CN102504061A - Super chelating ion exchange resin - Google Patents
Super chelating ion exchange resin Download PDFInfo
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- CN102504061A CN102504061A CN2011103225037A CN201110322503A CN102504061A CN 102504061 A CN102504061 A CN 102504061A CN 2011103225037 A CN2011103225037 A CN 2011103225037A CN 201110322503 A CN201110322503 A CN 201110322503A CN 102504061 A CN102504061 A CN 102504061A
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- 0 *CC*(CCN)(CC1CCC**(C2)[C@]2CCCC1)Cc(cc1)cc(C=O)c1O Chemical compound *CC*(CCN)(CC1CCC**(C2)[C@]2CCCC1)Cc(cc1)cc(C=O)c1O 0.000 description 2
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- Treatment Of Water By Ion Exchange (AREA)
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 PS side chain connects the macromolecular material of quaternary ammonium group and Schiff's base and three kinds of functional groups of amidoxim, as chelating ion exchange resin, belongs to field of functional materials.Be used for the detection and the removal of water resources and drink heavy metal ion.
Technical background
Two big serial ion exchange resin, film or the filamentary material that is carried functional group such as Schiff's base, amidoxim, amido, carboxyl, phosphonate group, sulfydryl, carbonyl by PS and polyacrylic ester and produce is the normal functional materialss that use of 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 metals ion.Traditional ion exchanging function material only has the function or the effect of pre-concentration, separation, enrichment, recovery heavy metal ion; But do not possess detection, identification, analytic function, especially can't indicate or in time show the saturated adsorbed state of ion exchanging function material metals ion.Fluorescence chemical sensor detection technique and the ion intelligent identification technology of report etc. can be realized the original position identification of multiple metals ion and detect in recent years, these technology have trace routine easy, detect sensitive, identification sensitivity, analyzing and testing characteristics such as circulation ratio height as a result.But the chemical structure of present employed metal ion sensor and metals 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 metals 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 metals 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 the industrial and mining enterprises sanitary sewage disposal pond is disposed and seawater in extract metals ion.
In view of the problem of art methods and material existence, the present invention provides a kind of super chelating ion exchange resin, and described super chelating ion exchange resin refers to PS 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-Functional group; 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 logical formula I:
refers to crosslinked or uncrosslinked polystyrene resin ball in its formula of (I), 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 the super chelating ion exchange resin of logical formula I provided by the invention each water system in 1~14pH value scope; Present different state of charge; Complex ability to metals ion changes to some extent, especially to the complexing high adsorption capacity of heavy metal ion, and then produces the function of separation of heavy metal ions.
Behind the super chelating ion exchange resin adsorbing metal ions of logical formula I of the present invention; Can use inexpensive hydrochloric acid, nitric acid, Sodium Sulphide or ammonium sulfide to make things convenient for its adsorbed metals ion of desorption; And recovery metals ion; The super chelating ion exchange resin of described logical formula I also is able to regeneration simultaneously, recycles safe and effective.
The preparation raw material of the super chelating ion exchange resin of logical formula I of the present invention comprises: chloromethylated polystyrene macroporous resin ball (abbreviating the chlorine ball as), two (2-cyanoethyl) amine, 5-chloromethyl salicylic aldehyde, anthranilic acid, para-amino benzoic acid, Ortho-Aminophenol, 2-amino-1-naphthoic acid, 2-EL-970,6-quinolylamine, 5-amino-oxine and ETHYLE ACETATE, diox, acetone and other organic solvent all belong to commodity, are easy to buy.The technology of preparing of the super chelating ion exchange resin of described logical formula I 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, the super chelating ion exchange resin of logical formula I provided by the invention has functions such as multiple metal-ion fluorescent chromogenic assay, impurity elimination separation, extracting and enrichings, so be that industrial and mining enterprises handle waste water and the efficient material that reclaims multiple metals ion.
Super chelating ion exchange resin of the present invention makes through following steps:
Step 1,
The chlorine ball is dispersed in swelling in the organic solvent, and alkali reagent with two (2-cyanoethyl) amine reactions 20~150 hours, filters under the room temperature as acid binding agent, processes logical formula II weakly alkaline polystyrene functional resin balls (abbreviating PS-BN as), sees that reaction formula is 1.:
Wherein
of reaction formula described in 1. refers 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 ETHYLE ACETATE; The consumption of said 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 said chlorine ball/two (2-cyanoethyl) amine/alkali reagent is 1: 0.2~5: 0.2~2.
