CN1229340C - 3 oxide heteroperfluoro-nonyl fluorocarbon surfactant, its systhesizing method and usages - Google Patents
3 oxide heteroperfluoro-nonyl fluorocarbon surfactant, its systhesizing method and usages Download PDFInfo
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Abstract
The present invention relates to a sulfonyl compound with 3-oxyheteroperfluoro nonyl, a synthesis method and an application method thereof. The sulfonyl compound has a molecular formula of C6F13OC2F4SOnR, wherein R=NR<1>4 or N (R<2>) (CH2) mNR<3>4X, n is 2 or 3, and m is between 1 and 12, wherein R<1> is H or is alkyl of C1 to C4; R<2> is H or C1 to C3; R<2> is alkyl of C1 to C5; X is halogen. The sulfonyl compound has the advantages of simple synthesis method and commercial process. The sulfonyl compound has excellent surface activity in a water solution, can lower the surface tension of the water solution to 16 to 20 mN/m, is a kind of good surface active agents, and can be used in industries such as cosmetics, printing and dyeing, medicine, photosensitive materials, etc.
Description
Technical Field
The patent relates to a 3-oxa-perfluorononyl compound, a synthetic method and application thereof. Omega-iodine-3-oxa-perfluorononane sulfonyl fluoride is used as a raw material to generate 3-oxa-perfluorononane sulfonyl fluoride through fluorination, and the 3-oxa-perfluorononane sulfonyl fluoride is further used to synthesize a cationic surfactant and an anionic surfactant containing the 3-oxa-perfluorononane sulfonyl.
Background
Among the fluorine-containing materials, there are known solid materials such as polytetrafluoroethylene (Teflon) plastics and fluororubbers, and further, there are freon gas and inert liquid, which have been known to be environmental problems. These gaseous and liquid materials also have important application values. The fluorine-containing material has excellent heat resistance, chemical resistance and other advantages
Common surfactants or hydrocarbon surfactants have been studied and used for many years and are primarily fluorocarbon surfactants synthesized herein. Since fluorine atoms replace hydrogen atoms, namely fluorocarbon chains replace hydrocarbon chains, nonpolar groups in the surfactant not only have hydrophobic properties but also have unique oleophobic properties.
Fluorocarbon surfactants are generally solid products, and are not volatile like many other fluorocarbons, so they are not significantly toxic to the atmosphere and the environment.
Fluorocarbon surfactants exhibit high surface activity in water, i.e., very low surface tension, due to the hydrophobic and oleophobic fluorocarbon chains and the weak interaction between the fluorocarbon chains. The surface tension of the fluorocarbon surfactant with a plurality of different structures in a water solution with very low concentration can be 15-16 mN/m. This is a surface activity that cannot be achieved by any other non-fluorocarbon surfactant; the fluorocarbon surfactant has high stability, high chemical stability of acid resistance, high concentrated alkali resistance, strong oxidant resistance and the like due to the unique geometric dimension, electronegativity and other factors of fluorine atoms; non-fluorinated surfactants are not useful in these media; fluorocarbon surfactants can be used in combination with many non-fluorine surfactants, not only enhancing the use effect but also reducing the total concentration due to synergistic effects. This is very useful for reducing the cost of practical use of fluorocarbon surfactants; these characteristics are not possessed by any non-fluorine surfactants.
Perfluorocarbon surfactants have been widely used in industry, but less fluorocarbon surfactants containing ether linkages have been synthesized. Industrially, the perfluoroalkyl ether sulfonate surfactant has very good effect only in inhibiting the chromic acid mist (refer to the chemical bulletin, 1977, 35, 209), and has less application in other aspects. The perfluoroalkyl ether sulfonate surfactant can reduce the surface tension of the aqueous solution to 16-18mN/m, while the common surfactant can only reduce the surface tension of the aqueous solution to about 30 mN/m. The surfactant has the characteristics of acid resistance, alkali resistance, higher surface activity and the like, and has good application prospect in industry.
Disclosure of Invention
The invention aims to provide a 3-oxaperfluorononane sulfonyl compound.
The invention also aims to provide a synthesis method of the compound.
The molecular formula of the 3-oxaperfluorononane sulfonyl compound is as follows: c6F13OC2F4SOnR, N ═ 2 or 3, and when N is 2, R ═ N (R)2)(CH2)mNR3 3When X, n is 3, R is NR1 4(ii) a m is 1-12. Wherein R is1H or C1-4Alkyl of R2H or C1-3Alkyl of R3＝C1-5X ═ halogen.
