CN1478731A - Preparation method of triazene polymer chelant and its application - Google Patents
Preparation method of triazene polymer chelant and its application Download PDFInfo
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- CN1478731A CN1478731A CNA031387535A CN03138753A CN1478731A CN 1478731 A CN1478731 A CN 1478731A CN A031387535 A CNA031387535 A CN A031387535A CN 03138753 A CN03138753 A CN 03138753A CN 1478731 A CN1478731 A CN 1478731A
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Abstract
A process for preparing triazene as high-molecular chelating agent features that the functional group "-S-" is introduced to the adjacent position of amino in a compound. It has strong chelating action to heavy metal ions (such as Cd and Hg) and excellent regeneration performance.
Description
Technical field
The present invention relates to a kind of functional polymer inner complex, high-molecule chelated preparation method of reagent thereof of particularly a kind of triazene and application.
Background technology
The preparation method of high-molecule chelated reagent is varied, but mainly contains two kinds of route of synthesis, and a kind of is that the monomer that contains chelate group is produced through methods such as addition polymerization, polycondensations, this synthetic operation complicated condition, synthetic cost height; Another kind is to utilize synthetic or natural polymer, introduces the side group with chelating function by the polymer chemistry reaction and comes synthetic macromolecule, and this synthetic major advantage is that macromolecular scaffold is ready-made, and is wide in variety, cheap, and raw material sources are convenient.Therefore, present most of functional polymer is to utilize various macromolecular scaffolds to carry out polymer chemistry to react [1-4] that produces.Singh is a skeleton with Amberlite XAD-2 in recent years, by-N=N-and the small molecule coupled a series of functional polymers [5-8] that prepared that contain functional group, the separation and concentration that is used for various water quality heavy metal ion has been obtained very good effect.We have made AATP-XAD-2 with adjacent glycyl thiophenol by-N=N-N H-and Amberlite XAD-2 coupling, and are used for tap water, Sang Gan river and Fenhe River water Cd, Cu, and Ni, the separation and concentration of Zn has been obtained very good effect.
Summary of the invention
The present invention is based on the problem of above-mentioned existence, purpose provides a kind of separation and concentration heavy metal ion Cd, Cu, Ni, the high-molecule chelated preparation method of reagent thereof of triazene and the application of Zn and regenerability excellence.
Preparation method of the present invention follows these steps to carry out successively: the preparation of (1) adjacent glycyl thiophenol: add 25 milliliters of raw materials in 100 milliliters of three-necked bottles, stir down and make into weakly alkaline with the solid sodium carbonate neutralization, drip diacetyl oxide again to the solid that is creamy white, temperature of reaction should be above 40 ℃.Remove excess raw material with the deionized water wash product, get the adjacent glycyl thiophenol of pure product; (2) preparation of AATP-XAD-2: the AmberliteXAD-2 pre-treatment, use hydrochloric acid, sodium hydroxide and deionized water with Amberlite XAD-2 pre-treatment; Amberlite XAD-2 is nitrated, get the Amberlite XAD-2 that 5 grams were handled, stir and add 10 milliliters of concentrated nitric acids and 25 milliliters of vitriol oils down, 50 ℃ are reacted half an hour down, reaction mixture poured in the frozen water filter, to slightly acidic, get the nitrated Amberlite XAD-2 of xanchromatic with deionized water wash; (3) reduction of nitrated AmberliteXAD-2 adds 100 milliliters of 1.5mol L with nitrated Amberlite XAD-2
-1NaOH and the mixing solutions of 15 gram thiourea peroxides in, in 40-50 ℃ of following reaction 5h, filter, washing, red poly-4-amino-benzene ethene; (4) the amino cinnamic diazotization of poly-4-is with 100 milliliters of 2mol L
-1Salt acid soak half an hour, filter, remove excessive acid with deionized water wash.The poly-4-amino-benzene ethene of acidifying is added 200 milliliters of 1mol L
-1HCl, in ice-water bath, be cooled to below 5 ℃, drip with ice-water bath and be cooled to 1%NaNO below 5 ℃
2Become blue to potassium iodide starch paper; (5) preparation of AATP-XAD-2 is dissolved in the adjacent glycyl thiophenol that makes in 100 milliliter of 95% ethanol, and above-mentioned diazotization thing is added wherein, reaction below 5 ℃ 24 hours, filters, with getting brown product A ATP-XAD-2 behind ethanol and the deionized water wash.
Its molecular structural formula is as (I) formula:
Ultimate analysis, differential thermal analysis and infrared spectrum test and target product coincide.
The high-molecule chelated reagent A ATP-XAD-2 of this triazene is applied to Cd in the water body, Cu, Ni, the good material of Zn separation and concentration.
Preparation method and the advantages of application of the high-molecule chelated reagent A ATP-XAD-2 of triazene of the present invention with positively effect are: compare with the preparation method of Singh: (1) in sodium hydroxide medium with the nitrated XAD-2 of thiourea peroxide reduction, low than tin protochloride and hydrochloric acid reduction method temperature of reaction, the reduction efficiency height; (2)-N=N-NH-coupling base on nitrogen-atoms to the avidity of metal ion-the N=N-base on nitrogen-atoms affine big to metal ion, obtained higher enrichment multiple; (3) AATP-XAD-2 compares sulfydryl with TSA-XAD-2 and has been subjected to protection, and the stability of AATP-XAD-2 is improved, and prolong work-ing life.The present invention and Singh method have that related parameter contrast sees Table 1, table 2.
With environmental standard sample (GSBZ 50009-88) to AATP-XAD-2 separation and concentration Cd, Cu, Ni, the validity of Zn is tested, and the results are shown in Table 3.
Table 1 AATP-XAD-2 preparation parameter of the present invention and the contrast of Singh method
Parameter present method Singh method
Cost (unit/10g) 100 150
Reduction temperature (℃) 40-50 90
Recovery time (h) 5 12
Productive rate (%) 92 90
Table 2 AATP-XAD-2 performance perameter of the present invention and the contrast of Singh method
Enrichment factor is reused the rate of recovery (%) loading capacity (μ mol/g) 15 times
Ion
Present method Singh method present method Singh method present method Singh method
Cd 300 200 96 95 210 197.5
Cu 200 180 96 96 150 106.9
Ni 300 200 93 90 285 309.9
Zn 200 200 95 93 59.2 47.4
Table 3 standard model (GSBZ50009-88) measurement result
Standard model ingredient standard value (mg L
-1) measured value (n=5) (mg L
-1)
Cu 1.00±0.05 1.20±0.06
Zn 0.500±0.025 0.58±0.03
Cd 0.150±0.008 0.14±0.01
Ni 1.00±0.05 0.96±0.08
Distinguishing feature of the present invention is that method is simple, and is with low cost, and the product separation concentration effect is good, and stable performance can be used for the separation and concentration of heavy metal ion in the water body.
Embodiment
Embodiment 1:(1) add 25 milliliters of raw materials in 100 milliliters of three-necked bottles, stir down and make into weakly alkaline with the solid sodium carbonate neutralization, drip diacetyl oxide again to being creamy white solid, temperature of reaction should be above 40 ℃.Remove excess raw material with the deionized water wash product, get the adjacent glycyl thiophenol of pure product;
(2) preparation of AATP-XAD-2,1. Amberlite XAD-2 pre-treatment uses hydrochloric acid, sodium hydroxide and deionized water with Amberlite XAD-2 pre-treatment; 2. Amberlite XAD-2 is nitrated, get the Amberlite XAD-2 that 5 grams were handled, stir and add 10 milliliters of concentrated nitric acids and 25 milliliters of vitriol oils down, 50 ℃ are reacted half an hour down, reaction mixture poured in the frozen water filter, to slightly acidic, get yellow nitrated Amberlite XAD-2 with deionized water wash; 3. the reduction of nitrated Amberlite XAD-2 adds 100 milliliters of 1.5mol L with nitrated Amberlite XAD-2
-1NaOH and the mixing solutions of 15 gram thiourea peroxides in, in 40-50 ℃ of following reaction 5h, filter, washing, red poly-4-amino-benzene ethene; 4. the amino cinnamic diazotization of poly-4-is with 100 milliliters of 2mol L
-1Salt acid soak half an hour, filter, remove excessive acid with deionized water wash.The poly-4-amino-benzene ethene of acidifying is added 200 milliliters of 1mol L
-1HCl, in ice-water bath, be cooled to below 5 ℃, drip with ice-water bath and be cooled to 1%NaNO below 5 ℃
2Become blue to potassium iodide starch paper; 5. the preparation of AATP-XAD-2 is dissolved in the adjacent glycyl thiophenol that makes in 100 milliliter of 95% ethanol, and above-mentioned diazotization thing is added wherein, reaction below 5 ℃ 24 hours, filters, with getting brown product A ATP-XAD-2 behind ethanol and the deionized water wash.Ultimate analysis, differential thermal analysis and infrared spectrum test and target product coincide.
Embodiment 2: the high-molecule chelated reagent of triazene in water body to Cd, Cu, Ni, the embodiment that the Zn separation and concentration is used: 1 gram AATP-XAD-2 packs in 1 (cm) * 10 (cm) glass column, measure Cd in tap water, Sang Gan river and the Fenhe River water, Cu, Ni with Perkin ElmerAA-6800 type atomic absorption photometer, Zn the results are shown in Table 4.
Table 4 tap water, Sang Gan river and Fenhe River water sample measurement result
Measured value (n=5) (g L
-1)
Sample
Cu Zn Cd Ni
Tap water 0.122 ± 0.047 0.082 ± 0.051-0.002 ± 0.042
Sang Gan river 0.935 ± 0.053 0.213 ± 0.067 0.022 ± 0.054 0.040 ± 0.063
Fenhe River water 0.320 ± 0.072 0.146 ± 0.045 0.014 ± 0.045 0.036 ± 0.044
Annotating "-" does not measure.
Claims (2)
1. high-molecule chelated preparation method of reagent thereof of triazene, this method follows these steps to carry out successively:
(1) preparation of adjacent glycyl thiophenol: in 100 milliliters of three-necked bottles, add 25 milliliters of raw materials, stir down and be neutralized to weakly alkaline with solid sodium carbonate, drip diacetyl oxide again to the solid that is creamy white, temperature of reaction should be above 40 ℃, remove excess raw material with the deionized water wash product, get the adjacent glycyl thiophenol of pure product;
(2) preparation of AATP-XAD-2:
1. Amberlite XAD-2 pre-treatment uses hydrochloric acid, sodium hydroxide and deionized water with the AmberliteXAD-2 pre-treatment;
2. Amberlite XAD-2 is nitrated, get the Amberlite XAD-2 that 5 grams were handled, stir and add 10 milliliters of concentrated nitric acids and 25 milliliters of vitriol oils down, 50 ℃ are reacted half an hour down, reaction mixture poured in the frozen water filter, to slightly acidic, get the nitrated Amberlite XAD-2 of xanchromatic with deionized water wash;
3. the reduction of nitrated Amberlite XAD-2 adds 100 milliliters of 1.5mol L with nitrated Amberlite XAD-2
-1NaOH and the mixing solutions of 15 gram thiourea peroxides in, in 40-50 ℃ of following reaction 5h, filter, washing, red poly-4-amino-benzene ethene;
4. the amino cinnamic diazotization of poly-4-is with 100 milliliters of 2mol L
-1Salt acid soak half an hour, filter, remove excessive acid with deionized water wash, the poly-4-amino-benzene ethene of acidifying is added 200 milliliters of 1molL
-1HCl, in ice-water bath, be cooled to below 5 ℃, drip with ice-water bath and be cooled to 1%NaNO below 5 ℃
2Become blue to potassium iodide starch paper;
5. the preparation of AATP-XAD-2 is dissolved in the adjacent glycyl thiophenol that makes in 100 milliliter of 95% ethanol, and above-mentioned diazotization thing is added wherein, reaction below 5 ℃ 24 hours, filters, with getting brown product A ATP-XAD-2 behind ethanol and the deionized water wash;
Its molecular structural formula is as (I) formula:
The high-molecule chelated reagent A ATP-XAD-2 of a kind of triazene of claim 1 in water body as separation and concentration Cd, Cu, Ni, the application of Zn.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300124C (en) * | 2005-07-05 | 2007-02-14 | 雁北师范学院 | Double heterocyclic tri azene compound and its preparing method and use |
| CN100376887C (en) * | 2005-04-29 | 2008-03-26 | 农业部环境保护科研监测所 | Test paper for detecting heavy metal cadmium rapidly, preparation method and application |
| CN102583685A (en) * | 2012-02-15 | 2012-07-18 | 天津理工大学 | Method for removing trace mercury in water solution |
-
2003
- 2003-06-30 CN CN 03138753 patent/CN1197788C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376887C (en) * | 2005-04-29 | 2008-03-26 | 农业部环境保护科研监测所 | Test paper for detecting heavy metal cadmium rapidly, preparation method and application |
| CN1300124C (en) * | 2005-07-05 | 2007-02-14 | 雁北师范学院 | Double heterocyclic tri azene compound and its preparing method and use |
| CN102583685A (en) * | 2012-02-15 | 2012-07-18 | 天津理工大学 | Method for removing trace mercury in water solution |
| CN102583685B (en) * | 2012-02-15 | 2014-04-16 | 天津理工大学 | Method for removing trace mercury in water solution |
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