JPH0228590B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a fluorine-containing compound that selectively captures metal ions, particularly uranyl ions, from natural water such as seawater, mineral water, groundwater, river lake water, or wastewater in a high yield, and a method for producing the same. Regarding. In recent years, due to the problem of depletion of fossil fuels, the use of electronic energy as an alternative energy source has attracted attention. The estimated reserves of uranium, the raw material, are around 1 million tons, and judging from future demand forecasts, it cannot be said to be abundant. In contrast, approximately 4.5 billion tons of uranium are dissolved in all seawater.
If this can be extracted efficiently, seawater can become an inexhaustible source of uranium. Currently, titanic acid, ion exchange resins, chelate resins, etc. are known as adsorbents for uranium. Nothing of high practicality has been found. Recently, macrocyclic hexaketones that selectively include and incorporate uranyl ions (Tabushi et al., Nature,
280, 665 (1979), but the synthesis of such cyclic compounds generally requires a large number of steps;
Furthermore, it is necessary to use a dilution method, which is disadvantageous from an industrial perspective. Based on a new idea, the present inventors have developed fluorine-containing ionophores that utilize the properties of polyfluoroalkyl groups. In other words, if one or more polyfluoroalkyl groups are introduced into a group capable of clathrating metal ions, polyfluoroalkyl groups have extremely low affinity for organic solvents, so that they can be bonded to each other within or between molecules. We thought that the residues that could associate and interact with metal ions would also come close to each other, forming an inclusion field similar to that of cyclic ionophores. As a result of carrying out molecular design based on this concept, we have discovered a fluorine-containing compound that selectively includes uranyl ions and can be produced in high yield and at low cost, leading to the completion of the present invention. The present invention can thus include useful metal ions such as uranyl ions in an organic solvent,
The present invention provides a novel fluorine-containing compound that extracts metal ions dissolved in water or transports metal ions in an organic liquid membrane, and a method for producing the same. The novel fluorine-containing compound according to the present invention has the general formula [In the formula, R _f is a perfluoroalkyl group having 3 to 10 carbon atoms, and R ₁ is a hydrogen atom or a perfluoroalkyl group having 1 to 10 carbon atoms.
3 alkyl group, R ₂ is an alkyl group having 1 to 3 carbon atoms, an aryl group, or a substituted aryl group substituted with an alkyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, a is 0 or 1 , l and n are integers from 1 to 4. ] Represented. It is important that the compound of the present invention is dissolved in an organic solvent that hardly dissolves in water and does not mix with water, mainly for the purpose of collecting useful metals dissolved in water. Solubility in water depends on the length n of the hydrophilic oligoethylene oxide group and the balance of other hydrophobic residues, but due to the ease of obtaining raw materials,
Particularly important are those in which the length n of the oligoethylene oxide group is 1 to 3. Specific examples of the novel fluorine-containing compounds of the present invention include the following. The fluorine-containing compound according to the present invention is produced in high yield by the following production method. That is, the general formula [In the formula, R _f , R ₁ , R ₂ , l and a have the same meanings as above. ] The N-H proton of [Formula] of a fluorine-containing compound containing a urea bonding group or a carbonamide group in the molecule is converted to Na using CH ₃ ONa, NaH, (CH ₃ ) ₃ COK, etc. Or replace K with the general formula [In the formula, R _f , R ₁ , R ₂ , l and a have the same meanings as above, and M is a sodium atom or a potassium atom. ] After forming a compound represented by the general formula X(-CH ₂ CH ₂ O)- _o CH ₂ CH ₂ -X () [wherein, ] The compound of the present invention is produced by reacting with a dihalogenated oligoethylene glycol represented by the following formula. In such a reaction, the solvent may be methyl cellosolve, butyl cellosolve, butyl cellosolve,
Examples include butyl carbitol, dimethylformamide, dimethyl sulfoxide, etc., and the reaction temperature is 80°C.
~140°C and a reaction time of 5 to 16 hours are appropriate.
Metal halides and halogenated amine salts, which are reaction by-products, may precipitate as crystals at room temperature, but they may be included in the produced fluorine-containing compound and dissolved uniformly. In this case, purification can be achieved by once distilling off the solvent under reduced pressure at 140° C. or below, dissolving the residue in an alcoholic solvent such as ethanol, and then desalting with a cation exchange resin. The fluorine-containing compound of the formula used as a raw material for the above reaction is usually an easily available reactive perfluoroalkyl sulfonic acid or a halide or ester of these acids, and a general formula of [In the formula, R ₁ and l have the same meanings as above. ] The general formula obtained by reacting the diamine represented by [In the formula, R _f , R ₁ and l have the same meanings as above. ] A fluorine-containing compound represented by the general formula R ₂ —N=C=O [wherein R ₂ has the same meaning as above] is prepared in an aprotic solvent. ] or in the presence of a base catalyst such as pyridine or in the absence of a catalyst of the general formula [Formula] [wherein R ₂ has the same meaning as above. ] It can be produced with good yield by reacting with an acid anhydride represented by: In addition, regarding the compound of the general formula, when n is 1 or 2, it can be purchased at low cost, and when n is 3
In the above cases, see the literature (CJPedersen, J. Amer.