The compound of the invention may be C6F13OC2F4SO3NR1 4Or C6F13OC2F4SO2N(R2)(CH2)mNR3 3And (4) X. Such as: c6F13OC2F4SO2N(CH3)C3H6N(CH3)3 +X-，C6F13OC2F4SO2NH(CH2)3N(CH3)3 +X-，C6F13OC2F4SO3N(C2H5)4And the like.
The synthesis method of the 3-oxa-perfluorononane sulfonyl compound can respectively prepare the raw materials of 3-oxa-perfluorononane sulfonyl fluoride and 3-oxa-perfluorononane sulfonate by the following method:
fluorinating omega-iodine-3-oxaperfluorononane sulfonyl fluoride with antimony trifluoride in the presence of a catalyst to obtain 3-oxaperfluorononane sulfonyl fluoride, wherein the reaction formula is as follows:
the invention relates to a synthesis method of potassium and sodium 3-oxaperfluorononanoate compounds, which comprises the following steps: hydrolysis of 3-oxaperfluorononanesulfonyl fluoride in a base gives the sulfonate salt, the reaction formula is as follows:
M＝Na，K
the compounds of the present invention can be prepared by the following methods, respectively:
the molecular formula of the invention is C6F13OC2F4SO3NR1 4 +Synthesis of tetraalkylammonium 3-oxaperfluorononanesulfonate compound: in organic solvent, the molecular formula is C6F13OC2F4SO23-oxaperfluorononanesulfonyl fluoride of F and of formula NR1 3Trialkylamine and having the molecular formula CH3Si(OR1)3Trialkoxymethylsilyl reaction to obtain 3-oxaperfluorononaneTetraalkylammonium sulfonate, wherein the molar ratio of 3-oxaperfluorononanesulfonyl fluoride, trialkylamine and trialkoxymethylsilane is 1: 0.5-3, the reaction temperature is 5-60 ℃, and the reaction is carried out for 1-10 hours.
Such as 3-oxaperfluorononanesulfonyl fluoride, triethylamine and triethoxymethylsilane, to give 3-oxaperfluorononanesulfonic acid tetraethylammonium, the reaction scheme is as follows:
the molecular formula of the invention is C6F13OC2F4SO2N(R2)(CH2)mNR3 2Synthesis of 3-oxaperfluorononanesulfonamide: in organic solvent, the molecular formula is C6F13OC2F4SO23-oxaperfluorononanesulfonyl fluoride of F and having the formula HN (R)2)(CH2)mNR3 2The N, N-dialkyl diamine is obtained by reacting in organic base or inorganic base for 0.5 to 6.5 hours at the temperature of between 20 and 100 ℃. Wherein the mol ratio of the 3-oxaperfluorononane sulfonyl fluoride to the N, N-dialkyl diamine to the alkali is 1: 0.5-3.
Such as C6F13OCF2CF2SO2NHCH2CH2CH2N(CH3)2Synthesis of Compound C by the action of N, N-dimethylethylenediamine and Sulfonyl fluoride6F13OCF2CF2SO2NHCH2CH2CH2N(CH3)2The reaction formula is as follows:
the molecular formula of the invention is C6F13OC2F4SO2N(R2)(CH2)mNR3 3Synthesis of compound of X: in organic solvent, the molecular formula is C6F13OC2F4SO2N(R2)(CH2)mNR3 23-oxaperfluorononanesulfonamide, and R3X and inorganic base or organic base react at 10-65 deg.c for 1-7 hr to obtain the product. Wherein, 3-oxaperfluorononanesulfonamide, R3The molar ratio of X to alkali is 1: 1-8: 0-3 respectively. The base is organic base or inorganic base, and the organic base can be triethylamine, ethylenediamine, propylenediamine, butylenediamine, diethylamine, propylamine, ethylamine, pyridine, bipyridine, etc. The inorganic base is monovalent metal or divalent metal hydroxide, carbonate or bicarbonate, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate or sodium bicarbonate.
Such as: c6F13OCF2CF2SO2N(CH3)CH2CH2CH2N(CH3)3Synthesizing compound I, under the alkaline condition, 3-oxa perfluoro-nonane sulfonamide under the action of methyl iodide to obtain compound C6F13OCF2CF2SO2N(CH3)CH2CH2CH2N(CH3)3I, the reaction formula is as follows:
the organic solvent in the present invention may be ethyl acetate, acetone, chloroform, dichloromethane, carbon tetrachloride, pyridine, tetrahydrofuran, etc.
Drawings
FIG. 1 shows the surface tension (78 ℃) of the compound 2 of the present invention in an aqueous solution.
FIG. 2 shows the surface tension (25 ℃) of the compound 3 of the present invention in an aqueous solution.
The main advantages of the invention are:
1 the surface tension of the potassium 3-oxaperfluorononanesulfonate compound of the present invention in an aqueous solution was tested. The results show that the potassium 3-oxaperfluorononanesulfonate also has good capability of reducing the surface tension of an aqueous solution, the Critical Micelle Concentration (CMC) value is 8.62mmol/L, and the maximum capability of reducing the surface tension of the aqueous solution is about 20 mN/m. From the results of comparison of the surface tension data, the application of the potassium 3-oxaperfluorononanesulfonate in industrial production has great potential.
2 changing the cation part in the surfactant has an effect on the surface activity of the surfactant, when the cation of the 3-oxa perfluorononane sulfonate is ammonium ion, the solubility of the surfactant in water is increased, the corresponding CMC value is changed to be O.996mmol/L, and the surface tension of the aqueous solution can be reduced to 17-18 mN/m. Organic ammonium ions can increase the solubility of some surfactants (Abstracts of the after national symposium on Colloid and Interface Chemistry, Chinese Chemistry Society, Wuhan, 1991: 310.), are highly desirable surfactants, and in addition, have the excellent properties of fluorocarbons, which have good application prospects as surfactants.
3 the synthesis of the 3-oxaperfluorononane sulfonic acid tetraethylammonium compound takes the reaction of triethylammonium and triethoxymethylsilicon as raw materials to react with 3-oxaperfluorononane sulfonyl fluoride to synthesize the compound 3-oxaperfluorononane sulfonic acid tetraethylammonium, has good reaction yield, and easily obtains the raw materials of ethylammonium and triethoxymethylsilicon, thereby being a synthesis route with industrial value.
4 the invention synthesizes two series of anion and cation of the 3-oxa-perfluorononyl fluorocarbon surfactant, which show good surface activity, can be used in industries of cosmetics, printing and dyeing, medicines, photosensitive materials and the like, and has good industrial application value.
Detailed Description
The following examples will help to understand the present invention, but do not limit the contents of the present invention.
EXAMPLE 1 Synthesis of Compounds 1 and 2
1M=Na，2M=K
Synthesis of 3-oxaperfluorononyl sulfonyl fluoride, 0.06mol of antimony trifluoride and 5mL of antimony pentachloride are added into a three-necked bottle provided with a condenser tube and a dropping funnel, the three-necked bottle is heated to 30-75 ℃ in an oil bath, about 5mL of chlorine gas is introduced within 2 hours, the temperature is raised to 115 ℃, 0.048mol of 9-iodo-3-oxaperfluorononyl sulfonyl fluoride is dropwise added within 1 hour under magnetic stirring, the reaction is continued for 4 hours, and the product 3-oxaperfluorononyl sulfonyl fluoride is evaporated out, wherein the yield is 83.6%.
0.01mol of 3-oxaperfluorononyl sulfonyl fluoride is added into 0.021mol of sodium hydroxide solution, magnetic stirring is carried out, reflux reaction is carried out for 1 hour under the heating of oil bath, and the compound 1 is obtained with the yield of 98 percent. The same procedure gave 100% yield of compound 2.
Compound 1C8F17S03Na
White solid with melting point higher than 295.0 deg.C
IR(KBr)：υ＝1255，1205，1162cm-1．
19F NMR，δF：-4.78(3F，t，CF3)，-5.61(2F，m，OCF2)，-6.68(2F，t，OCF2)，-41.91(2F，S，CF2SO3)，-45.81(2F，S，CF2)，-46.52(2F，d，CF2)，-49.15(2F，d，CF2)，-49.78～-49.88(2F，m，CF3CF2)。
Elemental analysis: calculated value (%): c17.84, F60.04. Found (%): c17.56, F59.53.
Compound 2C8F17SO3K
White solid, melting point 254.0 deg.C
IR(KBr)，υ＝1251，1203，1150cm-1.
19F NMR：δF：-4.77(3F，t，CF3)，-5.61(2F，m，OCF2)，-6.66(2F，m，OCF2)，-41.9(2F，s，CF2SO3)，-45.82(2F，m，CF2)，-46.53(2F，s，CF2)，-49.16(2F，s，CF2)，-49.77～-49.87(2F，m，CF3CF2)。
Elemental analysis: calculated value (%): c17.33, F58.30. Found (%): c17.55, F59.26.
EXAMPLE 2 Synthesis of Compound 3
0.01mol of sulfonyl fluoride was added dropwise to a solution of 0.012mol of triethylamine and 0.012mol of triethoxymethylsilicon in 30mL of chlorobenzene, and the mixture was stirred at room temperature for 8 hours to precipitate a white precipitate, which was filtered and then recrystallized from chlorobenzene to give 3 in 92% yield.
Compound 3C16H20F17NO4S
White solid, melting point: 178.4 deg.C
IR(KBr)：υ＝1266，1204，1123cm-1。
19F NMR，δF：-4.77(3F，t，CF3)，-5.58(2F，m，OCF2)，-6.63(2F，m，OCF2)，-41.90(2F，s，CF2SO3)，-45.80(2F，m，CF2)，-46.54(2F，m，CF2)，-49.16(2F，s，CF2)，-49.77～-49.88(2F，m，CF3CF2)。
1H NMR，δH：3.47(8H，q，CH2)，1.37(12H，t，CH3)。
Elemental analysis: calculated value (%): c29.77, H3.1, N2.17, F50.08. Found (%): c29.61, H3.3, N2.08, F51.23.
EXAMPLE 3 Synthesis of Compounds 4 and 5
0.01mol of sulfonyl fluoride and 0.02mol of N, N-dimethyl propane diamine are added into a mixture of 0.01mol of potassium hydroxide and 20mL of ethyl acetate, the mixture is magnetically stirred, reflux reaction is carried out for 2 hours, the mixture is filtered while the mixture is hot, solid is separated out after the filtrate is cooled, and the solid is recrystallized by ethanol to obtain CF3(CF2)5OCF2CF2SO2NHCH2CH2CH2N(CH3)2The yield thereof was found to be 72.4%.
3.5mmol of methyl iodide was added dropwise to 0.5mmol of CF in ice bath3(CF2)5OCF2CF2SO2NHCH2CH2CH2N(CH3)2And 20mL of ethyl acetate, stirred magnetically at room temperature for 48 hours, the solvent was evaporated, and the column was washed with ether to isolate Compound 4 in 66.6% yield.
Compound 4C14H16F17IN2O3S
Pale yellow solid, melting point: 105.1 deg.C
IR(KBr)：υ＝3508，3159，3008，1203，1144cm-1。
19F NMR，δF：-5.39(3F，t，CF3)，-5.65(2F，m，OCF2)，-7.07(2F，m，OCF2)，-40.84(2F，s，CF2SO3)，-46.32(2F，s，CF2)，-47.04(2F，m，CF2)，-49.57(2F，m，CF2)，-50.41(2F，m，CF3CF2)。
1HNMR，δH：3.35～3.29(2H，m，CH2N)，3.19(2H，t，CH=NH)，3.05(9H，s，CH3)，1.86(2H，m，CH2)。
Elemental analysis: calculated value (%): c22.64, H2.16, N3.77, F43.53. Found (%): c22.22, H2.22, N3.71, F42.90.
8mmol of methyl iodide was added dropwise to 0.5mmol of CF in ice bath3(CF2)5OCF2CF2SO2NHCH2CH2CH2N(CH3)2And 5mL of a mixture of acetone and O.8mmol of potassium hydroxide, magnetically stirring the mixture for 4 hours, heating the mixture to room temperature, stirring the mixture for 72 hours, evaporating the solvent under reduced pressure, and recrystallizing the mixture with ethanol to obtain a compound 5 with a yield of 72.3%.
Compound 5C15H18F17IN2O3S
White solid, melting point 294.1 deg.C
IR(KBr)：υ＝3009，1243，1207，1149cm-1.
19F NMR，δF：-4.61(3F，t，CF3)，-5.49(2F，t，OCF2)，-6.41(2F，d，OCF2)，-39.30(2F，S，CF2SO3)，-45.62(2F，s，CF2)，-46.34(2F，d，CF2)，-48.86(2F，s，CF2)，-49.69(2F，d，CF3CF2)。
1HNMR，δH：3.81(2H，t，CH2N(CH3)3)，3.7～3.5(2H，m，CH2N)，3.49(9H，s，CH3)，3.26(3H，s，CH3)2.07(2H，m，CH2)。
Elemental analysis: calculated value (%): c23.97, H2.39, N3.71, F42.84. Found (%): c23.63, H2.06, N3.34, F40.84.
Claims (6)
1, a 3-oxaperfluorononanesulfonyl compound having the formula: c6F13OC2F4SOnR, N ═ 2 or 3, and when N is 2, R ═ N (R)2)(CH2)mNR3 3When X, n is 3, R is NR1 4(ii) a m is 1-12; wherein R is1H or C1-4Alkyl of R2H or C1-3Alkyl of R3＝C1-5X ═ halogen.
2, a process as claimed in claim 13-oxaperfluorononanesulfonyl compound characterized by having the following formula C6F13OC2F4SO2N(CH3)C3H6N(CH3)3 +X-、C6F13OC2F4SO2NH(CH2)3N(CH3)3 +X-Or C6F13OC2F4SO3N(C2H5)4。
The method for synthesizing a 3-oxaperfluorononanesulfonyl compound according to claim 1, wherein the compound is prepared by the following steps:
(1) in organic solvent, the molecular formula is C6F13OC2F4SO23-oxaperfluorononanesulfonyl fluoride of F and of formula NR1 3Trialkylamine and having the molecular formula CH3Si(OR1)3The trialkoxymethylsilane is reacted to obtain 3-oxaperfluorononanesulfonic acid tetraalkylammonium, wherein the molar ratio of the 3-oxaperfluorononanesulfonyl fluoride to the trialkylamine to the trialkoxymethylsilane is 1: 0.5-3, the reaction temperature is 5-60 ℃, and the reaction time is 1-10 hours; or
(2) In organic solvent and at 20-100 deg.C, the molecular formula is C6F13OC2F4SO23-oxaperfluorononanesulfonyl fluoride of F and having the formula HN (R)2)(CH2)mNR3 2Reacting N, N-dialkyl diamine in organic or inorganic base for 0.5-6.5 hr to obtain C6F13OC2F4SO2N(R2)(CH2)mNR3 2The 3-oxaperfluorononanesulfonamide, wherein the molar ratio of the 3-oxaperfluorononanesulfonyl fluoride to the N, N-dialkyl diamine to the base is 1: 0.5 to 3; in organic solvent and at 10-65 deg.C, the molecular formula is C6F13OC2F4SO2N(R2)(CH2)mNR3 23-oxaperfluorononanesulfonamide, an organic or inorganic base, R3Reacting X for 1-7 hours to obtain a compound with a molecular formula of C6F13OC2F4SO2N(R2)(CH2)mNR3 3X, wherein, 3-oxaperfluorononanesulfonamide, R3The molar ratio of X to alkali is 1: 1-8: 0-3 respectively;
wherein R1, R2, R3, m and X are as described in claim 1.
The method for synthesizing a 3-oxaperfluorononanesulfonyl compound according to claim 3, wherein said organic base is: triethylamine, ethylenediamine, propylenediamine, butylenediamine, diethylamine, propylamine, ethylamine, pyridine, bipyridine; the inorganic base is a hydroxide, carbonate or bicarbonate of a monovalent metal or a divalent metal.
The method for synthesizing a 3-oxaperfluorononanesulfonyl compound according to claim 3, wherein the organic solvent is ethyl acetate, acetone, chloroform, dichloromethane, carbon tetrachloride, pyridine or tetrahydrofuran.
The use of a 3-oxaperfluorononanesulfonyl compound as claimed in claim 1, characterized by its use as a surfactant.
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| CN103130691B (en) * | 2013-03-07 | 2014-09-17 | 武汉大学 | Chromium fog inhibitor and preparation method thereof |
| CN105664784B (en) * | 2015-12-31 | 2018-06-01 | 山东华夏神舟新材料有限公司 | fluorine-containing surfactant and preparation method thereof |
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