, it is Ortho-Aminophenol that anthranilic acid in embodiment 1 step 3 is changed, namely make brown color PS-BNSAH-3 super chelating ion exchange resin, the analysis showed that the cl content 4.33% of PS-BNSAH-3 super chelating ion exchange resin, nitrogen content 12.07%.
The preparation of embodiment 4 PS-BNSAH-4 super chelating ion exchange resins
Method and operation steps according to embodiment 1, it is the 5-amino-8-hydroxyquinoline that anthranilic acid in embodiment 1 step 3 is changed, namely make sorrel PS-BNSAH-4 super chelating ion exchange resin, the analysis showed that the cl content 3.83% of PS-BNSAH-4 super chelating ion exchange resin, nitrogen content 13.72%.
The preparation of embodiment 5 PS-BNSAH-5 super chelating ion exchange resins
Method and operation steps according to embodiment 1, be that 4 chlorinity are that 14.7% polystyrene porous small ball is changed as degree of crosslinking is 2, chlorinity is 17.3% polystyrene porous small ball with the degree of crosslinking in embodiment 1 step 2, namely make the PS-BNSAH-5 super chelating ion exchange resin, the analysis showed that the cl content 3.83% of PS-BNSAH-5 super chelating ion exchange resin, nitrogen content 12.91%.
5000 milliliters of preparation 50.00mg/L solder(ing)acids, functional quality percentage ratio is that 20% hydrochloric acid and mass percent are that 30% aqueous sodium carbonate is adjusted solder(ing)acid pH=2,4,6,8,10 respectively, Continuous leaching is equipped with the ion exchange column 2 hours of 100 gram PS-BNSAH-1～5 super chelating ion exchange resins, uses flame atomic absorption spectrophotometer to measure Zn in the solder(ing)acid
2+Change in concentration, calculate the amount (in every gram resin absorption zine ion mmole number) of PS-BNSAH-1～5 super chelating ion exchange resins absorption zine ion, the results are shown in accompanying drawing 1.
Embodiment 7 PS-BNSAH-1～4 super chelating ion exchange resins absorption Zn
2+And Cu
2+The fluorescence developing situation
Use the solder(ing)acid of pH=6 and the fluorescence developing situation that copper chloride solution floods respectively PS-BNSAH-1～4 super chelating ion exchange resins to see Table 1.
The fluorescence developing situation of table 1PS-BNSAH-1～4 super chelating ion exchange resins
Claims (2)
1. super chelating ion exchange resin, the chemical structure shown in (I) that it is characterized in that having general formula:
General formula (I)
In its formula of (I)
Refer to crosslinked or uncrosslinked polystyrene resin ball, Q be selected from replace or unsubstituted phenyl ring, pyridine ring or quinoline ring in a kind of.
2. according to the preparation method of super chelating ion exchange resin claimed in claim 1, it is characterized in that comprising the steps:
Step 1,
Chloromethylated polystyrene macroporous resin ball (referred to as the chlorine ball) is dispersed in swelling in the organic solvent, alkali reagent is as acid binding agent, reacted 20～150 hours with two (2-cyanoethyl) amine under the room temperature, filter out resin balls, dry after the water washing, make general formula (II) weakly alkaline polystyrene functional resin balls (referred to as PS-BN), see that reaction formula is 1.:
Wherein reaction formula is described in 1.
Refer to crosslinked or uncrosslinked polystyrene resin ball, described organic solvent refers to 1,4-dioxane, acetone, 1,2-ethylene dichloride, ethanol, propyl alcohol, Virahol or ethyl acetate, the consumption of described organic solvent is 2～20 times of chlorine ball quality, described alkali reagent refers to salt of wormwood or yellow soda ash, and the mass ratio of described chlorine ball/pair (2-cyanoethyl) amine/alkali reagent is 1: 0.2～5: 0.2～2;
Step 2,
The 5-chloromethyl salicylaldehyde is dissolved in the organic solvent, add again the prepared general formula of step 1 (II) PS-BN, stirring at room reaction 20～80 hours, filter, behind organic solvent washing, make general formula (III) the polystyrene functional resin balls (being called for short PS-BNS) that side chain connects salicylic aldehyde and quaternary ammonium group, see that reaction formula is 2.:
Wherein reaction formula is described in 2.
