CN103537325A - Preparation method of difunctional group weak-base anion exchange resin - Google Patents
Preparation method of difunctional group weak-base anion exchange resin Download PDFInfo
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Abstract
The invention discloses a preparation method of difunctional group weak-base anion exchange resin, which adopts a one-step functional group process for preparation. The preparation method comprises the following steps: sufficiently swelling resin chloromethylated beads by use of an inertia organic solvent, and completely pumping the organic solvent to obtain the sufficiently-swelled resin chloromethylated beads; dissolving long-chain secondary amine and short-chain secondary amine at a mass ratio of (1-30):1 in a polar solvent, and uniformly mixing to obtain a mixed solution; at 0-5 DEG C, dropwise adding the mixed solution into the sufficiently-swelled resin chloromethylated beads, and stirring for reaction for 2-4 hours; at 30-55 DEG C, stirring for reaction for 8-12 hours; completely pumping the reaction liquid, and washing to neutrality; and extracting and drying to obtain the difunctional group weak-base anion exchange resin, wherein the total mass of the long-chain secondary amine and short-chain secondary amine is 0.3-2.1 times that of the non-swelled resin chloromethylated beads. The preparation method disclosed by the invention has the advantages of easiness in synthesis, simplicity in operation, low cost and broad application prospect.
Description
Technical field
The present invention relates to the preparation method field of ion exchange resin, be specifically related to a kind of preparation method of dual-function base weak-base anion-exchange resin.
Background technology
Dual-functional group anion exchange resin is on a resinoid skeleton, to have the anion exchange resin of two kinds of Different Alkali sexual function groups.At present, the external existing dual-functional group strong-base anion-exchange resin that adopts is for report (Peter V.Bonnesen, Environ.Sci.Technol.2000, the 34:3761-3766 of the selective absorption of aqueous solution inorganic anion; B.H.Gu, Environ.Sci.Technol.2000,34:1075-1080), but undeclared this resinoid preparation method.Correlative study shows, the short chain function base on resin makes ion exchange resin have higher adsorption capacity and dynamics preferably, but selectively poor; And long-chain function base can effectively improve the adsorptive selectivity of resin, but its adsorption capacity is low, and dynamic performance is poor.And dual-functional group alkalescence anion-exchange resin can well utilize both advantages, both can improve its dynamics, can strengthen again that it is selective.The advantages such as compare with strong-base anion-exchange resin, it is easy that weak-base anion-exchange resin has desorption and regeneration, and processing cost is low.At present, there is not yet the report of dual-function base weak-base anion-exchange resin abroad.Domestic Pan third (CN1712135A) to take chloromethylation styrene-divinylbenzene polymer (resin chlorine ball) be base material, adopt two step functionalizing legal systems for dual-function base weak-base anion-exchange resin, first adopt long-chain secondary amine to carry out aminated reaction with the abundant resin chlorine ball of swelling, after filtration, drip washing makes single function weak base resin; Gained list function weak base resin after swelling, reacts with short chain secondary amine again, after filtration, extracting, the process such as dry make dual-function base weak-base anion-exchange resin.Its operating procedure is complicated, and cost is higher, and adopts the reaction of substep functionalizing, and in initial reaction liquid, aminated reagent concentration is lower, easily causes prepared resin strong-base group mass contg higher.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of dual-function base weak-base anion-exchange resin, solve resin strong-base group mass contg synthetic in existing dual-function base weak-base anion-exchange resin preparation method higher, the shortcoming that operating procedure is complicated, cost is higher.