Chem.Soc., 89 , 7017 (1967)). Table 1 shows the chloroform solution (7.0×10 ^-4 M, 20ml) of the fluorine-containing compound according to the present invention and each metal salt (uranyl acetate, NaCl, MgCl ₂ , CaCl ₂ , CoCl ₂ ,
NiCl ₂ , CuCl ₂ , ZnCl ₂ ) aqueous solution (7.0×10 ^-4 M,
This is a summary of the results of liquid-liquid extraction of the metal salts prepared separately (20 ml) and stirred with a magnetic stirrer at 37°C for 24 hours. The extraction amount was determined by quantifying the metal ions remaining in the aqueous solution (uranyl ion: arsenazo method, other metal ions: atomic absorption method). [Table] The compound of the present invention has a low inclusion ability for light metal ions and ordinary heavy metal ions, but has an extremely high inclusion ability for uranyl ions.
Such a highly selective capture ability for uranyl ions of the compound of the present invention is extremely useful in practice. Table 2 shows that uranyl acetate is dissolved in artificial seawater.
These are the results of an extraction experiment conducted in the same manner as in Table 1. [Table] As can be seen from this result, the compound of the present invention is
Almost unaffected by coexisting metal ions,
It is possible to selectively include uranyl ions. Table 3 shows natural seawater 1 (collected at Komaiko Beach, containing 3.3 μg of uranium).
30 ml of chloroform solution containing 1 mg of the compound of the invention
This shows the results of a uranium extraction experiment obtained by catalyzing uranium under stirring at room temperature for 48 hours. [Table] The compound of the present invention can capture uranyl ions in good yield even from natural seawater where many types of ions coexist, and is extremely useful in practice. The clathrated uranyl ion can be easily recovered by contacting it with a mineral acid such as hydrochloric acid, nitric acid, or sulfuric acid, or an aqueous solution of ammonium carbonate, caustic soda, sodium bicarbonate, or soda carbonate.
Moreover, the compound of the present invention can be repeatedly reused, which is very advantageous industrially. Since the compounds of the present invention are soluble in many organic solvents that are immiscible with water, they can be prepared by impregnating a porous polymer membrane with the solution or by adding an emulsifier.
By forming a (W/O)/W type emulsion (an emulsion in which a W/O type emulsion is dispersed in water), it is possible to use it as an ion carrier for a liquid thin film. It is also possible to support it on a solid support and use it as an adsorbent for uranyl ions. Next, synthesis examples of the compounds of the present invention will be shown to further specifically illustrate the present invention. Synthesis example 1 2 with cooling condenser and stirrer
In a three-necked round bottom flask, add N-methyl-1,3-
Weigh out 264 g (3.0 mol) of diaminopropane and 400 g of fully dehydrated isopropyl ether under a nitrogen atmosphere, and add 422 g (1.05 mol) of perfluorohexylsulfonyl fluoride at room temperature while stirring thoroughly.
was dripped. After stirring at 50°C for 3 hours, the isopropyl ether was removed under reduced pressure. The yellow solid residue was dissolved in 500 ml of ethanol, and it was gradually poured into 8 ml of distilled water under stirring to ripen the crystals. The supernatant liquid was removed by decantation, and decantation was performed three times using 5 portions of distilled water each time.
The crystals were collected, water was sufficiently removed, washed with 1 portion of ethyl acetate, and dried under reduced pressure at 70°C. 440g of pale yellow crystals. mp=171.0−172.0℃ [Table] IR spectrum 1370cm ^-1 (−SO ₂ Nνas) NMR spectrum (CD ₃ OD solvent, TMS standard) 1.80ppm (m, 2H), 2.65ppm (s, 3H),
3.05ppm (t, 2H), 3.26ppm (t, 2H) 500ml with dry silica gel tube and stirrer
N-(3-methylaminopropyl) perfluorohexyl sulfonamide in a 3-necked round bottom flask.
47 g (0.1 mol) and 250 ml of sufficiently dehydrated tetrahydrofuran were weighed out under a nitrogen atmosphere, and dissolved with stirring at room temperature. Methyl isocyanate 6.0g (0.105
20ml of tetrahydrofuran solution containing
was added dropwise at room temperature with vigorous stirring. After the addition was completed, the mixture was stirred at room temperature for 3 hours, and tetrahydrofuran was distilled off under reduced pressure to obtain 53 g of a pale yellow solid.