Refer to crosslinked or uncrosslinked polystyrene resin ball, described organic solvent refers to 1,4-dioxane, tetrahydrofuran (THF), acetone, 1,2-ethylene dichloride, chloroform, methylene dichloride, acetonitrile or ethyl acetate, the consumption of described organic solvent is 2～20 times of PS-BN quality, and the mass ratio of described 5-chloromethyl salicylaldehyde/PS-BN is 0.2～2: 1;
Step 3,
In dehydrated alcohol, add Q-NH
2, after the stirring and dissolving, dropping into again the prepared general formula of step 2 (III) PS-BNS, Glacial acetic acid is as catalyzer, and 60～80 ℃ of temperature controls reacted 2～80 hours, made general formula (IV) PS-BNSA polystyrene functional resin balls, saw that reaction formula is 3.:
Wherein reaction formula is described in 3.
Refer to crosslinked or uncrosslinked polystyrene resin ball, Q be selected from replace or unsubstituted phenyl ring, pyridine ring or quinoline ring in a kind of, PS-BNS and Q-NH
2Mass ratio be 0.2～2: 1, the consumption of described dehydrated alcohol is 2～20 times of PS-BNS quality;
Step 4,
In ethanol or methyl alcohol, add oxammonium hydrochloride, stir lower soda-lime adjusting pH value to 6.0～8.5 of using, filter and remove solids, add general formula (IV) PS-BNSA polystyrene functional resin balls in the gained filtrate, 75～85 ℃ of temperature controls, stirring reaction 2～80 hours is through filtration, deionized water wash three times, drying, make general formula (I) super chelating ion exchange resin ball, see that reaction formula is 4.:
Wherein reaction formula is described in 4.
Refer to crosslinked or uncrosslinked polystyrene resin ball, Q be selected from replace or unsubstituted phenyl ring, pyridine ring or quinoline ring in a kind of, described soda-lime is composite and get according to mass ratio 1: 3 by yellow soda ash or salt of wormwood and calcium oxide (being also referred to as unslaked lime), the mass ratio of described PS-BNSA/ oxammonium hydrochloride/soda-lime is 1: 0.2～5: 0.2～5, and the consumption of described ethanol or methyl alcohol is 2～10 times of PS-BNSA quality.
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| JP2015188809A (en) * | 2014-03-27 | 2015-11-02 | 島根県 | Arsenic adsorptive resin particle |
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| CN113278096B (en) * | 2021-05-24 | 2022-06-03 | 江苏海洋大学 | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof |
| CN113713783B (en) * | 2021-09-06 | 2023-09-15 | 核工业北京化工冶金研究院 | Benzimidazole-amidoxime fiber, and preparation method and application thereof |
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| US6379876B1 (en) * | 2000-06-13 | 2002-04-30 | Eastman Kodak Company | Thermally processable imaging element comprising an ion exchanged reducing agent |
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| CN101481466A (en) * | 2009-02-12 | 2009-07-15 | 凯瑞化工有限责任公司 | Preparation of high temperature resistant strong alkalinity anion exchange resin |
-
2011
- 2011-10-14 CN CN 201110322503 patent/CN102504061B/en not_active Expired - Fee Related
Patent Citations (4)
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|---|---|---|---|---|
| EP0679167A1 (en) * | 1993-01-15 | 1995-11-02 | The Graver Company | Process for producing ion exchange membranes, and the ion exchange membranes produced thereby |
| US6379876B1 (en) * | 2000-06-13 | 2002-04-30 | Eastman Kodak Company | Thermally processable imaging element comprising an ion exchanged reducing agent |
| CN1513597A (en) * | 2003-07-18 | 2004-07-21 | 中国石油化工股份有限公司 | Anion-exchange resin catalyst for ethylene oxide hydration reaction and preparing process |
| CN101481466A (en) * | 2009-02-12 | 2009-07-15 | 凯瑞化工有限责任公司 | Preparation of high temperature resistant strong alkalinity anion exchange resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015188809A (en) * | 2014-03-27 | 2015-11-02 | 島根県 | Arsenic adsorptive resin particle |
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