The present invention is by the following technical solutions:
A preparation method for dual-function base weak-base anion-exchange resin, adopts a step functionalizing legal system standby, comprises the steps:
Step 1, utilize inert organic solvents by the abundant swelling of resin chlorine ball, drain afterwards the resin chlorine ball that inert organic solvents obtains abundant swelling, wherein said resin chlorine ball is the macropore styrene diethylene benzene copoly mer through chloromethylation;
Step 2, by long-chain secondary amine and short chain secondary amine in mass ratio 1～30:1 be dissolved in polar solvent and mix, obtain mixed solution;
Step 3, at 0～5 ℃, mixed solution prepared by step 2 is added drop-wise in the resin chlorine ball of abundant swelling prepared by step 1, stirring reaction 2～4h; Then at 30～55 ℃, stirring reaction 8～12h; Drain afterwards reactant liquor, water washing is to neutral, and extracting dryly obtains dual-function base weak-base anion-exchange resin, and wherein, the gross mass of described long-chain secondary amine and short chain secondary amine is 0.3～2.1 times of resin chlorine ball quality of not swelling.
The degree of cross linking of the macropore styrene diethylene benzene copoly mer described in step 1 is 2-25%.
Inert organic solvents described in step 1 is any one in benzene, nitrobenzene, carrene, dichloroethanes or DMF.
The secondary amine of long-chain described in step 2 is the secondary amine compound with the straight chained alkyl of 3～10 carbon atoms.
The secondary amine of short chain described in step 2 is the secondary amine compound with the straight chained alkyl of 1～2 carbon atom.
Polar solvent described in step 2 is ethanol.
Beneficial effect of the present invention:
1, the dual-function base weak-base anion-exchange resin that prepared by the present invention can be widely used in the separation and extraction of aqueous acid medium organic matter, long-chain secondary amine can improve the selective of resin, short chain secondary amine can improve adsorption capacity and the dynamic performance of resin, and it is better than commercialization weak-base anion-exchange resin 50%～400% to the adsorption selectivity of organic ion in high concentration inorganic salt solution.
2, preparation method provided by the invention, is easy to synthesize, simple to operate, and cost is lower, has broad application prospects.
The specific embodiment:
Below in conjunction with embodiment, the present invention is done further and explained.The following example is only for the present invention is described, but is not used for limiting practical range of the present invention.
A preparation method for dual-function base weak-base anion-exchange resin, is to adopt a step functionalizing legal system standby, comprises the steps:
Step 1, utilize inert organic solvents by resin chlorine ball swelling 8～12h with abundant swelling, drain afterwards the resin chlorine ball that inert organic solvents obtains abundant swelling, the macropore styrene diethylene benzene copoly mer that wherein said resin chlorine ball is 2-25% for the degree of cross linking through chloromethylation; Described inert organic solvents can be any one in benzene, nitrobenzene, carrene, dichloroethanes or DMF.
Step 2, by long-chain secondary amine, short chain secondary amine in mass ratio 1～30:1 be dissolved in polar solvent and mix, obtain mixed solution, wherein said long-chain secondary amine chemical formula is NH (R
1)
2, R
1for thering is the straight chained alkyl of 3～10 carbon atoms; Described short chain secondary amine chemical formula is NH (R
2)
2, R wherein
2for thering is the straight chained alkyl of 1～2 carbon atom; Described polar solvent can be water, methyl alcohol, ethanol, acetone, DMF or Isosorbide-5-Nitrae-dioxane any one or multiple, be preferably ethanol.
Step 3, at 0～5 ℃ preferably 5 ℃, mixed solution prepared by step 2 is added drop-wise in the resin chlorine ball of abundant swelling prepared by step 1, stirring reaction 2～4h, preferably 2h; Then at 30～55 ℃, stirring reaction 8～12h, preferably 8h; Drain afterwards reactant liquor, water washing is to neutral, absolute ethyl alcohol extracting, and heated-air drying obtains dual-function base weak-base anion-exchange resin, and wherein, the gross mass of described long-chain secondary amine and short chain secondary amine is 0.3～2.1 times of resin chlorine ball quality of not swelling.