I got it. Usually, the above procedure yields a product of sufficient purity to be used in the next reaction, but if necessary, it can be recrystallized from chloroform/n-hexane. mp=59.5−60.5℃ [Table] IR spectrum 1370cm ^-1 (-SO ₂ Nνas) 1645cm ^-1 (N-CO-NH-) NMR spectrum (CD ₃ COCD ₃ solvent, TMS standard) 1.80ppm (t, 2H) , 2.69ppm (s, 3H),
2.90ppm (s, 3H), 3.21ppm (t, 2H),
3.47ppm (t, 2H) 100 with cooling condenser and stirrer
In a 3-necked round bottom flask, add N-{3-(1,3
10 g (0.019 mol) of perfluorohexyl sulfonamide and 70 g of thoroughly dehydrated methyl cellosolve were weighed out and dissolved by heating. 3.7 g (0.019 mol) of sodium methylate methanol solution (28%) was added dropwise at 80°C.
After heating to 110℃ and removing methanol, 1.
2-bis(2-chloroethoxy)nitane 1.8g
(0.0095 mol) was added gradually. After reacting at 90°C for 8 hours, methyl cellosolve was distilled off under reduced pressure. The paste-like residue was dissolved in 100 ml of ethanol, 10 g of Amberlite CG-400Type-1 was added, and the mixture was stirred at room temperature for 1 hour. The ion exchange resin was separated and ethanol was distilled off under reduced pressure to obtain 10.5 g of a pale yellow paste. [Table] MNR spectrum (CD ₃ OD solvent, TMS standard) 1.70ppm (m, 4H), 2.70ppm (s, 6H),
2.83ppm (s, 6H), 3.25ppm (m, 12H),
3.61ppm (m, 8H) Synthesis example 2 N-{3-[1- Methyl-3
10 g (0.0155 mol) of (3,4-dichlorophenyl)propyl}perfluorohexylsulfonamide and 70 g of thoroughly dehydrated methyl cellosolve,
100ml with cooling condenser and stirrer
The mixture was weighed into a three-necked round bottom flask and dissolved by heating.
Sodium methylate methanol solution (28
%) 3g (0.016 mol) was added dropwise, the temperature was raised to 110°C to remove methanol, and 1,11-dichloro-
3,6,9-trioxaundecane 1.75g (0.08
mol) was added gradually. After reacting at 90°C for 8 hours, methyl cellosolve was distilled off under reduced pressure. Dissolve the paste-like residue in 100ml of ethanol, add 10g of Amberlite CG-400Type-1,
Stirred at room temperature for an hour. Separate ion exchange resin,
By distilling off the ethanol under reduced pressure, 11.1 g of a pale yellow paste was obtained. [Table] NMR spectrum (CD ₃ OD solvent, TMS standard) 1.78ppm (m, 4H), 2.94ppm (s, 6H), 3.10
−3.40ppm (m, 12H), 3.60ppm (m, 12H),
7.20−7.85ppm (m, 6H) Synthesis example 3 N-(3-methylaminopropyl) perfluorohexyl sulfonamide 90 ml of N-(3-methylaminopropyl) perfluorohexyl sulfonamide was added to a 300 ml three-necked round-bottomed flask equipped with a silica gel drying tube and a stirrer.
(0.191 mol) and 134 g of pyridine, and while stirring vigorously at room temperature, add 29.3 g of acetic anhydride.
(0.287 mol) was gradually added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 3 hours, and pyridine was distilled off under reduced pressure. 150 ml of distilled water to the resulting viscous solid residue
was added to ripen the crystals. White crystals were collected, further washed with water, and dried under reduced pressure at 70°C. Yield: 100g. mp=77.0~78.5℃ [Table] IR spectrum 1370cm ^-1 (-SO ₃ Nνas) 1640cm ^-1 (-CON) NMR spectrum (CD ₃ COCD ₃ solvent, TMS standard) 1.83ppm (m, 2H), 2.04ppm ( s, 3H),
3.05ppm (s, 3H), 3.27ppm (t, 2H),
3.48ppm (t, 2H) 100 with cooling condenser and stirrer
mL of N- in a 3-necked round bottom flask under a nitrogen atmosphere.
10.2 g (0.02 mol) of {3-(N-methylacetamino)propyl}perfluorohexylsulfonamide and 80 g of sufficiently dehydrated methyl cellosolve were weighed out and dissolved by heating. 4.6 g (0.024 mol) of sodium methylate methanol solution (28%) at 90 °C
was added dropwise, the temperature was raised to 110°C, methanol was distilled off, and 1.7 g of bis(2-chloroethyl) ether was added.
