CN103641738A - Fluorine-containing chelating agent and preparation method and application thereof - Google Patents
Fluorine-containing chelating agent and preparation method and application thereof Download PDFInfo
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- CN103641738A CN103641738A CN201310740612.XA CN201310740612A CN103641738A CN 103641738 A CN103641738 A CN 103641738A CN 201310740612 A CN201310740612 A CN 201310740612A CN 103641738 A CN103641738 A CN 103641738A
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- 0 CC(C)(C(*)(*)C(C)=O)OC(*1)(*1F)F Chemical compound CC(C)(C(*)(*)C(C)=O)OC(*1)(*1F)F 0.000 description 1
- IRPSIXAKZHLMMM-UHFFFAOYSA-N CC(C)([N](C)(N)N)[N](C(C)(C)[N](N)(N)N)(N)N Chemical compound CC(C)([N](C)(N)N)[N](C(C)(C)[N](N)(N)N)(N)N IRPSIXAKZHLMMM-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a fluorine-containing chelating agent and a preparation method and application thereof. The structural formula of the fluorine-containing chelating agent is shown in the specification; and the preparation method comprises the following steps: with iminodiacetic acid as a reaction substrate, protecting carboxyl through an esterification reaction between carboxyl and alcohol; establishing a basic skeleton of the fluorine-containing chelating agent through an amidation reaction between imino group and fluorine-containing acyl halide or an amination reaction between imino group and fluorine-containing halogenated hydrocarbon; and de-protecting for releasing carboxyl through a hydrolysis reaction of ester. The fluorine-containing chelating agent disclosed by the invention has good dissolving property in supercritical carbon dioxide, can be mixed and dissolved in the supercritical carbon dioxide under mild conditions, has a strong chelating effect on metal ions and can be applied to the extraction of heavy metal ions from the supercritical carbon dioxide medium, also can be used in the purifying treatment and resource recycling of pollutants such as wastewater, soil and electronic waste containing heavy metal ions and used for cleaning high-precision electronic devices such as small-size integrated circuits and the like.
Description
Technical field
The invention belongs to Green Chemistry chemical technology field, be specifically related to a kind of fluorine-containing sequestrant and its preparation method and application.
Background technology
Developing rapidly when bringing great wealth to the mankind of industry also produced severe negative impact to environment.A large amount of electronic wastes that a large amount of liquid and waste slag produced and process of consumption of production process discharge produces etc. include a considerable number of heavy metal ion, and above-mentioned heavy metal ion is startling to the pollution of the physical environments such as water body soil.For heavy-metal pollution thing, traditional treatment process (as landfill method and chemical precipitation method etc.) can be alleviated to a certain extent or eliminate ground environment pollution problem in more among a small circle, but the secondary pollution that traditional method produces is but long-range to the harm of the overall situation such as body of groundwater or microbial population and destruction.Along with being showing improvement or progress day by day of science and technology and improving constantly of environmental protection standard, the research of the environmentally friendly chemical process in various countries and application pay attention to day by day, in the purifying treatment of heavy metal contaminants and pollutent, the recycling of valuable metal has caused increasing concern.