Described resin chlorine ball preparation is as follows:
Styrene monomer adds a certain amount of diluted sodium hydroxide solution or styrene monomer is directly filtered to remove polymerization inhibitor through the resin column of strong basic anion-exchange resin is housed;
In 250mL beaker, add 88～96g styrene, 4～12g divinylbenzene, 50～100g atoleine, standby after stirring.In 1000mL three-neck flask, add 450g distilled water, 3.75g gelatin, be warming up to 40～45 ℃, under agitation add above-mentioned styrene, divinylbenzene and atoleine mixed liquor, add 1g benzoyl peroxide, speed with 0.5 ℃/min is warming up to 75～78 ℃, insulation 5h, is slowly warming up to 85 ℃, insulation 4h, reaction finishes, leach resin spheroid, hot wash, packs apparatus,Soxhlet's into after draining, select ethanol to make solvent extraction clean, then heated-air drying, sieves, and the resin Archon of getting suitable particle size is standby;
Resin Archon is soaked in the chloromethyl ether of 4～6 times of its weight, at 30 ℃, soaks 2h, under mechanical agitation, add the anhydrous zinc chloride of resin Archon weight 30～60% to make catalyst, at 30～50 ℃, carry out chloromethylation 10～12h.After reaction finishes, leach the resin Archon of chloromethylation, water and ethanol are washed chlorination mother solution remaining in most spheroid respectively, and then heated-air drying obtains resin chlorine ball, and chlorinty is 12～19.5%.
Embodiment 1
Step 1, in 250mL there-necked flask, adding the degree of cross linking is 10% resin chlorine ball 30g, the benzene swelling 8h with 40mL, drains filtrate.
Step 2,16g dibutyl amine and 3g diethylamine are joined in 20mL industrial alcohol, and stir, obtain mixed solution.
Step 3, under stirring, mixed solution is added drop-wise in there-necked flask and is mixed with resin chlorine ball, controlling solution temperature is 5 ℃, reaction 2h; Rising temperature to 45 ℃, stirring reaction 8h; Drain afterwards amination mother liquor, water washing is to neutral, absolute ethyl alcohol extracting, heated-air drying can make dibutyl amine-diethylamine dual-function base weak-base anion-exchange resin, this resin weak base exchange capacity is 3.2mmo1/g, according to exchange capacity and determination of elemental analysis, to calculate the mol ratio of dibutyl amino and diethylin content in resin be 1.5:1.
Embodiment 2
Step 1, in 250mL there-necked flask, adding the degree of cross linking is 8% resin chlorine ball 30g, the nitrobenzene swelling 12h with 40mL, drains filtrate.
Step 2,50g dioctylamine and 2g dimethylamine are joined in 50mL industrial alcohol, and stir, obtain mixed solution.
Step 3, under stirring, mixed solution is added drop-wise in there-necked flask and is mixed with resin chlorine ball, controlling solution temperature is 5 ℃, reaction 2h; Rising temperature to 55 ℃, stirring reaction 8h; Drain afterwards amination mother liquor, water washing is extremely neutral, absolute ethyl alcohol extracting, and heated-air drying can make dioctylamine-dimethylamine dual-function base weak-base anion-exchange resin, this resin weak base exchange capacity is 3.1mmo1/g, and wherein the mol ratio of dioctylamine base and dimethylamino content is 1.4:1.
Embodiment 3
Step 1, in 250mL there-necked flask, adding the degree of cross linking is 6% resin chlorine ball 30g, the carrene swelling 12h with 40mL, drains filtrate.
Step 2,30g dihexylamine and 4g dimethylamine are joined in 30mL industrial alcohol, and stir, obtain mixed solution.
Step 3, under stirring, mixed solution is added drop-wise in there-necked flask and is mixed with resin chlorine ball, controlling solution temperature is 5 ℃, reaction 2h; Rising temperature to 50 ℃, stirring reaction 8h; Drain afterwards amination mother liquor, water washing is extremely neutral, absolute ethyl alcohol extracting, and heated-air drying can make dihexylamine-dimethylamine dual-function base weak-base anion-exchange resin, this resin weak base exchange capacity is 3.7mmo1/g, and wherein the mol ratio of dihexylamine base and dimethylamino content is 0.6:1.
Embodiment 4
Step 1, in 250mL there-necked flask, adding the degree of cross linking is 2% resin chlorine ball 30g, with the dichloroethanes swelling 12h of 40mL,, drain filtrate.
Step 2,60g didecylamine and 2g dimethylamine are added in 50mL industrial alcohol, and stir, obtain mixed solution.
Step 3, under stirring, mixed solution is added drop-wise in there-necked flask and is mixed with resin chlorine ball, controlling solution temperature is 5 ℃, reaction 2h; Rising temperature to 55 ℃, stirring reaction 8h; Drain afterwards amination mother liquor, water washing is extremely neutral, absolute ethyl alcohol extracting, and heated-air drying can make didecylamine-dimethylamine dual-function base weak-base anion-exchange resin, this resin weak base exchange capacity is 2.9mmo1/g, and wherein the mol ratio of didecyl amido and dimethylamino content is 1.3:1.
Embodiment 5
Step 1, in 250mL there-necked flask, adding the degree of cross linking is 25% resin chlorine ball 30g, with the nitrobenzene swelling 12h of 40mL,, drain filtrate.
Step 2,7g di-n-propylamine and 3g dimethylamine are added in 30mL industrial alcohol, and stir, obtain mixed solution.
Step 3, under stirring, mixed solution is added drop-wise in there-necked flask and is mixed with resin chlorine ball, controlling solution temperature is 0 ℃, reaction 4h; Rising temperature to 30 ℃, stirring reaction 12h; Drain afterwards amination mother liquor, water washing is extremely neutral, absolute ethyl alcohol extracting, and heated-air drying can make di-n-propylamine-dimethylamine dual-function base weak-base anion-exchange resin, this resin weak base exchange capacity is 2.3mmo1/g, and wherein the mol ratio of dipropyl amido and dimethylamino content is 0.3:1.
Embodiment 6
Step 1, in 250mL there-necked flask, adding the degree of cross linking is 8% resin chlorine ball 60g, with the DMF swelling 12h of 80mL,, drain filtrate.
Step 2,16g di-n-propylamine and 16g diethylamine are added in 30mL industrial alcohol, and stir, obtain mixed solution.
Step 3, under stirring, mixed solution is added drop-wise in there-necked flask and is mixed with resin chlorine ball, controlling solution temperature is 3 ℃, reaction 2h; Rising temperature to 40 ℃, stirring reaction 10h; Drain afterwards amination mother liquor, water washing is extremely neutral, absolute ethyl alcohol extracting, and heated-air drying can make di-n-propylamine-diethylamine dual-function base weak-base anion-exchange resin, this resin weak base exchange capacity is 3.4mmo1/g, and wherein the mol ratio of dipropyl amido and diethylin content is 0.4:1.
Claims (6)
1. a preparation method for dual-function base weak-base anion-exchange resin, is characterized in that, adopts a step functionalizing legal system standby, comprises the steps:
Step 1, utilize inert organic solvents by the abundant swelling of resin chlorine ball, drain afterwards the resin chlorine ball that inert organic solvents obtains abundant swelling, wherein said resin chlorine ball is the macropore styrene diethylene benzene copoly mer through chloromethylation;
Step 2, by long-chain secondary amine and short chain secondary amine in mass ratio 1～30:1 be dissolved in polar solvent and mix, obtain mixed solution;
Step 3, at 0～5 ℃, mixed solution prepared by step 2 is added drop-wise in the resin chlorine ball of abundant swelling prepared by step 1, stirring reaction 2～4h; Then at 30～55 ℃, stirring reaction 8～12h; Drain afterwards reactant liquor, water washing is to neutral, and extracting dryly obtains dual-function base weak-base anion-exchange resin, and wherein, the gross mass of described long-chain secondary amine and short chain secondary amine is 0.3～2.1 times of resin chlorine ball quality of not swelling.
2. the preparation method of dual-function base weak-base anion-exchange resin according to claim 1, is characterized in that, the degree of cross linking of the styrene diethylene benzene copoly mer of macropore described in step 1 is 2-25%.
3. the preparation method of dual-function base weak-base anion-exchange resin according to claim 1, is characterized in that, inert organic solvents described in step 1 is any one in benzene, nitrobenzene, carrene, dichloroethanes or DMF.
4. the preparation method of dual-function base weak-base anion-exchange resin according to claim 1, is characterized in that, the secondary amine of long-chain described in step 2 is the secondary amine compound with the straight chained alkyl of 3～10 carbon atoms.
5. the preparation method of dual-function base weak-base anion-exchange resin according to claim 1, is characterized in that, the secondary amine of short chain described in step 2 is the secondary amine compound with the straight chained alkyl of 1～2 carbon atom.
6. the preparation method of dual-function base weak-base anion-exchange resin according to claim 1, is characterized in that, polar solvent described in step 2 is ethanol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504131A (en) * | 2016-01-26 | 2016-04-20 | 重庆希尔康血液净化器材研发有限公司 | Preparing method for resin for clearing away beta2-microglobulin in blood purification |
| CN106866863A (en) * | 2015-12-11 | 2017-06-20 | 北京大学深圳研究生院 | A kind of preparation method of porous polymer microballoon anion filler |
| CN107899621A (en) * | 2017-10-26 | 2018-04-13 | 东南大学 | A kind of aromatic sulphonic acid selective ion exchange resin and preparation method and application |
| CN111426764A (en) * | 2020-04-09 | 2020-07-17 | 中国科学院地质与地球物理研究所 | Method for testing age of hydrothermal sulfide in quaternary seabed |
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|---|---|---|---|---|
| CN86108388A (en) * | 1986-12-13 | 1988-07-06 | 核工业部北京第五研究所 | Synthesizing of marcopore double functional group anion exchange resin |
| US6059975A (en) * | 1997-09-02 | 2000-05-09 | Lockheed Martin Energy Research Corporation | Bifunctional anion-exchange resins with improved selectivity and exchange kinetics |
| CN1712135A (en) * | 2005-05-10 | 2005-12-28 | 南京大学 | Production of dual-function base weak-base anion-exchange resin |
-
2013
- 2013-10-21 CN CN201310494765.0A patent/CN103537325A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108388A (en) * | 1986-12-13 | 1988-07-06 | 核工业部北京第五研究所 | Synthesizing of marcopore double functional group anion exchange resin |
| US6059975A (en) * | 1997-09-02 | 2000-05-09 | Lockheed Martin Energy Research Corporation | Bifunctional anion-exchange resins with improved selectivity and exchange kinetics |
| CN1712135A (en) * | 2005-05-10 | 2005-12-28 | 南京大学 | Production of dual-function base weak-base anion-exchange resin |
Non-Patent Citations (1)
| Title |
|---|
| PETERV.BONNESEN ET AL: ""Development of Bifunctional Anion-Exchange Resins with Improved Selectivity and Sorptive Kinetics for Pertechnetate:Batch-Equilibrium Experiments"", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866863A (en) * | 2015-12-11 | 2017-06-20 | 北京大学深圳研究生院 | A kind of preparation method of porous polymer microballoon anion filler |
| CN105504131A (en) * | 2016-01-26 | 2016-04-20 | 重庆希尔康血液净化器材研发有限公司 | Preparing method for resin for clearing away beta2-microglobulin in blood purification |
| CN107899621A (en) * | 2017-10-26 | 2018-04-13 | 东南大学 | A kind of aromatic sulphonic acid selective ion exchange resin and preparation method and application |
| CN111426764A (en) * | 2020-04-09 | 2020-07-17 | 中国科学院地质与地球物理研究所 | Method for testing age of hydrothermal sulfide in quaternary seabed |
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