(0.012 mol) was added gradually. After reacting at 90°C for 8 hours, the mixture was cooled to room temperature and the precipitated sodium chloride was separated. Methyl cellosolve was distilled off, the resulting residue was dissolved in 100 ml of ethanol, 10 g of Amberlite CG-400Type-1 was added, and the mixture was stirred for 1 hour at room temperature. The ion exchange resin was separated and ethanol was distilled off under reduced pressure to obtain 10.0 g of a slightly yellow solid. mp=53.5℃ [Table] NMR spectrum (CD ₃ OD solvent, TMS standard) 1.80ppm (m, 4H), 2.08ppm (d, 6H),
2.96ppm (d, 6H), 3.20-3.50ppm (m, 12H),
3.61ppm (t, 4H) Synthesis example 4 In the same manner as in Synthesis Example 1-(ii) using N-(3-methylaminopropyl) perfluorooctyl sulfonamide and β-naphthyl isocyanate. was synthesized. Next, 14.8 g (0.02 mol) of this compound and 1.7 g of bis(2-chloroethyl) ether
(0.012 mol) in the same manner as in Synthesis Example 3-(ii) to obtain 14.0 g of a pale yellow paste. [Table] NMR spectrum (CD ₃ OD solution, TMS standard) 1.72ppm (m, 4H), 2.92ppm (s, 6H), 3.10
−3.45ppm (m, 12H), 3.63ppm (t, 4H), 7.00
-7.80ppm (m, 14H) Synthesis example 5 Using N-(3-methylaminopropyl) perfluorooctyl sulfonamide and p-methylphenyl isocyanate, in the same manner as in Synthesis 1-(ii), was synthesized. Next, using this compound and 1,11-dichloro-3,6,9-trioxaundecane, a yellow paste was obtained in the same manner as in Synthesis Example 2. [Table] NMR spectrum (CD ₃ COCD ₃ solution, TMS standard) 1.73ppm (m, 4H), 2.90ppm (s, 6H),
2.95ppm (s, 6H) 3.10-3.50ppm (m, 20H),
3.62ppm (t, 4H), 7.85ppm (m, 8H) Synthesis example 6 Using N-(3-methylaminopropyl) perfluorooctyl sulfonamide and p-nitrophenyl isocyanate, in the same manner as in Synthesis Example 1-(ii), was synthesized. Next, using this compound and 1,2-bis(2-chloroethoxy)ethane, a yellow paste was obtained in the same manner as in Synthesis Example 1-(iii). [Table] NMR spectrum (CD ₃ COCD ₃ solution, TMS standard) 1.72ppm (m, 4H), 2.93ppm (s, 6H), 3.10
−3.50ppm (m, 16H), 3.63ppm (t, 4H),
7.70ppm (m, 8H) [Table] Synthesis example 7 Using N-(3-methylaminopropane) perfluorohexylsulfonamide and phenyl isocyanate, in the same manner as in Synthesis Example 1-(ii), was synthesized. This compound was then reacted with 1,11-dichloro-3,6,9-trioxaundecane in the same manner as in Synthesis Example 2 to obtain a yellow paste. [Table] NMR spectrum (CD ₃ COCD ₃ solution, TMS standard) 1.72ppm (m, 4H), 2.90ppm (s, 6H), 3.10
−3.50ppm (m, 20H), 3.62ppm (t, 4H),
7.84ppm (m, 10H) [Table]

Claims (1)

[Claims] 1. General formula [In the formula, R _f is a perfluoroalkyl group having 3 to 10 carbon atoms, and R ₁ is a hydrogen atom or a perfluoroalkyl group having 1 to 10 carbon atoms.
3 alkyl group, R ₂ is an alkyl group having 1 to 3 carbon atoms, an aryl group, or an alkyl group having 1 to 3 carbon atoms, an aryl group substituted with a halogen atom or a nitro group, a is 0 or 1, l and n are integers of 1-4. ] A fluorine-containing compound represented by: 2 General formula [In the formula, R _f is a perfluoroalkyl group having 3 to 10 carbon atoms, and R ₁ is a hydrogen atom or a perfluoroalkyl group having 1 to 10 carbon atoms.
3 alkyl group, R ₂ is an alkyl group having 1 to 3 carbon atoms, an aryl group, or an alkyl group having 1 to 3 carbon atoms, an aryl group substituted with a halogen atom or a nitro group, M is a sodium atom or potassium The atom, a, is 0 or 1, and l is an integer of 1-4. ] A compound represented by the general formula X(-CH ₂ CH ₂ O)- _o CH ₂ CH ₂ -X [wherein, ] A general formula characterized by reacting with a compound represented by [In the formula, R _f , R ₁ , R ₂ , a, l and n have the same meanings as above. ] A method for producing a fluorine-containing compound represented by: