CN103641738B - Fluorine-containing sequestrant and its preparation method and application - Google Patents
Fluorine-containing sequestrant and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of fluorine-containing sequestrant and its preparation method and application, the structural formula of this fluorine-containing sequestrant is
Description
Technical field
The invention belongs to green chemistry chemical technology technical field, be specifically related to a kind of fluorine-containing sequestrant and its preparation method and application.
Background technology
Developing rapidly of industry also creates severe negative impact to environment while bringing great wealth to the mankind.A large amount of electronic wastes etc. that the liquid and waste slag produced in a large number and process of consumption of production process discharge produces include a considerable number of heavy metal ion, and the pollution of above-mentioned heavy metal ion to physical environments such as water body soil is startling.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 but is 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 investigation and application pay attention to day by day of the environmentally friendly chemical process in various countries, 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 field such as industrial and agricultural production and environment protection more and more because of the advantage of its uniqueness in recent years.Supercritical co is nontoxic, do not fire, cheap, critical condition easily reaches, there is the low-viscosity and high diffusivity coefficient that are similar to gas and the density and the solvating ability that are similar to liquid, can pass through to change pressure and/or the physicochemical property such as temperature regulating density and solvating ability under the condition not changing chemical constitution at its Near The Critical Point, 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.When adopting supercritical carbon dioxide extraction heavy metal ion, suitable sequestrant need be introduced so that can inner complex be formed with metal ion and be dissolved in supercritical CO 2 medium.Document reports 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 particularly the solubleness of inner complex in supercritical co that formed of sequestrant and metal ion is but very limited for sequestrant itself, it is very low that this not only result in corresponding efficiency of supercritical CO 2 extraction, and make 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 drawn the above-mentioned imines sequestrant advantage that extraction efficiency is high in common liquid-liquid extraction; also improve Problems existing in this quasi-chelate compound traditional preparation methods; but; be limited to the further investigation to 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) report a kind of sequestrant being applied to supercritical carbon dioxide extraction heavy metal ion, introduce perfluor (widow) polyether chain by giving in chelator molecule thus significantly improve the solubility property of sequestrant in supercritical co, but, because its chelating end group is except having except good sequestering power and extraction efficiency to mercury ion, weak to the coordination ability of most of heavy metal ion, extraction efficiency in supercritical co is very low, thus fundamentally limit the application of prepared sequestrant at supercritical carbon dioxide extraction heavy metal ions.
Summary of the invention
A technical problem to be solved by this invention is that the dissolving power in supercritical co overcoming the existence of existing sequestrant is poor, extraction efficiency is low, in supercritical carbon dioxide extraction application, the shortcoming such as high, the narrow application range of working pressure, provides a kind of solubility property in supercritical co excellent, strong to chelation of metal ion, that working pressure is lower in supercritical carbon dioxide extraction application fluorine-containing sequestrant.
Another technical problem that the present invention will solve is as above-mentioned fluorine-containing sequestrant provides a kind of preparation method simple to operate.The technical problem that the present invention also will solve is as above-mentioned fluorine-containing sequestrant provides a kind of novelty teabag.
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 is 0 or 1, m when being 0, R
fsubstituting group for formula (1) or formula (2):
When m is 1, R
fsubstituting group for formula (3) or formula (4):
The value of above-mentioned formula (1) and the middle n of formula (3) is 0 ~ 40, and the value of formula (2) and the middle p of formula (4) is 2 ~ 7.The value of n preferably 1 ~ 22 in above-mentioned formula (1) and formula (3), the value of formula (2) and the middle p of formula (4) preferably 5 ~ 7.
The preparation method of the fluorine-containing sequestrant of the present invention is made up of following step:
1, synthesis of iminodiacetic acid diester
After iminodiethanoic acid and thionyl chloride are reacted 4 ~ 8 hours at 35 ~ 60 DEG C, 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 terminates, underpressure distillation, obtains iminodiacetic acid (salt) acid diesters.
Above-mentioned alcohol is methyl alcohol, ethanol, Virahol or the trimethyl carbinol.
2, fluorine-containing sequestrant is synthesized
Be R by iminodiacetic acid (salt) acid diesters and general structure
fthe fluorine-containing carboxylic acid halides of-COX or general structure are R
f-CH
2the fluorine-containing halohydrocarbon of X, anhydrous sodium carbonate or Anhydrous potassium carbonate are that 1 ~ 1.25:1:0.50 ~ 0.75 mixes according to mol ratio, and DEG C reaction 6 ~ 18 hours in normal temperature ~ 80, 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
Wherein the value of n is the value of 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: be that 1:2 ~ 2.5 add in supercritical carbon dioxide extraction still by the matrix containing metal ion and fluorine-containing sequestrant by the mol ratio of metal ion and fluorine-containing sequestrant, working pressure scope be 10 ~ 20MPa, under extraction temperature is 40 ~ 60 DEG C 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 excellent, fully can disperse at low pressures and be dissolved in supercritical CO 2 medium, even can be miscible with supercritical co under the temperature, pressure condition of gentleness.Compared with sequestrant conventional at present, fluorine-containing sequestrant of the present invention is adopted (to comprise electronic waste from the matrix containing metal ion in supercritical co, the soil of heavy metal contamination, rare earth breeze and the waste water etc. containing heavy-metal pollution, also comprise sophisticated integrated circuits containing trace metal ion or other small size electronic devices and components etc.) in chelate extraction metal ion, extracting pressure is low, reduce energy expenditure and running cost, and it is 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 embodiments.
Embodiment 1
To prepare the fluorine-containing sequestrant of following formula, 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; 45 DEG C are heated under whipped state; isothermal reaction 5 hours, then add 117mL(2mol) ethanol, be warming up to 60 DEG C and react 12 hours at this temperature; after the ethanol that distillation removing is excessive; underpressure distillation again, obtains diethyl iminodiacetate 45.6g, and productive rate is 92%.
2, fluorine-containing sequestrant is synthesized
Under nitrogen protection and condensing reflux, by 49.8g(0.10mol) Propylene oxide hexafluoride tripolymer (CF containing acyl fluorides end group
3cF
2cF
2oCF (CF
3) CF
2oCF (CF
3) COF, thered is provided by Zhejiang Huanxin Fluorine Material Co., Ltd.) join and 20.8g(0.11mol be housed) diethyl iminodiacetate and 5.3g(0.05mol) and anhydrous sodium carbonate round-bottomed flask in, 50 DEG C are heated under whipped state, isothermal reaction 8 hours, then the aqueous sodium hydroxide solution of 400mL0.55mol/L is added, stir 10 hours at 40 DEG C, add the aqueous sulfuric acid of 220mL0.50mol/L again, stirring is continued 6 hours at 40 DEG C, be cooled to normal temperature, stratification, upper strata aqueous phase is with 1, 5, 5-tri-hydrogen octafluoropentanol (80mL × 3) extracts, merge organic phase and use anhydrous sodium sulfate drying, cross and filter anhydrous sodium sulphate, solvent in underpressure distillation removing filtrate, remaining mixture with silica gel column chromatogram method (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.
1HNMR（400MHz，CD
3COCD
3）：9.8～10.9（2H），4.0～4.3（4H）ppm。
13CNMR（100MHz，CD
3COCD
3）：174.3，172.9，136～106，53.1ppm。
Adopt document (Macromolecules2012,45, situ high pressure infrared spectrum monitoring system 4907-4919) reported and on-line monitoring method thereof measure the fluorine-containing sequestrant solvation dispersion process in supercritical CO 2 medium obtained respectively at 40,50,60,70 and 80 DEG C, result shows that fluorine-containing sequestrant can be miscible with critical carbon dioxide medium under above-mentioned each temperature condition, miscible pressure is gentle, maximumly be no more than 20MPa, show that the solubility property of this fluorine-containing sequestrant in supercritical CO 2 medium is excellent.
Embodiment 2
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in the fluorine-containing sequestrant step 2 of synthesis, under nitrogen protection and condensing reflux, by 100g(0.025mol) polyhexafluoropropylene oxide (CF containing 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 accordingly containing 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, method synthesis 530-537) reported, wherein provided by du pont company containing the polyhexafluoropropylene oxide of carboxylic end group) join and 5.68g(0.03mol be housed) diethyl iminodiacetate and 1.73g(0.0125mol) and Anhydrous potassium carbonate round-bottomed flask in, 60 DEG C are heated under whipped state, isothermal reaction 12 hours, then the potassium hydroxide aqueous solution of 100mL0.50mol/L is added, stir 12 hours at 40 DEG C, add the aqueous sulfuric acid of 50mL0.50mol/L again, stirring is continued 6 hours at 40 DEG C, 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.
1HNMR（400MHz，CD
3COCD
3）：9.8～10.9（2H），4.0～4.3（4H）ppm。
13CNMR（100MHz，CD
3COCD
3）：174.3，173.1，136～106，52.9ppm。
Embodiment 3
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in the fluorine-containing sequestrant step 2 of synthesis, under nitrogen protection and condensing reflux, by 140g(0.02mol) polyhexafluoropropylene oxide (CF containing 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 accordingly containing 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, method synthesis 530-537) reported, wherein provided by du pont company containing the polyhexafluoropropylene oxide of carboxylic end group) join and 4.75g(0.025mol be housed) diethyl iminodiacetate and 2.1g(0.015mol) and Anhydrous potassium carbonate round-bottomed flask in, 60 DEG C are heated under whipped state, isothermal reaction 12 hours, then the aqueous sodium hydroxide solution of 100mL0.50mol/L is added, stir 16 hours at 50 DEG C, add the aqueous hydrochloric acid of 100mL0.50mol/L again, stirring is continued 10 hours at 40 DEG C, be cooled to normal temperature, stratification, upper strata aqueous phase is with 1, 1, 2, 2-tetrahydrochysene ten trifluoro octanol (50mL × 3) extracts, merge organic phase and use anhydrous sodium sulfate drying, cross and 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.
1HNMR（400MHz，CD
3COCD
3）：9.8～10.9（2H），4.0～4.3（4H）ppm。
13CNMR（100MHz，CD
3COCD
3）：174.3，173.1，136～106，52.9ppm。
Embodiment 4
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
In the synthesis of iminodiacetic acid diethyl ester step 1 of embodiment 1, the equimolar methyl alcohol of ethanol used is replaced, and other steps are identical with embodiment 1, obtains iminodiacetic acid (salt) dimethyl phthalate.In the synthesis 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 is housed) iminodiacetic acid (salt) dimethyl phthalate and 6.9g(0.05mol) and Anhydrous potassium carbonate round-bottomed flask in, stirring at normal temperature 16 hours, then the aqueous sodium hydroxide solution of 300mL0.80mol/L is added, stir 12 hours at 30 DEG C, add the aqueous sulfuric acid of 200mL0.60mol/L again, stirring is continued 6 hours at 30 DEG C, 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.
1HNMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），4.8～5.0（4H）ppm。
13CNMR（100MHz，CD
3COCD
3）：173.1，162.3，119～109，52.6ppm。
Embodiment 5
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
In the synthesis oxalic acid diethyl ester step 1 of embodiment 1, the equimolar Virahol of ethanol used is replaced, and other steps are identical with embodiment 1, obtains iminodiethanoic acid diisopropyl ester.In the synthesis 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, the Reactive Synthesis under nitrogen protection and condensing reflux by 19 fluorine capric acid and phosphorus tribromide) join and 23.9g(0.11mol be housed) iminodiethanoic acid diisopropyl ester and 5.3g(0.05mol) and anhydrous sodium carbonate round-bottomed flask in, 45 DEG C are heated under whipped state, isothermal reaction 12 hours, then the aqueous sodium hydroxide solution of 275mL0.80mol/L is added, stir 10 hours at 45 DEG C, add the aqueous sulfuric acid of 220mL0.50mol/L again, stirring is continued 8 hours at 40 DEG C, 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.
1HNMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），4.9～5.2（4H）ppm。
13CNMR（100MHz，CD
3COCD
3）：173.4，162.8，119～109，52.6ppm。
Embodiment 6
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in the fluorine-containing sequestrant step 2 of synthesis, under nitrogen protection and condensing reflux, by 33.5g(0.10mol) dimerization of hexafluoropropene oxide body (CF containing chloromethyl end group
3cF
2cF
2oCF (CF
3) CH
2cl, first by the dimerization of hexafluoropropene oxide body (CF containing carboxyl end groups
3cF
2cF
2oCF (CF
3) COOH, being provided by Zhejiang Huanxin Fluorine Material Co., Ltd.) method reported by document (J.Fluor.Chem.2009,130,938-941) reduces the dimerization of hexafluoropropene oxide body (CF obtained containing methylol end group
3cF
2cF
2oCF (CF
3) CH
2oH) intermediate, this intermediate reacts with thionyl chloride and to obtain the above-mentioned dimerization of hexafluoropropene oxide body containing chloromethyl end group) join and 22.7g(0.12mol be housed) diethyl iminodiacetate and 6.9g(0.05mol) and Anhydrous potassium carbonate round-bottomed flask in, 60 DEG C are heated under whipped state, isothermal reaction 12 hours, then the potassium hydroxide aqueous solution of 300mL0.80mol/L is added, stir 14 hours at 60 DEG C, add the aqueous sulfuric acid of 200mL0.60mol/L again, stirring is continued 10 hours at 50 DEG C, be cooled to normal temperature, stratification, upper strata aqueous phase is with 1, 5, 5-tri-hydrogen octafluoropentanol (100mL × 3) extracts, 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:
1HNMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.4～2.8（2H）ppm。
13CNMR（100MHz，CD
3COCD
3）：173.3，136～106，60.6，46.8ppm。
Adopt document (Macromolecules2012,45, situ high pressure infrared spectrum monitoring system 4907-4919) reported and on-line monitoring method thereof measure the fluorine-containing sequestrant solvation dispersion process in supercritical CO 2 medium obtained respectively at 40,50,60,70 and 80 DEG C, result shows that fluorine-containing sequestrant can be miscible with critical carbon dioxide medium under above-mentioned each temperature condition, miscible pressure is gentle, maximumly be no more than 25MPa, show that the solubility property of this fluorine-containing sequestrant in supercritical CO 2 medium is excellent.
Embodiment 7
To prepare the fluorine-containing sequestrant of following formula, 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 the fluorine-containing sequestrant step 2 of synthesis, under nitrogen protection and condensing reflux, by 100.8g(0.025mol) polyhexafluoropropylene oxide (CF containing brooethyl end group
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) CH
2br, mean polymerisation degree is 24, first presses the corresponding polyhexafluoropropylene oxide (CF containing carboxyl end groups of method reduction that document (J.Fluor.Chem.2009,130,938 ~ 941) is reported
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) COOH), obtain the polyhexafluoropropylene oxide (CF containing methylol end group
3cF
2cF
2o (CF (CF
3) CF
2o)
22cF (CF
3) CH
2oH) intermediate, this intermediate reacts with phosphorus tribromide and to obtain the above-mentioned polyhexafluoropropylene oxide containing brooethyl end group under nitrogen protection and condensing reflux) join and 6.52g(0.03mol be housed) iminodiethanoic acid diisopropyl ester and 2.1g(0.015mol) and Anhydrous potassium carbonate round-bottomed flask in, 80 DEG C are heated under whipped state, react 18 hours under constant temperature, then the aqueous sodium hydroxide solution of 100mL0.60mol/L is added, stir 16 hours at 60 DEG C, add the aqueous hydrochloric acid of 100mL0.60mol/L again, stirring is continued 12 hours at 50 DEG C, 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:
1HNMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.4～2.8（2H）ppm。
13CNMR（100MHz，CD
3COCD
3）：173.1，136～106，60.3，47.5ppm。
Embodiment 8
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in the fluorine-containing sequestrant step 2 of synthesis, under nitrogen protection and condensing reflux, by 26.9g(0.10mol) 1-chloro-2, 2, 3, 3, 4, 4, 5, 5, 5-nine amyl fluoride is (by 1, the fluoro-1-amylalcohol of 1-dihydro nine (wishing love by ladder to change into industrial development company limited and provide) reacts with thionyl chloride and prepares under nitrogen protection and condensing reflux) join and 22.7g(0.12mol be housed) diethyl iminodiacetate and 5.3g(0.05mol) and anhydrous sodium carbonate round-bottomed flask in, 30 DEG C are heated under whipped state, isothermal reaction 15 hours, then the aqueous sodium hydroxide solution of 300mL0.80mol/L is added, stir 12 hours at 30 DEG C, add the aqueous sulfuric acid of 150mL0.80mol/L again, stirring is continued 6 hours at 30 DEG C, 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:
1HNMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.4～2.8（2H）ppm。
13CNMR（100MHz，CD
3COCD
3）：173.3，122～104，60.8，51.5ppm。
Embodiment 9
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
The synthesis of iminodiacetic acid diethyl ester of the present embodiment is identical with embodiment 1, in the fluorine-containing sequestrant step 2 of synthesis, 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-octane is (by 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, the fluoro-1-octanol (Chemical Co., Ltd. provides by AlfaAesar) of 8-15 under nitrogen protection and condensing reflux with thionyl chloride Reactive Synthesis) join and 11.4g(0.06mol be housed) diethyl iminodiacetate and 3.5g(0.025mol) Anhydrous potassium carbonate round-bottomed flask in, 40 DEG C are heated under whipped state, isothermal reaction 16 hours, then the aqueous sodium hydroxide solution of 200mL0.60mol/L is added, stir 12 hours at 40 DEG C, add the aqueous hydrochloric acid of 150mL0.80mol/L again, stirring is continued 6 hours at 40 DEG C, after being cooled to normal temperature, stratification, upper strata aqueous phase is with 1, 5, 5-tri-hydrogen octafluoropentanol (70mL × 3) extracts, 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:
1HNMR（400MHz，CD
3COCD
3）：9.9～11.2（2H），3.2～3.4（4H），2.5～2.8（2H）ppm。
13CNMR（100MHz，CD
3COCD
3）：173.2，122～104，60.8，51.1ppm。
Embodiment 10
To prepare the fluorine-containing sequestrant of following formula, its concrete preparation method is as follows:
In the synthesis oxalic acid diethyl ester step 1 of embodiment 1, the equimolar trimethyl carbinol of ethanol used is replaced, and other steps are identical with embodiment 1, obtains iminodiethanoic acid di tert butyl carbonate.In the synthesis fluorine-containing sequestrant step 2 of embodiment 1, the equimolar iminodiethanoic acid di tert butyl carbonate of diethyl iminodiacetate used is replaced, the equimolar Anhydrous potassium carbonate of anhydrous sodium carbonate is replaced, 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 fluorine-containing sequestrant in supercritical carbon dioxide systems extracting heavy metal ions of embodiment 1.Its concrete using method is:
10mL is contained 2.5mg/mLCu
2+, 10mL contains 2.5mg/mLPb
2+and 10mL contains 2.5mg/mLAg
+aqueous nitric acid pour in the round-bottomed flask that 60g sand is housed stir 3 hours, with Rotary Evaporators underpressure distillation fully except anhydrating, the sand of the uniform loading metal ion obtained is as the solid state substrate model containing heavy metal ion.60g above-mentioned solid state substrate model and the fluorine-containing sequestrant of 1.0g is added in supercritical carbon dioxide extraction still, heating makes extraction kettle temperature be elevated to 40 DEG C and keep constant temperature, open and stir, pass into carbonic acid gas to extraction kettle make the pressure of extraction kettle be elevated to 16MPa and keep 20 minutes, open high-pressure circulation pump, supercritical carbon dioxide extraction 40 minutes are used under the pressure of 16MPa, 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, Brooker company of Germany) measure Cu
2+, Pb
2+and Ag
+residual (with not adding the sand of 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 fluorine-containing sequestrant in supercritical carbon dioxide systems extracting heavy metal ions of embodiment 6.Its concrete using method is:
10mL is contained 2.5mg/mLLa
3+, 2.5mg/mLCe
4+and 2.5mg/mLEu
3+aqueous nitric acid join in the supercritical carbon dioxide extraction still that the fluorine-containing sequestrant of 600mg is housed as the liquid matrix model containing rare earth ion, heating makes extraction kettle temperature be elevated to 60 DEG C and keep constant temperature, open and stir, pass into carbonic acid gas to extraction kettle make the pressure of extraction kettle be elevated to 20MPa and keep 20 minutes, open high-pressure circulation pump, supercritical carbon dioxide extraction 40 minutes are used under the pressure of 20MPa, 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, Brooker company of Germany) 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 (1)
1. a preparation method for fluorine-containing sequestrant, the structural formula of this sequestrant is as follows:
In formula m be 0 or the value of 1, n be 0 or 1; When wherein m is 0, R
ffor formula (1) substituting group;
When m is 1, R
ffor formula (3):
It is characterized in that it is prepared from by following step:
(1) synthesis of iminodiacetic acid diester
After iminodiethanoic acid and thionyl chloride are reacted 4 ~ 8 hours at 35 ~ 60 DEG C, 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 terminates, underpressure distillation, obtains iminodiacetic acid (salt) acid diesters;
Above-mentioned alcohol is methyl alcohol, ethanol, Virahol or the trimethyl carbinol;
(2) fluorine-containing sequestrant is synthesized
Be R by iminodiacetic acid (salt) acid diesters and general structure
fthe fluorine-containing carboxylic acid halides of '-COX or general structure are R
f'-CH
2the fluorine-containing halohydrocarbon of X, anhydrous sodium carbonate or Anhydrous potassium carbonate are that 1 ~ 1.25:1:0.50 ~ 0.75 mixes according to mol ratio, DEG C reaction 6 ~ 18 hours in normal temperature ~ 80, 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
f' be
Wherein the value of n is 0 or 1, general structure R
fin '-COX, X is F, Cl or Br, general structure R
f'-CH
2in X, X is Cl or Br.
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| 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 |
| 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 |
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 |
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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 |
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