CN101406816A - Method for producing sulfuric acid fluorinated surfactants - Google Patents
Method for producing sulfuric acid fluorinated surfactants Download PDFInfo
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- CN101406816A CN101406816A CNA2008101220681A CN200810122068A CN101406816A CN 101406816 A CN101406816 A CN 101406816A CN A2008101220681 A CNA2008101220681 A CN A2008101220681A CN 200810122068 A CN200810122068 A CN 200810122068A CN 101406816 A CN101406816 A CN 101406816A
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Abstract
The invention discloses a preparation method for a sulfuric acid ester salt fluorine surfactant. The method comprises the following steps: taking 4-perfluoro alkene oxygen group benzene sulfonyl chloride and 2-methylamino alcohol as raw materials, taking inorganic base or organic base as an acid-binding agent, and carrying out an amidation reaction in an organic solvent 1 to obtain N- ethoxyl-N-methyl-4-perfluoro alkene oxygen group benzene sulfonyl chloride; and carrying out the esterification reaction of N-ethoxyl-N-methyl-4-perfluoro alkene oxygen group benzene sulfonyl chloride and sulfur trioxide in an organic solvent 2 for 1.5 to 15 hours, carrying out distillation to remove the solvent when the esterification reaction is finished, adding water for dissolution, then adding inorganic base aqueous solution with the mass content of between 10 and 50 percent into the solution till the reaction system is neutral, stirring the reaction system for reaction, and finally obtaining sulphuric acid 2-( N-methyl-4- perfluoro alkene oxygen group benzene sulfonyl chloride)ethyl ester sodium. The preparation method has a convenient raw material source, a simple synthesis method and few wastes. In particular, sulfur trioxide (SO3) and N- ethoxyl-N-methyl-4- perfluoro alkene oxygen group benzene sulfonyl chloride are adopted to carry out the esterification reaction, thereby bringing about high reaction yield.
Description
(1) technical field
The present invention relates to a kind of preparation method of sulfuric acid fluorinated surfactants, particularly the preparation method of sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium.
(2) background technology
Since the 1950's, the fluorine surfactant development is very fast.1974, Mizuno etc. were raw material with the hexafluoropropylene trimer, had synthesized a series of fluorine surfactants, were 0.01% o'clock in mass concentration, and the surface tension of the aqueous solution is about 30mN/m[JP 51011084,1976].2003, St é b é has reported " starlike " non-ion fluorin surfactant with two hydrophilic chains and parents' oil chain, in concentration is 0.002%～0.02% o'clock, just the surface tension of the aqueous solution can be dropped to [Journal of Fluorine Chemistry about 30mN/m, 2003,119 (2): 191-205].2006, Nakamura synthesized the fluorine surfactant of multi-branched shape from glycerin oligomer, and the surface tension of its 0.1% aqueous solution drops to 20mN/m following [JP 2006137689,2006].
The anion fluorocarbon surfactant is the most important kind of fluorine surfactant, mainly be divided into carboxylic acid type, sulphonic acid ester salt type, sulfuric acid type and phosphate ester salt type four big classes [fluorine surfactant [M]. Beijing, China Light Industry Press, 1998:7].Sulfuric acid type surfactant is one of important kind of anion surfactant, and report [NL6600939,1966] was just arranged as far back as the sixties in last century, at present, and about the still constantly appearance of report of sulfuric acid type surfactant, as i-C
14H
29OSO
3Na, i-C
14H
29O (EO)
3SO
3The Na[Speciality Petrochemicals, 2002, (5): 4-7].Straight chain perfluoroalkyl sulfuric acid is as (CF
2)
mCH
2CH
2CH[(CH
2)
nH] OSO
3M, at m, the n combination is suitable, and working concentration is 3.4 * 10
-4Mol/L～10.0 * 10
-4During mol/L, the surface tension of the aqueous solution can be dropped to about 20mN/m, working concentration only is 1/10th of a general hydrocarbon sulfuric acid type surfactant, and better result of use [JP 2003113155,2003] is but arranged.But rarely have document to relate to the preparation method of the sulfuric acid fluorinated surfactants that contains perfluor at present.
(3) summary of the invention
It is convenient to the purpose of this invention is to provide a kind of raw material sources, and synthetic method is simple, the preparation method of the sulfuric acid fluorinated surfactants that contains perfluor that reaction yield is high.
The technical solution used in the present invention is:
A kind of structural formula is suc as formula the preparation method of sulfuric acid fluorinated surfactants shown in (I)-sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium, described method comprises: with the 2-methylaminoethanol shown in 4-perfluoro alkene oxygen base benzene sulfonyl chloride shown in the formula (II) and the formula (III) is raw material, with inorganic base or organic base is acid binding agent, carried out amidation process 6～24 hours under 0～150 ℃ in organic solvent 1, reaction finishes afterreaction liquid A post processing and obtains the N-ethoxy shown in the formula (IV)-N-methyl-4-perfluoro alkene oxygen base benzsulfamide; Get N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and sulfur trioxide in organic solvent 2, carried out esterification 1.5～15 hours in 60～120 ℃, esterification finishes the back distillation except that desolvating, add water 100mL, stir 5min, drip mass fraction again and be 10%～50% inorganic base aqueous solution to neutral, under 50～100 ℃, stir and got reactant liquor B in 1～5 hour, reactant liquor B post processing obtains sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium, in formula (I), formula (II), the formula (IV), n is 2 or 3:
Preferably when n was 3, described sulfuric acid fluorinated surfactants was sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester in the present invention.
Amidation process of the present invention, the ratio of raw material 4-perfluoro alkene oxygen base benzene sulfonyl chloride, 2-methylaminoethanol, acid binding agent amount of substance is 1: 1～5: 1～3.Proportioning is 1: 2.5: 2 preferably, and best proportioning is 1: 1.6: 1.5.The preferable reaction temperature of described amidation process is 60～120 ℃, and optimal reaction temperature is 80～100 ℃.Amidation process reaction time 6～24h, the preferable reaction time is 12～20h, optimum reacting time is 16～18h.
It is one of following that organic solvent 1 in the described amidation process of the preparation method of sulfuric acid fluorinated surfactants of the present invention is generally: acetonitrile, ethyl acetate, dichloroethanes, trichloroethanes, carrene, chloroform, chlorobenzene, dichloro-benzenes, nitrobenzene, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, thiophene, dimethyl sulfoxide (DMSO) etc.Preferred chlorobenzene, described organic solvent 1 is 1～3: 1 with the ratio of 4-perfluoro alkene oxygen base benzene sulfonyl chloride quality, preferable ratio is 2: 1.
In amidation process of the present invention, acid binding agent can also can be used organic base with inorganic base, as the inorganic base of acid binding agent can be one of following or the combination of two or more arbitrary proportions: NaOH, calcium hydroxide, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus, ammonium carbonate, sodium thiosulfate etc., or be one of following or the combination of two or more arbitrary proportions as the organic base of acid binding agent: triethylamine, diethylamine, ethamine, aniline, methylphenylamine, phenyl ethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, propylamine, diisopropylamine etc.The ratio of the amount of substance of 4-perfluoro alkene oxygen base benzene sulfonyl chloride and acid binding agent is 1: 1～3, and proportioning is 1: 2 preferably, and best proportioning is 1: 1.5.
Amidation process of the present invention, the reactant liquor post-processing step is recommended as: after amidation process finished, organic solvent was removed in the reactant liquor distillation, wash thickness grease, leave standstill,, get white crystal N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide with the chlorobenzene recrystallization.
Comparatively concrete, described method is carried out according to following steps: the 4-perfluoro alkene oxygen base benzene sulfonyl chloride that adds metering in the solvent chlorobenzene successively, 2-methylaminoethanol and acid binding agent, 4-perfluoro alkene oxygen base benzene sulfonyl chloride, the ratio of 2-methylaminoethanol and acid binding agent amount of substance is 1: 1～5: 1～3, in temperature is 80～100 ℃, amidation process takes place, 16～18 hours reaction time, amidation process finishes the back distillation except that desolvating, washing gained thickness grease, leave standstill, with the chlorobenzene recrystallization, get white crystal N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide.