Supercritical carbon dioxide extraction method is applied in the fields such as industrial and agricultural production and environment protection more and more because of its unique advantage in recent years.Supercritical co is nontoxic, do not fire, cheap, critical condition easily reaches etc., there is low-viscosity and the high spread coefficient that is similar to gas and density and the solvating ability that is similar to liquid, at its Near The Critical Point, can, by changing the physicochemical property such as pressure and/or temperature regulating density and solvating ability under the condition that does not change chemical constitution, be a kind of generally acknowledged eco-friendly green medium.But in view of carbonic acid gas is a kind of non-polar molecule, (weight) metal ion itself can not be dissolved among supercritical co.While adopting supercritical carbon dioxide extraction heavy metal ion, need introduce suitable sequestrant forming inner complex and be dissolved in supercritical CO 2 medium with metal ion.Document has been reported some traditional sequestrants in succession, as methyl ethyl diketone, crown ether and phosphoric acid ester etc., above-mentioned sequestrant can be dissolved in supercritical co to a certain extent, but the solubleness of the sequestrant inner complex that particularly sequestrant and metal ion form in supercritical co itself is but very limited, this has not only caused corresponding efficiency of supercritical CO 2 extraction very low, and makes extracting operation pressure very high.Chinese invention patent 200910097402.7 discloses a kind of couple-(O; the disubstituted phosphoryl of O-) imines sequestrant; this patent of invention has been drawn above-mentioned imines sequestrant high advantage of extraction efficiency in common liquid-liquid extraction; also improved the problem existing in this type of sequestrant tradition preparation method; but; be limited to the further investigation of supercritical carbon dioxide systems molecular interaction and understanding, the solubleness of above-mentioned sequestrant in supercritical co is still lower, is about 10
-2(mole fraction).Document (J.Mater.Res., 1995, 10, 3, 530-537) reported a kind of sequestrant that is applied to supercritical carbon dioxide extraction heavy metal ion, by give in chelator molecule, introduce perfluor (widow) thus polyether chain has significantly improved the solubility property of sequestrant in supercritical co, but, because its chelating end group is except having good sequestering power and extraction efficiency to mercury ion, a little less than the coordination ability of most of heavy metal ion, extraction efficiency in supercritical co is very low, thereby fundamentally limited prepared sequestrant in the application of supercritical carbon dioxide extraction heavy metal ions.
Summary of the invention
A technical problem to be solved by this invention is to overcome that the dissolving power in supercritical co that existing sequestrant exists is poor, extraction efficiency is low, the shortcoming such as high, the narrow application range of working pressure in supercritical carbon dioxide extraction application, provide a kind of solubility property in supercritical co good, strong to chelation of metal ion, in supercritical carbon dioxide extraction application the lower fluorine-containing sequestrant of working pressure.
Another technical problem that the present invention will solve is to provide a kind of preparation method simple to operate for above-mentioned fluorine-containing sequestrant.The technical problem that the present invention also will solve is to provide a kind of new purposes for above-mentioned fluorine-containing sequestrant.
Solving the problems of the technologies described above adopted technical scheme is: the structural formula of this fluorine-containing sequestrant is as follows:
In formula m be 0 or 1, m be 0 o'clock, R
fsubstituting group for formula (1) or formula (2):
M is 1 o'clock, R
fsubstituting group for formula (3) or formula (4):
In above-mentioned formula (1) and formula (3), the value of n is 0～40, and in formula (2) and formula (4), the value of p is 2～7.The value of n preferably 1～22 in above-mentioned formula (1) and formula (3), the value of the middle p of formula (2) and formula (4) preferably 5～7.
The preparation method of the fluorine-containing sequestrant of the present invention is comprised of following step:
1, synthesis of iminodiacetic acid diester
Iminodiethanoic acid is reacted after 4～8 hours at 35～60 ℃ with thionyl chloride, add alcohol, the mol ratio of iminodiethanoic acid and thionyl chloride, alcohol is 1:2.2～3:4～12, continue reaction 8～32 hours, after reaction finishes, underpressure distillation, obtains iminodiacetic acid (salt) acid diesters.
Above-mentioned alcohol is methyl alcohol, ethanol, Virahol or the trimethyl carbinol.
2, synthetic fluorine-containing sequestrant
By iminodiacetic acid (salt) acid diesters and general structure, be R
fthe fluorine-containing carboxylic acid halides of-COX or general structure are R
f-CH
2fluorine-containing halohydrocarbon, anhydrous sodium carbonate or the Anhydrous potassium carbonate of X is that mix 1～1.25:1:0.50～0.75 according to mol ratio, and in normal temperature～80, ℃ reaction is 6～18 hours, and reaction product, through hydrolysis, separation and purification, obtains fluorine-containing sequestrant.
Above-mentioned general structure R
f-COX or general structure R
f-CH
2in X, R
ffor
The value that wherein value of n is 0～40, p is 2～7, general structure R
fin-COX, X is F, Cl or Br, general structure R
f-CH
2in X, X is Cl or Br.
The purposes of fluorine-containing sequestrant of the present invention in supercritical carbon dioxide systems extracting heavy metal ions.Its using method is: by the matrix that contains metal ion and fluorine-containing sequestrant, by the mol ratio of metal ion and fluorine-containing sequestrant, be that 1:2～2.5 add in supercritical carbon dioxide extraction still, in working pressure scope, be that 10～20MPa, extraction temperature are under 40～60 ℃ of conditions, extracting heavy metal ions 30～60 minutes.