The 5-chloromethyl salicylic aldehyde of 0.2~2 times of relative PS-BN quality is dissolved in the organic solvent; Add the prepared logical formula II PS-BN of step 1 again; Stirring at room reaction 20~80 hours is filtered, behind organic solvent washing; Make the logical formula III 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
of reaction formula described in 2. refers to crosslinked or uncrosslinked polystyrene resin ball; Described organic solvent refers to 1; 4-dioxane, THF, acetone, 1; 2-ethylene dichloride, chloroform, methylene dichloride, acetonitrile or ETHYLE ACETATE, the consumption of said organic solvent are 2~20 times of PS-BN quality.
Step 3,
In absolute ethyl 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 the prepared logical formula III PS-BNS of step 2 again, Glacial acetic acid min. 99.5 is as catalyzer; 60~80 ℃ of temperature controls; Reacted 2~80 hours, and made logical 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 said absolute ethyl alcohol is 2~20 times of PS-BNS quality.
Step 4,
In ethanol or methyl alcohol, add oxammonium hydrochloride, stir down and use soda-lime to regulate pH value to 6.0~8.5, filter and remove solids; Add logical formula IV PS-BNSA polystyrene functional resin balls in the gained filtrating; 75~85 ℃ of temperature controls, stirring reaction 2~80 hours is through filtration, deionized water wash three times, drying process; Make the logical super chelating ion exchange resin ball of formula I, see that reaction formula is 4.:
Wherein
of reaction formula described in 3. refers 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 quicklime (being also referred to as unslaked lime); The mass ratio of said PS-BNSA/ oxammonium hydrochloride/soda-lime is 1: 0.2~5: 0.2~5, and the consumption of said ethanol or methyl alcohol is 2~10 times of PS-BNSA quality.
Following embodiment further specifies super chelating ion exchange resin of logical formula I provided by the invention and preparation method thereof, and its purpose is to understand better content of the present invention.Therefore, unlisted super chelating ion exchange resin of logical formula I and preparation method thereof should not be regarded as the restriction to protection domain of the present invention among the embodiment.
Description of drawings
Fig. 1 is that pH is to the super chelating ion exchange resin absorption in PS-BNSAH-1~5 Zn
2+Influence.
Specific embodiment
The preparation of the super chelating ion exchange resin of embodiment 1 PS-BNSAH-1
The preparation of step 1 PS-BN-1
Taking by weighing commercially available degree of crosslinking is that 4 chlorinity are 14.7% PS porous small ball 100 grams and 180 grams 1, and the 4-dioxane splashes into two (2-cyanoethyl) amine of 200 grams continuously under the room temperature, and stirring reaction added yellow soda ash 80 grams after 60 hours, continued 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 salicylic aldehyde 80 grams and be dissolved in 400 milliliters of ETHYLE 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 makes 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 absolute ethyl 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 min. 99.5 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, progressively add soda-lime 116 grams under stirring, adjustment pH value is filtered and is removed solids after 7.0, the PS-BNSA-1 that the adding step 2 makes in the filtrating, and 65~75 ℃ of temperature controls reacted 48 hours.Filter, deionized water wash 3 times, oven dry makes the super chelating ion exchange resin ball of the 258.4 orange red PS-BNSAH-1 of gram.Ultimate analysis: cl content 3.68%, nitrogen content 11.76%.
The preparation of the super chelating ion exchange resin of embodiment 2 PS-BNSAH-2
Method and operation steps according to embodiment 1; It is the 2-EL-970 that anthranilic acid in embodiment 1 step 3 is changed; Promptly make the super chelating ion exchange resin of yellow PS-BNSAH-2; Through analyzing the cl content 4.47% of learning the super chelating ion exchange resin of PS-BNSAH-2, nitrogen content 15.63%.
The preparation of the super chelating ion exchange resin of embodiment 3 PS-BNSAH-3
Method and operation steps according to embodiment 1; It is Ortho-Aminophenol that anthranilic acid in embodiment 1 step 3 is changed; Promptly make the super chelating ion exchange resin of pale brown look PS-BNSAH-3; Through analyzing the cl content 4.33% of learning the super chelating ion exchange resin of PS-BNSAH-3, nitrogen content 12.07%.
The preparation of the super chelating ion exchange resin of embodiment 4 PS-BNSAH-4
Method and operation steps according to embodiment 1; It is 5-amino-oxine that anthranilic acid in embodiment 1 step 3 is changed; Promptly make the super chelating ion exchange resin of sorrel PS-BNSAH-4; Through analyzing the cl content 3.83% of learning the super chelating ion exchange resin of PS-BNSAH-4, nitrogen content 13.72%.
The preparation of the super chelating ion exchange resin of embodiment 5 PS-BNSAH-5
Method and operation steps according to embodiment 1; With the degree of crosslinking in embodiment 1 step 2 is that 4 chlorinity are that 14.7% PS porous small ball is changed to degree of crosslinking is 2, chlorinity is 17.3% PS porous small ball; Promptly make the super chelating ion exchange resin of PS-BNSAH-5; Through analyzing the cl content 3.83% of learning the super chelating ion exchange resin of PS-BNSAH-5, nitrogen content 12.91%.
Embodiment 6 pH are to the super chelating ion exchange resin absorption in PS-BNSAH-1~5 Zn
2+Influence
5000 milliliters of preparation 50.00mg/L solder(ing)acids; Functional quality percentage ratio is that 20% hydrochloric acid and mass percent are 30% aqueous sodium carbonate adjustment solder(ing)acid pH=2,4,6,8,10 respectively; Continuously the ion exchange column 2 hours of 100 gram PS-BNSAH-1~5 super chelating ion exchange resins is equipped with in drip washing, uses flame atomic absorption spectrophotometer to measure Zn in the solder(ing)acid
2+Concentration change, calculate the amount (in every gram resin absorption zine ion mmole number) of PS-BNSAH-1~5 super chelating ion exchange resin absorption zine ion, the result sees accompanying drawing 1.
The super chelating ion exchange resin absorption in embodiment 7 PS-BNSAH-1~4 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 PS-BNSAH-1~4 super chelating ion exchange resins respectively to see table 1.
The fluorescence developing situation of table 1 PS-BNSAH-1~4 super chelating ion exchange resins
Claims (2)
1. super chelating ion exchange resin is characterized in that having chemical structure shown in the logical formula I:
2. according to the preparation method of the described super chelating ion exchange resin of claim 1, it is characterized in that comprising the steps:
Step 1,
Chloromethylated polystyrene macroporous resin ball (abbreviating the chlorine ball as) is dispersed in swelling in the organic solvent; Alkali reagent is as acid binding agent; With two (2-cyanoethyl) amine reactions 20~150 hours, filter out resin balls, the water washing after drying under the room temperature; Process logical formula II weakly alkaline polystyrene functional resin balls (abbreviating PS-BN as), see that reaction formula is 1.:
Wherein
of reaction formula described in 1. refers 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 ETHYLE ACETATE; The consumption of said 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 said chlorine ball/two (2-cyanoethyl) amine/alkali reagent is 1: 0.2~5: 0.2~2;
Step 2,
5-chloromethyl salicylic aldehyde is dissolved in the organic solvent; Add the prepared logical formula II PS-BN of step 1 again; Stirring at room reaction 20~80 hours is filtered, behind organic solvent washing; Make the logical formula III 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
of reaction formula described in 2. refers to crosslinked or uncrosslinked polystyrene resin ball; Described organic solvent refers to 1; 4-dioxane, THF, acetone, 1; 2-ethylene dichloride, chloroform, methylene dichloride, acetonitrile or ETHYLE ACETATE; The consumption of said organic solvent is 2~20 times of PS-BN quality, and the mass ratio of said 5-chloromethyl salicylic aldehyde/PS-BN is 0.2~2: 1;
Step 3,
In absolute ethyl alcohol, add Q-NH
2, after the stirring and dissolving, dropping into the prepared logical formula III PS-BNS of step 2 again, Glacial acetic acid min. 99.5 is as catalyzer, and 60~80 ℃ of temperature controls reacted 2~80 hours, made logical 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, 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 said absolute ethyl alcohol is 2~20 times of PS-BNS quality;
Step 4,
In ethanol or methyl alcohol, add oxammonium hydrochloride, stir down and use soda-lime to regulate pH value to 6.0~8.5, filter and remove solids; Add logical formula IV PS-BNSA polystyrene functional resin balls in the gained filtrating; 75~85 ℃ of temperature controls, stirring reaction 2~80 hours is through filtration, deionized water wash three times, drying; Make the logical super chelating ion exchange resin ball of formula I, see that reaction formula is 4.:
Wherein
of reaction formula described in 3. refers 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 quicklime (being also referred to as unslaked lime); The mass ratio of said PS-BNSA/ oxammonium hydrochloride/soda-lime is 1: 0.2~5: 0.2~5, and the consumption of said ethanol or methyl alcohol is 2~10 times of PS-BNSA quality.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113278096A (en) * | 2021-05-24 | 2021-08-20 | 江苏海洋大学 | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof |
CN113713783A (en) * | 2021-09-06 | 2021-11-30 | 核工业北京化工冶金研究院 | Benzimidazole-amidoxime fiber, and preparation method and application thereof |
Families Citing this family (1)
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JP6330416B2 (en) * | 2014-03-27 | 2018-05-30 | 島根県 | Arsenic adsorptive resin particles |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113278096A (en) * | 2021-05-24 | 2021-08-20 | 江苏海洋大学 | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof |
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 |
CN113713783A (en) * | 2021-09-06 | 2021-11-30 | 核工业北京化工冶金研究院 | Benzimidazole-amidoxime fiber, and preparation method and application 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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