Second step reaction of the present invention is with intermediate product N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and sulfur trioxide (SO
3) carry out esterification, N-ethoxy in the described esterification-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and SO
3The ratio of amount of substance be 1: 1～3, proportioning is 1: 1.8 preferably, best proportioning is 1: 1.3.The preferable reaction temperature of esterification is 75～115 ℃, and optimal reaction temperature is 85～100 ℃.The preferable reaction time in reaction time is 6～15h, and optimum reacting time is 10～12h.During concrete operations, sulfur trioxide can be dissolved in earlier in a small amount of organic solvent 2 and add reaction system.
Esterification used oleum, the concentrated sulfuric acid, chlorosulfonic acid to participate in usually in the past.But the effect of N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and oleum, the concentrated sulfuric acid, chlorosulfonic acid esterification is not as good as SO
3SO
3Active high, use SO
3Esterification speed is fast, and good product purity and generation spent acid are few.
The organic solvent 2 of esterification of the present invention is following one or more any combination: chloroform, cyclohexane, n-hexane, normal heptane, nitro benzene,toluene,xylene, oxolane, thiophene, pyridine; Preferred cyclohexane; Described organic solvent 2 is 1～5: 1 with the ratio of the quality of N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide.
After esterification is finished, be 1～1.5 in order to the alkali in the inorganic base aqueous solution of neutralization with N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide amount of substance ratio: 1.Proportioning is 1.1: 1 preferably, and best proportioning is 1.3: 1.Alkali and N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide reaction temperature is preferably 20～100 ℃, and the best is 60～75 ℃.Be preferably 2～4h during neutralization reaction, the best is 3～4h.Used alkali is following one or more any combination in the used inorganic base aqueous solution: NaOH, calcium hydroxide, sodium carbonate, sodium acid carbonate, sodium thiosulfate, potassium hydroxide, potash, saleratus, cesium carbonate, calcium carbonate, ammonium carbonate, carbonic hydroammonium, ammoniacal liquor.
After the described esterification, in and afterreaction liquid post-processing step as follows: in and afterreaction liquid filter, get the filter cake washing, drying, with the benzinum recrystallization, faint yellow solid powder sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium.
Comparatively concrete, esterification is carried out according to following steps: intermediate product N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and the SO that adds metering in organic solvent 2 successively
3, can be during operation earlier with SO
3Be dissolved in and add reaction system in a small amount of solvent, N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and SO
3The ratio of amount of substance be 1: 1～3, be 85～100 ℃ in temperature.Esterification takes place, reaction time 10～12h.Esterification finishes the back distillation except that desolvating, and adds water 100mL dilution, drips inorganic base aqueous solution at 60～75 ℃.Inorganic base is 1～1.5: 1 with the ratio of the amount of substance of N-ethoxy-N-methyl-4-perfluorinated nonene oxygen base benzsulfamide, dropwises back insulation reaction 3～4h.Cool to room temperature filters, washing, and drying, the benzinum recrystallization gets faint yellow solid powder sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium.
Beneficial effect of the present invention is mainly reflected in: raw material sources of the present invention are convenient, and synthetic method is simple, and refuse is few, particularly adopts sulfur trioxide (SO
3) carry out esterification with N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide, the reaction yield height, the aqueous solution that sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) the ethyl ester sodium that uses the inventive method to make is prepared, surface tension is low.
(4) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
The preparation of embodiment 1N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide
In the 500mL four-hole boiling flask, add the 225mL chlorobenzene, 124.5g (0.2mol) 4-perfluorinated nonene oxygen base benzene sulfonyl chloride (Lianyungang Thailand tall and erect new material Co., Ltd), 15.0g (0.2mol) 2-methylaminoethanol, 21.2g (0.2mol) natrium carbonicum calcinatum, stir, be warming up to 100 ℃, keep temperature to stir 12h.The reactant liquor decompression distillation, to solvent-free deviate from till.Be cooled to room temperature, washing gained thickness grease leaves standstill, and with the chlorobenzene recrystallization, gets white crystal N-ethoxy-N-methyl-4-perfluorinated nonene oxygen base benzsulfamide 122.6g, yield 92.7%.
The preparation of embodiment 2N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide
React according to embodiment 1 method, but the 2-methylaminoethanol feeds intake and is 75.1g (1.0mol), 21.2g (0.1mol) natrium carbonicum calcinatum changes 24g (0.6mol) NaOH into, and the amidation process temperature changes 120 ℃ into, keeps temperature to stir 24h.The reactant liquor decompression distillation, to solvent-free deviate from till.Be cooled to room temperature, washing gained thickness grease leaves standstill, and with the chlorobenzene recrystallization, gets white crystal N-ethoxy-N-methyl-4-perfluorinated nonene oxygen base benzsulfamide 124.7.0g, yield 94.3%.
The preparation of embodiment 3N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide
React according to embodiment 1 method, but solvent changes the 270mL trichloroethanes into, and the 2-methylaminoethanol feeds intake and is 24.0g (0.32mol), and 21.2g (0.1mol) natrium carbonicum calcinatum changes 40.5g (0.4mol) triethylamine into, the amidation process temperature changes 80 ℃ into, keeps temperature to stir 16h.The reactant liquor decompression distillation, to solvent-free deviate from till.Be cooled to room temperature, washing gained thickness grease leaves standstill, and with the chlorobenzene recrystallization, gets white crystal N-ethoxy-N-methyl-4-perfluorinated nonene oxygen base benzsulfamide 123.0g, yield 93.0%.
The preparation of embodiment 4N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide
React according to embodiment 1 method, but solvent changes the 270mL trichloroethanes into, and the 2-methylaminoethanol feeds intake and is 37.6g (0.5mol), and 21.2g (0.1mol) natrium carbonicum calcinatum changes 21.9g (0.3mol) diethylamine into, the amidation process temperature changes 100 ℃ into, keeps temperature to stir 12h.The reactant liquor decompression distillation, to solvent-free deviate from till.Be cooled to room temperature, washing gained thickness grease leaves standstill, and with the chlorobenzene recrystallization, gets white crystal N-ethoxy-N-methyl-4-perfluorinated nonene oxygen base benzsulfamide 121.2g, yield 91.6%.
The preparation of embodiment 5 sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium
Add the 100mL cyclohexane in the 250mL four-hole boiling flask, the N-ethoxy that 66.1g (0.1mol) embodiment 1 makes-N-methyl-4-perfluorinated nonene oxygen base benzsulfamide stirs and is warming up to 75 ℃, drips 24.0g (0.3mol) SO
3Cyclohexane (20mL) solution, dropwise and keep temperature to stir 15h.The reactant liquor decompression distillation, to solvent-free deviate from till.Be cooled to room temperature, add water 100mL, stir and be warming up to 60 ℃, drip water (100mL) solution of 15.9g (0.15mol) natrium carbonicum calcinatum, dropwise back insulation reaction 3h.Cool to room temperature filters, washing, and drying, the benzinum recrystallization gets faint yellow solid powder sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium 74.1g, yield 97.1%.The critical micelle concentration of its aqueous solution (CMC) is 8.0 * 10
-4Mol/L, the surface tension (γ of the aqueous solution at this moment
CMC) be 23.1mN/m.
The preparation of embodiment 6 sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium
React according to embodiment 5, but 24.0g (0.3mol) sulfur trioxide changes 11.65g (0.1mol) chlorosulfonic acid into, solvent changes toluene into, esterification reaction temperature changes 85 ℃ into, 15.9g (0.15mol) water of natrium carbonicum calcinatum (100mL) solution changes water (30mL) solution of 5.2g (0.13mol) NaOH into, the neutralization reaction temperature changes 75 ℃ into.The remaining reaction condition is identical with embodiment 5.Sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium yield 94.2%.
The preparation of embodiment 7 sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium
React according to embodiment 5, but solvent changes chlorobenzene into, 24.0g (0.3mol) sulfur trioxide changes 14.4g (0.18mol) sulfur trioxide into, esterification reaction temperature changes 115 ℃ into, 15.9g (0.15mol) water of natrium carbonicum calcinatum (100mL) solution changes water (100mL) solution of 14.4g (0.15mol) ammonium carbonate into, the neutralization reaction temperature changes 60 ℃ into.The remaining reaction condition is identical with embodiment 5.Sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium yield 92.9%.
The preparation of embodiment 8 sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium
React according to embodiment 5, it is 98% sulfuric acid that but 24.0g (0.3mol) sulfur trioxide changes 19.6g (0.2mol) mass fraction into, reaction time of esterification changes 6h into, 15.9g (0.15mol) water of natrium carbonicum calcinatum (100mL) solution changes water (30mL) solution of 4.0g (0.10mol) NaOH into, the neutralization reaction temperature changes 75 ℃ into.The remaining reaction condition is identical with embodiment 5.Sulfuric acid 2-(N-methyl-4-perfluorinated nonene oxygen base benzene sulfonamido) ethyl ester sodium yield 91.2%.
Claims (10)
1, a kind of structural formula is suc as formula the preparation method of sulfuric acid fluorinated surfactants shown in (I), it is characterized in that described method comprises: with the 2-methylaminoethanol shown in 4-perfluoro alkene oxygen base benzene sulfonyl chloride shown in the formula (II) and the formula (III) is raw material, with inorganic base or organic base is acid binding agent, in organic solvent 1, under 0～150 ℃, carried out amidation process 6～24 hours, after reaction finishes, get reactant liquor A post processing and obtain the N-ethoxy shown in the formula (IV)-N-methyl-4-perfluoro alkene oxygen base benzsulfamide; Get N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and sulfur trioxide in organic solvent 2, carried out esterification 1.5～15 hours in 60～120 ℃, esterification finishes the back distillation except that desolvating, be dissolved in water, add mass content again and be 10%～50% inorganic base aqueous solution to reaction system and be neutral, in 20～100 ℃ of following stirring reactions 1～5 hour, get reactant liquor B post processing and obtain sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium, in formula (I), formula (II), the formula (IV), n is 2 or 3.
2, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1 is characterized in that the ratio of described amidation process raw material 4-perfluoro alkene oxygen base benzene sulfonyl chloride, 2-methylaminoethanol, acid binding agent amount of substance is 1: 1～5: 1～3.
3, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1, it is characterized in that the organic solvent 1 in the described amidation process is one of following example: acetonitrile, ethyl acetate, dichloroethanes, trichloroethanes, carrene, chloroform, chlorobenzene, dichloro-benzenes, nitrobenzene, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, thiophene, dimethyl sulfoxide (DMSO), described organic solvent 1 is 1～3: 1 with the ratio of 4-perfluoro alkene oxygen base benzene sulfonyl chloride quality.
4, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1, it is characterized in that described inorganic base as acid binding agent is one of following or the combination of two or more arbitrary proportions: NaOH, calcium hydroxide, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus, ammonium carbonate, sodium thiosulfate, or described organic base as acid binding agent is one of following or the combination of two or more arbitrary proportions: triethylamine, diethylamine, ethamine, aniline, methylphenylamine, phenyl ethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, propylamine, diisopropylamine.
5, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1, it is characterized in that described amidation process reactant liquor post-processing step is: after amidation process finishes, organic solvent is removed in reactant liquor A distillation, wash thickness grease, leave standstill, with the chlorobenzene recrystallization, get white crystal N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide.
6, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1 is characterized in that N-ethoxy in the described esterification-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and SO
3The ratio of amount of substance be 1: 1～3.
7, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1 is characterized in that after the described esterification that used alkali is 1～1.5 with N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide amount of substance ratio in the used inorganic base aqueous solution: 1.
8, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1 is characterized in that after the described esterification that used alkali is following one or more any combination in the used inorganic base aqueous solution of neutralization: NaOH, calcium hydroxide, sodium carbonate, sodium acid carbonate, sodium thiosulfate, potassium hydroxide, potash, saleratus, cesium carbonate, calcium carbonate, ammonium carbonate, carbonic hydroammonium, ammoniacal liquor.
9, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1, the organic solvent 2 that it is characterized in that described esterification is following one or more any combination: chloroform, cyclohexane, n-hexane, normal heptane, nitro benzene,toluene,xylene, oxolane, thiophene, pyridine, described organic solvent 2 is 1～5: 1 with the ratio of the quality of 4-perfluoro alkene oxygen base benzene sulfonyl chloride.
10, the preparation method of sulfuric acid fluorinated surfactants as claimed in claim 1, after it is characterized in that described esterification, reactant liquor B post-processing step is as follows: reactant liquor B filters, get the filter cake washing, dry, with the benzinum recrystallization, get faint yellow solid powder sulfuric acid 2-(N-methyl-4-perfluoro alkene oxygen base benzene sulfonamido) ethyl ester sodium.
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