Fluorine-containing sequestrant preparation method of the present invention is simple, yield is high, in supercritical CO 2 medium, solubility property is good, under lower pressure, can fully disperse and be dissolved in supercritical CO 2 medium, even can be miscible with supercritical co under gentle temperature, pressure condition.Compare with at present conventional sequestrant, adopt fluorine-containing sequestrant of the present invention from the matrix that contains metal ion, (to comprise electronic waste in supercritical co, the soil of heavy metal contamination, rare earth breeze and waste water of containing heavy-metal pollution etc., also comprise the accurate unicircuit that contains trace metal ion or other small size electronic devices and components etc.) in chelate extraction metal ion, extracting pressure is low, energy expenditure and running cost have been reduced, and strong to metal ion-chelant extracting power, extraction efficiency is high, be suitable for large-scale production and be widely used in the extraction of metal ion in supercritical CO 2 medium.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but the invention is not restricted to these embodiment.
Embodiment 1
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
1, synthesis of iminodiacetic acid diethyl ester
Under nitrogen protection and condensing reflux; by 71.4g(0.6mol) thionyl chloride dropwise add 33.3g(0.25mol is housed) in the round-bottomed flask of iminodiethanoic acid; under whipped state, be heated to 45 ℃; isothermal reaction 5 hours, then add 117mL(2mol) ethanol, is warming up to 60 ℃ and at this temperature, react 12 hours; after excessive ethanol is removed in distillation; underpressure distillation again, obtains diethyl iminodiacetate 45.6g, and productive rate is 92%.
2, synthetic fluorine-containing sequestrant
Under nitrogen protection and condensing reflux, by 49.8g(0.10mol) the Propylene oxide hexafluoride tripolymer (CF that contains acyl fluorides end group
3cF
2cF
2oCF (CF
3) CF
2oCF (CF
3) COF, by Zhejiang, Huan Xinfu material limited-liability company provides) join 20.8g(0.11mol is housed) diethyl iminodiacetate and 5.3g(0.05mol) in the round-bottomed flask of anhydrous sodium carbonate, under whipped state, be heated to 50 ℃, isothermal reaction 8 hours, then the aqueous sodium hydroxide solution that adds 400mL0.55mol/L, at 40 ℃, stir 10 hours, the aqueous sulfuric acid that adds again 220mL0.50mol/L, at 40 ℃, continue to stir 6 hours, be cooled to normal temperature, stratification, upper strata water is with 1, 5, 5-tri-hydrogen octafluoropentanol (80mL * 3) extractions, merge organic phase and use anhydrous sodium sulfate drying, remove by filter anhydrous sodium sulphate, the solvent in filtrate is removed in underpressure distillation, silica gel column chromatogram method for remaining mixture is (with 1, 2-ethylene dichloride is eluent) purify, obtain the fluorine-containing sequestrant 53.2g of colorless oil, productive rate is 87%, spectral data is as follows:
FT-IR(liquid-film method): 3543,2996,1744,1689,1621,1472,1404,1299,1244,1154,989cm
-1.
1H?NMR（400MHz，CD
3COCD
3）：9.8～10.9（2H），4.0～4.3（4H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：174.3，172.9，136～106，53.1ppm。
Adopt document (Macromolecules2012,45,4907-4919) the situ high pressure infrared spectrum monitoring system of report and on-line monitoring method thereof are measured respectively the fluorine-containing sequestrant solvation dispersion process in supercritical CO 2 medium obtaining at 40,50,60,70 and 80 ℃, result shows that fluorine-containing sequestrant can be miscible with critical carbon dioxide medium under above-mentioned each temperature condition, miscible pressure is gentle, maximum is no more than 20MPa, shows that the solubility property of this fluorine-containing sequestrant in supercritical CO 2 medium is good.
Embodiment 2
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in synthetic fluorine-containing sequestrant step 2, under nitrogen protection and condensing reflux, by 100g(0.025mol) polyhexafluoropropylene oxide (CF that contains acid chloride end groups
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) COCl, mean polymerisation degree is 24, by the polyhexafluoropropylene oxide (CF that contains accordingly carboxylic end group
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) COOH) and thionyl chloride press document (J.Mater.Res., 1995, 10, 3, 530-537) method of report is synthetic, the polyhexafluoropropylene oxide that wherein contains carboxylic end group is provided by du pont company) join 5.68g(0.03mol is housed) diethyl iminodiacetate and 1.73g(0.0125mol) in the round-bottomed flask of Anhydrous potassium carbonate, under whipped state, be heated to 60 ℃, isothermal reaction 12 hours, then the potassium hydroxide aqueous solution that adds 100mL0.50mol/L, at 40 ℃, stir 12 hours, the aqueous sulfuric acid that adds again 50mL0.50mol/L, at 40 ℃, continue to stir 6 hours, other steps are identical with embodiment 1.Obtain the fluorine-containing sequestrant 81.9g of colorless oil, productive rate is 80%, and spectral data is as follows:
FT-IR(liquid-film method): 3543,2996,1744,1689,1621,1472,1404,1299,1244,1154,989cm
-1.
1H?NMR（400MHz，CD
3COCD
3）：9.8～10.9（2H），4.0～4.3（4H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：174.3，173.1，136～106，52.9ppm。
Embodiment 3
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in synthetic fluorine-containing sequestrant step 2, under nitrogen protection and condensing reflux, by 140g(0.02mol) polyhexafluoropropylene oxide (CF that contains acid chloride end groups
3cF
2cF
2o (CF (CF
3) CF
2o)
40cF (CF
3) COCl, mean polymerisation degree is 42, by the polyhexafluoropropylene oxide (CF that contains accordingly carboxylic end group
3cF
2cF
2o (CF (CF
3) CF
2o)
40cF (CF
3) COOH) and thionyl chloride press document (J.Mater.Res., 1995, 10, 3, 530-537) method of report is synthetic, the polyhexafluoropropylene oxide that wherein contains carboxylic end group is provided by du pont company) join 4.75g(0.025mol is housed) diethyl iminodiacetate and 2.1g(0.015mol) in the round-bottomed flask of Anhydrous potassium carbonate, under whipped state, be heated to 60 ℃, isothermal reaction 12 hours, then the aqueous sodium hydroxide solution that adds 100mL0.50mol/L, at 50 ℃, stir 16 hours, the aqueous hydrochloric acid that adds again 100mL0.50mol/L, at 40 ℃, continue to stir 10 hours, be cooled to normal temperature, stratification, upper strata water is with 1, 1, 2, ten trifluoro octanol (50mL * 3) extractions of 2-tetrahydrochysene, merge organic phase and use anhydrous sodium sulfate drying, remove by filter anhydrous sodium sulphate, other steps are identical with embodiment 1, obtain the fluorine-containing sequestrant 107.7g of colorless oil, productive rate is 76%, spectral data is as follows:
FT-IR(liquid-film method): 3547,2989,1747,1691,1619,1475,1398,1297,1241,1154,989cm
-1.
1H?NMR（400MHz，CD
3COCD
3）：9.8～10.9（2H），4.0～4.3（4H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：174.3，173.1，136～106，52.9ppm。
Embodiment 4
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
In the synthesis of iminodiacetic acid diethyl ester step 1 of embodiment 1, ethanol used is replaced with equimolar methyl alcohol, and other steps are identical with embodiment 1, obtain iminodiacetic acid (salt) dimethyl phthalate.In the synthetic fluorine-containing sequestrant step 2 of embodiment 1, under nitrogen protection and condensing reflux, by 23.3g(0.10mol) perfluor butyryl chloride (CF
3cF
2cF
2cOCl) join 19.3g(0.12mol be housed) iminodiacetic acid (salt) dimethyl phthalate and 6.9g(0.05mol) in the round-bottomed flask of Anhydrous potassium carbonate, stirring at normal temperature 16 hours, then the aqueous sodium hydroxide solution that adds 300mL0.80mol/L, at 30 ℃, stir 12 hours, the aqueous sulfuric acid that adds again 200mL0.60mol/L, at 30 ℃, continue to stir 6 hours, be cooled to normal temperature, other steps are identical with embodiment 1, obtain the fluorine-containing sequestrant 29.0g of colorless oil, productive rate is 88%, and spectral data is as follows:
FT-IR(liquid-film method): 3552,2991,1746,1691,1398,1299,1244,1163,985cm
-1.
1H?NMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），4.8～5.0（4H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：173.1，162.3，119～109，52.6ppm。
Embodiment 5
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
In the synthetic oxalic acid diethyl ester step 1 of embodiment 1, ethanol used is replaced with equimolar Virahol, and other steps are identical with embodiment 1, obtain iminodiethanoic acid diisopropyl ester.In the synthetic fluorine-containing sequestrant step 2 of embodiment 1, under nitrogen protection and condensing reflux, by 57.7g(0.10mol) 19 fluorine caprinoyl bromine (CF
3(CF
2)
7cF
2cOBr, by 19 fluorine capric acid and phosphorus tribromide, under nitrogen protection and condensing reflux, react synthetic) join 23.9g(0.11mol is housed) iminodiethanoic acid diisopropyl ester and 5.3g(0.05mol) in the round-bottomed flask of anhydrous sodium carbonate, under whipped state, be heated to 45 ℃, isothermal reaction 12 hours, then the aqueous sodium hydroxide solution that adds 275mL0.80mol/L, at 45 ℃, stir 10 hours, the aqueous sulfuric acid that adds again 220mL0.50mol/L, at 40 ℃, continue to stir 8 hours, be cooled to normal temperature, other steps are identical with embodiment 1, obtain the fluorine-containing sequestrant 51g of colorless oil, productive rate is 81%, spectral data is as follows:
FT-IR(liquid-film method): 3555,2993,1748,1689,1399,1298,1241,1156,987cm
-1.
1H?NMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），4.9～5.2（4H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：173.4，162.8，119～109，52.6ppm。
Embodiment 6
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in synthetic fluorine-containing sequestrant step 2, under nitrogen protection and condensing reflux, by 33.5g(0.10mol) the dimerization of hexafluoropropene oxide body (CF that contains chloromethyl end group
3cF
2cF
2oCF (CF
3) CH
2cl, first by the dimerization of hexafluoropropene oxide body (CF that contains carboxyl end groups
3cF
2cF
2oCF (CF
3) COOH, by Zhejiang, Huan Xinfu material limited-liability company provides) by document (J.Fluor.Chem.2009,130,938-941) the method reduction of report obtains the dimerization of hexafluoropropene oxide body (CF that contains methylol end group
3cF
2cF
2oCF (CF
3) CH
2oH) intermediate, this intermediate reacts with thionyl chloride and gets final product to obtain the above-mentioned dimerization of hexafluoropropene oxide body that contains chloromethyl end group) join 22.7g(0.12mol is housed) diethyl iminodiacetate and 6.9g(0.05mol) in the round-bottomed flask of Anhydrous potassium carbonate, under whipped state, be heated to 60 ℃, isothermal reaction 12 hours, then the potassium hydroxide aqueous solution that adds 300mL0.80mol/L, at 60 ℃, stir 14 hours, the aqueous sulfuric acid that adds again 200mL0.60mol/L, at 50 ℃, continue to stir 10 hours, be cooled to normal temperature, stratification, upper strata water is with 1, 5, 5-tri-hydrogen octafluoropentanol (100mL * 3) extractions, other steps are identical with embodiment 1, obtain the fluorine-containing sequestrant 36.2g of colorless oil, productive rate is 84%, spectral data is as follows:
1H?NMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.4～2.8（2H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：173.3，136～106，60.6，46.8ppm。
Adopt document (Macromolecules2012,45,4907-4919) the situ high pressure infrared spectrum monitoring system of report and on-line monitoring method thereof are measured respectively the fluorine-containing sequestrant solvation dispersion process in supercritical CO 2 medium obtaining at 40,50,60,70 and 80 ℃, result shows that fluorine-containing sequestrant can be miscible with critical carbon dioxide medium under above-mentioned each temperature condition, miscible pressure is gentle, maximum is no more than 25MPa, shows that the solubility property of this fluorine-containing sequestrant in supercritical CO 2 medium is good.
Embodiment 7
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
The step 1 of the present embodiment is identical with embodiment 5, obtains iminodiethanoic acid diisopropyl ester.In synthetic fluorine-containing sequestrant step 2, under nitrogen protection and condensing reflux, by 100.8g(0.025mol) polyhexafluoropropylene oxide (CF that contains brooethyl end group
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) CH
2br, mean polymerisation degree is 24, the method reduction of first pressing document (J.Fluor.Chem.2009,130,938～941) report contains the polyhexafluoropropylene oxide (CF of carboxyl end groups accordingly
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) COOH), obtain the polyhexafluoropropylene oxide (CF that contains methylol end group
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) CH
2oH) intermediate, this intermediate reacts with phosphorus tribromide and gets final product to obtain the above-mentioned polyhexafluoropropylene oxide that contains brooethyl end group under nitrogen protection and condensing reflux) join 6.52g(0.03mol is housed) iminodiethanoic acid diisopropyl ester and 2.1g(0.015mol) in the round-bottomed flask of Anhydrous potassium carbonate, under whipped state, be heated to 80 ℃, under constant temperature, react 18 hours, then the aqueous sodium hydroxide solution that adds 100mL0.60mol/L, at 60 ℃, stir 16 hours, the aqueous hydrochloric acid that adds again 100mL0.60mol/L, at 50 ℃, continue to stir 12 hours, other steps are identical with embodiment 3, obtain the fluorine-containing sequestrant 77.6g of colorless oil, productive rate is 76%, spectral data is as follows:
1H?NMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.4～2.8（2H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：173.1，136～106，60.3，47.5ppm。
Embodiment 8
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in synthetic fluorine-containing sequestrant step 2, under nitrogen protection and condensing reflux, by 26.9g(0.10mol) 1-chloro-2, 2, 3, 3, 4, 4, 5, 5, 5-nine amyl fluorides are (by 1, the fluoro-1-amylalcohol of 1-dihydro nine (like to change into industrial development company limited and provide by ladder is uncommon) reacts preparation under nitrogen protection and condensing reflux with thionyl chloride) join 22.7g(0.12mol is housed) diethyl iminodiacetate and 5.3g(0.05mol) in the round-bottomed flask of anhydrous sodium carbonate, under whipped state, be heated to 30 ℃, isothermal reaction 15 hours, then the aqueous sodium hydroxide solution that adds 300mL0.80mol/L, at 30 ℃, stir 12 hours, the aqueous sulfuric acid that adds again 150mL0.80mol/L, at 30 ℃, continue to stir 6 hours, other steps are identical with embodiment 4, obtain the fluorine-containing sequestrant 30g of colorless oil, productive rate is 82%, spectral data is as follows:
1H?NMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.4～2.8（2H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：173.3，122～104，60.8，51.5ppm。
Embodiment 9
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in synthetic fluorine-containing sequestrant step 2, under nitrogen protection and condensing reflux, by 20.9g(0.05mol) 1-chloro-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-15 fluoro-octanes are (by 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, it is synthetic that the fluoro-1-octanol of 8-15 (being provided by A Faaisha Chemical Co., Ltd.) reacts with thionyl chloride under nitrogen protection and condensing reflux) join 11.4g(0.06mol is housed) diethyl iminodiacetate and 3.5g(0.025mol) in the round-bottomed flask of Anhydrous potassium carbonate, under whipped state, be heated to 40 ℃, isothermal reaction 16 hours, then the aqueous sodium hydroxide solution that adds 200mL0.60mol/L, at 40 ℃, stir 12 hours, the aqueous hydrochloric acid that adds again 150mL0.80mol/L, at 40 ℃, continue to stir 6 hours, be cooled to after normal temperature, stratification, upper strata water is with 1, 5, 5-tri-hydrogen octafluoropentanol (70mL * 3) extractions, other steps are identical with embodiment 3, obtain the fluorine-containing sequestrant 20.6g of colorless oil, productive rate is 80%, spectral data is as follows:
1H?NMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.5～2.8（2H）ppm。
13C?NMR（100MHz，CD
3COCD
3）：173.2，122～104，60.8，51.1ppm。
Embodiment 10
The fluorine-containing sequestrant of preparing following formula of take is example, and its concrete preparation method is as follows:
In the synthetic oxalic acid diethyl ester step 1 of embodiment 1, ethanol used is replaced with the equimolar trimethyl carbinol, and other steps are identical with embodiment 1, obtain iminodiethanoic acid di tert butyl carbonate.In the synthetic fluorine-containing sequestrant step 2 of embodiment 1, diethyl iminodiacetate used is replaced with equimolar iminodiethanoic acid di tert butyl carbonate, anhydrous sodium carbonate is replaced with equimolar Anhydrous potassium carbonate, other steps are identical with embodiment 1, obtain the fluorine-containing sequestrant 55g of colorless oil, productive rate is 90%.
Embodiment 11
The purposes of the fluorine-containing sequestrant of embodiment 1 in supercritical carbon dioxide systems extracting heavy metal ions.Its concrete using method is:
10mL is contained to 2.5mg/mL Cu
2+, 10mL contains 2.5mg/mL Pb
2+and 10mL contains 2.5mg/mL Ag
+aqueous nitric acid pour in the round-bottomed flask that 60g sand is housed and stir 3 hours, with Rotary Evaporators underpressure distillation, fully except anhydrating, the sand of the uniform loading metal ion obtaining is as the solid state substrate model that contains heavy metal ion.In supercritical carbon dioxide extraction still, add the above-mentioned solid state substrate model of 60g and the fluorine-containing sequestrant of 1.0g, heating makes extraction kettle temperature be elevated to 40 ℃ and keep constant temperature, open and stir, to extraction kettle, passing into the pressure that carbonic acid gas makes extraction kettle is elevated to 16MPa and keeps 20 minutes, open high-pressure circulation pump, under the pressure of 16MPa, use supercritical carbon dioxide extraction 40 minutes, close heating and the stirring of extraction kettle, lower the temperature and be decompressed to normal pressure, collect the solid state substrate in extraction kettle, after solid state substrate dissolves with concentrated nitric acid, adopt icp ms (M90 type ICP-MS, Germany Brooker company) measure Cu
2+, Pb
2+and Ag
+residual (with the sand that does not add above-mentioned metal ion in contrast), result shows that the percentage extraction of above-mentioned three kinds of ions is not less than 97%.
Embodiment 12
The purposes of the fluorine-containing sequestrant of embodiment 6 in supercritical carbon dioxide systems extracting heavy metal ions.Its concrete using method is:
10mL is contained to 2.5mg/mL La
3+, 2.5mg/mL Ce
4+and 2.5mg/mL Eu
3+aqueous nitric acid as the liquid matrix model that contains rare earth ion, join in the supercritical carbon dioxide extraction still that the fluorine-containing sequestrant of 600mg is housed, heating makes extraction kettle temperature be elevated to 60 ℃ and keep constant temperature, open and stir, to extraction kettle, passing into the pressure that carbonic acid gas makes extraction kettle is elevated to 20MPa and keeps 20 minutes, open high-pressure circulation pump, under the pressure of 20MPa, use supercritical carbon dioxide extraction 40 minutes, close heating and stir, lower the temperature and be decompressed to normal pressure, collect the liquid matrix in extraction kettle, adopt icp ms (M90 type ICP-MS, Germany Brooker company) measure La
3+, Ce
4+and Eu
3+residual, result shows that the percentage extraction of above-mentioned three kinds of ions is not less than 95%.
Claims (7)
1. a fluorine-containing sequestrant, is characterized in that the structural formula of this sequestrant is as follows:
In formula m be 0 or 1, m be 0 o'clock, R
fsubstituting group for formula (1) or formula (2):
M is 1 o'clock, R
fsubstituting group for formula (3) or formula (4):
In above-mentioned formula (1) and formula (3), the value of n is 0～40, and in formula (2) and formula (4), the value of p is 2～7.
2. fluorine-containing sequestrant according to claim 1, is characterized in that: the value of described n is 1～22.
3. fluorine-containing sequestrant according to claim 1, is characterized in that: the value of described p is 5～7.
4. a preparation method for the fluorine-containing sequestrant of claim 1, is characterized in that it is comprised of following step:
(1) synthesis of iminodiacetic acid diester
Iminodiethanoic acid is reacted after 4～8 hours at 35～60 ℃ with thionyl chloride, add alcohol, the mol ratio of iminodiethanoic acid and thionyl chloride, alcohol is 1:2.2～3:4～12, continue reaction 8～32 hours, after reaction finishes, underpressure distillation, obtains iminodiacetic acid (salt) acid diesters;
Above-mentioned alcohol is methyl alcohol, ethanol, Virahol or the trimethyl carbinol;
(2) synthetic fluorine-containing sequestrant
By iminodiacetic acid (salt) acid diesters and general structure, be R
fthe fluorine-containing carboxylic acid halides of-COX or general structure are R
f-CH
2fluorine-containing halohydrocarbon, anhydrous sodium carbonate or the Anhydrous potassium carbonate of X is that mix 1～1.25:1:0.50～0.75 according to mol ratio, and in normal temperature～80, ℃ reaction is 6～18 hours, and reaction product, through hydrolysis and separation and purification, obtains fluorine-containing sequestrant;
Above-mentioned general structure R
f-COX or general structure R
f-CH
2in X, R
ffor
The value that wherein value of n is 0～40, p is 2～7, general structure R
fin-COX, X is F, Cl or Br, general structure R
f-CH
2in X, X is Cl or Br.
5. the preparation method of fluorine-containing sequestrant according to claim 4, is characterized in that: the value of described n is 1～22.
6. the preparation method of fluorine-containing sequestrant according to claim 4, is characterized in that: the value of described p is 5～7.
7. the purposes of the fluorine-containing sequestrant of claim 1 in supercritical carbon dioxide systems extracting heavy metal ions.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503679A (en) * | 2015-12-14 | 2016-04-20 | 陕西师范大学 | Fluorine-containing chelating agent based on thiourea ligand terminal and preparing method and application of fluorine-containing chelating agent |
| CN105949080A (en) * | 2016-05-09 | 2016-09-21 | 深圳市大物科技有限责任公司 | Method for preparation of heavy metal chelating agent from gutter oil or animal and vegetable oil |
| CN113548962A (en) * | 2021-08-13 | 2021-10-26 | 南京信息工程大学 | Recycling treatment method of fluorocarbon residual liquid generated in production of hexafluoroisopropyl methyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5641887A (en) * | 1994-04-01 | 1997-06-24 | University Of Pittsburgh | Extraction of metals in carbon dioxide and chelating agents therefor |
| US5872257A (en) * | 1994-04-01 | 1999-02-16 | University Of Pittsburgh | Further extractions of metals in carbon dioxide and chelating agents therefor |
-
2013
- 2013-12-26 CN CN201310740612.XA patent/CN103641738B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5641887A (en) * | 1994-04-01 | 1997-06-24 | University Of Pittsburgh | Extraction of metals in carbon dioxide and chelating agents therefor |
| US5872257A (en) * | 1994-04-01 | 1999-02-16 | University Of Pittsburgh | Further extractions of metals in carbon dioxide and chelating agents therefor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503679A (en) * | 2015-12-14 | 2016-04-20 | 陕西师范大学 | Fluorine-containing chelating agent based on thiourea ligand terminal and preparing method and application of fluorine-containing chelating agent |
| CN105503679B (en) * | 2015-12-14 | 2017-07-11 | 陕西师范大学 | The fluorine-containing chelating agent at end and its preparation method and application is coordinated based on thiocarbamide |
| CN105949080A (en) * | 2016-05-09 | 2016-09-21 | 深圳市大物科技有限责任公司 | Method for preparation of heavy metal chelating agent from gutter oil or animal and vegetable oil |
| CN105949080B (en) * | 2016-05-09 | 2017-11-03 | 深圳市大物科技有限责任公司 | The method that heavy metal chelant is prepared with gutter oil or vegetable and animals oils |
| CN113548962A (en) * | 2021-08-13 | 2021-10-26 | 南京信息工程大学 | Recycling treatment method of fluorocarbon residual liquid generated in production of hexafluoroisopropyl methyl ether |
| CN113548962B (en) * | 2021-08-13 | 2023-06-30 | 南京信息工程大学 | Resource treatment method for fluorocarbon residual liquid generated in production of hexafluoroisopropyl methyl ether |
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