CN102784586A - Fluorine-containing surfactant and preparation method thereof - Google Patents
Fluorine-containing surfactant and preparation method thereof Download PDFInfo
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- CN102784586A CN102784586A CN2012103017062A CN201210301706A CN102784586A CN 102784586 A CN102784586 A CN 102784586A CN 2012103017062 A CN2012103017062 A CN 2012103017062A CN 201210301706 A CN201210301706 A CN 201210301706A CN 102784586 A CN102784586 A CN 102784586A
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- containing surfactant
- fluorine
- perfluoro hexyl
- propyl group
- alkylamine
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Abstract
The invention relates to a fluorine-containing surfactant and a preparation method of the fluorine-containing surfactant. The fluorine-containing surfactant is N-propyl-N-ethoxyl-perfluoro hexyl sulfamide. The structural formula of the fluorine-containing surfactant is shown in the specification. The preparation method of the fluorine-containing surfactant comprises the steps of: 1) mixing alkylamine, triethylamine and isopropyl ether, carrying out ice-bath and adding perfluoro hexyl sulfamide, and heating to obtain N-propyl perfluoro hexyl sulfamide; and 2) dissolving N-propyl perfluoro hexyl sulfamide in ethanol and adding potassium hydroxide, reacting for 1-3 hours, then adding 2-chlorohydrin, and heating and reacting for 12-24 hours to obtain the target product. The surfactant provided by the invention can remarkably reduce the surface tension of a water phase system, and the preparation method and process are simple and convenient and easy to operate, and the yield is high.
Description
Technical field
The invention belongs to the surfactant field, particularly a kind of fluorine-containing surfactant and preparation method thereof.
Background technology
Current perfluoro octyl sulfonic acid and salt thereof (PFOS) are widely used on market and pay close attention to, and being has the effect that can not replace because of its application in industries such as fluorine material, fabric finishing agent, coating, pigment, additive.But recent discovers; PFOS is difficult in natural environment, degrade; And have very high bioaccumulation property, and accumulate in the mankind and the animal tissue easily and cause murder by poisoning, suffer the forbidding of countries in the world (comprising states such as European Union, the U.S., Canada) successively or limit the use of.Therefore, to substitute PFOS very urgent for the fluorocarbon surfactant of the new compliance with environmental protection requirements of exploitation.
Summary of the invention
Technical problem to be solved by this invention provides a kind of fluorine-containing surfactant and preparation method thereof, and fluorine-containing surfactant of the present invention has following performance characteristic: (1) has lower working concentration (less than 100mg/L); (2) have the good capillary effect of reduction aqueous phase system, when saturated, the surface tension of aqueous phase system is 28.64mN/m in the water; Fluorine-containing surfactant preparation method of the present invention, technology are easy, and productive rate is high, easy operating.
Fluorine-containing surfactant of the present invention is N-propyl group-N-ethoxy perfluoro hexyl sulfonamide, and structural formula is:
The preparation method of fluorine-containing surfactant of the present invention comprises:
(1) alkylamine, triethylamine and isopropyl ether is miscible, ice bath splashes into the perfluoro hexyl sulfuryl fluoride, and 60-70 ℃ is reacted 3-4h down and get N-propyl group perfluoro hexyl sulfonamide;
(2) the N-propyl group perfluoro hexyl sulfonamide that said step (1) is obtained is dissolved in ethanol and adds potassium hydroxide, and 40-50 ℃ is reacted 1-3h down, adds ethylene chlorhydrin then, 70-80 ℃ of reaction 12-24h, and products therefrom is said fluorine-containing surfactant.
(3) mol ratio of the alkylamine in the said step (1), triethylamine, perfluoro hexyl sulfuryl fluoride is 1:1.1～1.3:1.3～1.5, and the concentration range of alkylamine in isopropyl ether is that 0.04～0.08g/mL, the triethylamine concentration range in isopropyl ether is 0.06～0.15g/mL.
The perfluoro hexyl sulfuryl fluoride in the said step (1) and the reaction temperature of alkylamine are controlled at 60-70 ℃, and being lower than 60-70 ℃ of reaction yield can reduce, and is higher than 60-70 ℃, have side reaction and take place, and the reaction time is 3-4h.
Alkylamine in the said step (1) is one or more in methylamine, ethamine, propylamine, the butylamine, preferred n-propylamine.
N-propyl group perfluoro hexyl sulfonamide in the said step (1) is got by following purification procedures:
After step (1) reaction finishes, at first in reaction system, add distilled water, remove water behind the standing demix; Using mass concentration is that 0.5% salt acid elution is to neutral; Use the saturated common salt water washing again, isolate product, use anhydrous magnesium sulfate drying; Filter, obtain N-propyl group perfluoro hexyl sulfonamide after the decompression distillation.
The N-propyl group perfluoro hexyl sulfonamide in the said step (2) and the mol ratio of potassium hydroxide and ethylene chlorhydrin are 1:1～3:1～3, and the concentration range of N-propyl group perfluoro hexyl sulfonamide in ethanol is 0.25～0.5g/mL.
Selecting perfluoro hexyl sulfuryl fluoride, n-propylamine, triethylamine and ethylene chlorhydrin with reactant is example, above-mentioned preparation method's step 1) and step 2) chemical equation, distinguish as follows:
Fluorine-containing surfactant provided by the present invention has following architectural feature: (1) belongs to non-ionic surface active agent; (2) contain the perfluoroalkyl chain of six carbon; (3) contain a hydroxyl.
The present invention adopts the perfluoro hexyl sulfuryl fluoride as raw material, with the n-propylamine reaction, obtains obtaining target product N-propyl group-N-ethoxy perfluoro hexyl sulfonamide with the ethylene chlorhydrin reaction again behind the N-propyl group perfluoro hexyl sulfonamide.
Beneficial effect
Fluorine-containing surfactant provided by the invention has following performance characteristic: (1) has lower working concentration (less than 100mg/L); (2) have the good capillary effect of reduction aqueous phase system, when saturated, the surface tension of aqueous phase system is 28.64mN/m in the water; Preparation method provided by the invention, technology are easy, and productive rate is high, easy operating.
Description of drawings
Fig. 1 is the infrared spectrogram of the fluorine-containing surfactant N-propyl group-N-ethoxy perfluoro hexyl sulfonamide of instance 1 preparation of the present invention.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The preparation fluorine-containing surfactant
1) in the 100mL three-necked bottle, adds isopropyl ether 20mL as solvent; In the perfluoro hexyl sulfuryl fluoride: n-propylamine: the triethylamine ratio is 1:1.1:1.3; Add triethylamine 2.63g (0.026mol), n-propylamine 1.30g (0.022mol) successively; Put into ice-water bath, and guarantee that temperature maintenance is at 0 ℃ ~ 5 ℃.Get perfluoro hexyl sulfuryl fluoride 8.04g (0.020mol) in dropping funel, slowly splash in the three-necked bottle, agitator speed is made as 500r/min, and 30min dropwises.Connect reflux condensing tube, and then be heated to 60 ℃ with the oil bath of thermostatical oil bath, back flow reaction stopped reaction in 4 hours.
After reaction finishes, stop heating, cool to room temperature stops to stir.Change separatory funnel over to, spend deionised water 2 times, branch vibration layer; HCl with mass fraction 0.5% regulates pH to neutral, divides to fall water layer again; With saturated NaCl solution washing, and use the acetone extract organic facies; Extraction phase is used anhydrous MgSO
4Dry back simple filtration gets light yellow transparent liquid.Heating decompression distillation down obtains light yellow waxy solid N-propyl group perfluoro hexyl sulfonamide except that the isopropyl ether that desolvates, acetone and oven dry.
2) in the 100mL three-necked bottle, add dry N-propyl group perfluoro hexyl sulfonamide 8.82g (0.02mol), add the 30mL absolute ethyl alcohol subsequently, make the dissolving of waxy solid N-propyl group perfluoro hexyl sulfonamide, system is light yellow transparent liquid; Then add KOH 3.37g (0.06mol), be heated to 40 ℃, and under agitator, stir with 500r/min speed with the thermostatical oil bath.
Slowly drip ethylene chlorhydrin 4.83g (0.06mol) behind the reaction 1.5h, be warming up to 70 ℃ after dropwising and reflux and successive reaction 24h.
After reaction finishes, stop heating, cool to room temperature stops to stir, and system is divided two-layer, and the upper strata is the crocus transparency liquid, and lower floor is solid-state salt.Get filtrating with the vavuum pump decompress filter, filtrating is changed in the separatory funnel, use saturated NaHCO
3Washing, layering, the oily organic matter appears in lower floor, treats to separate the upper strata after the clarification of upper strata; With saturated NaCl solution washing lower floor organic matter 2 times, use acetone extract, extraction phase is used anhydrous MgSO
4Dry back simple filtration gets brown yellow transparent liquid.Decompression distillation is removed etoh solvent, acetone and oven dry and is obtained pale brown look grease N-propyl group-N-ethoxy perfluoro hexyl sulfonamide under the heating.
Can find out v by Fig. 1
O-H3389cm
-1The place is hydroxyl (characteristic peak OH) for wide and blunt crest; Near 3000-3300, do not have tangible absworption peak, the existence that does not have N-H is described; At 2974cm
-1The place and neighbouring be the peak of methyl and methylene; At 1471cm
-1The place is methylene deformation vibration peak; At 1387cm
-1The place is SO
2Absworption peak; At 1237cm
-1, 1209cm
-1, 1174cm
-1, 1149cm
-1, 1133cm
-1, 1120cm
-1The place is CF
2A series of absworption peaks; At 1052cm
-1The vibrations peak of C-N (tertiary amine) has appearred in the place.And SO
2The absworption peak of-F is 1468cm
-1, in spectrogram, do not find, raw material perfluoro hexyl sulfuryl fluoride complete reaction is described, whether find the primary amine characteristic peak in the spectrogram, explain and also do not have the raw material n-propylamine.
Can find out that by table 1 surface tension of fluorine-containing surfactant is 28.64mN/m; Surface-active is apparently higher than the surfactant of hydrocarbon class; And to compare surface-active strong slightly with the perfluoro octyl sulfonic acid of equal in quality concentration; But perfluoro octyl sulfonic acid is along with the increase of mass concentration can make the surface tension of water reduce to 21.13mN/m; And N-propyl group-N-ethoxy perfluoro hexyl sulfonamide is because its solubility in water is too small, thereby its mass concentration is improved is seriously restricting its high surface, but it can be through increasing its solubility in water with polymerization such as oxirane.
The fluorine-containing surfactant of table 1 instance 1 preparation and the surface tension contrast table of perfluoro octyl sulfonic acid
Claims (7)
1. fluorine-containing surfactant; It is characterized in that: said fluorine-containing surfactant is N-propyl group-N-ethoxy perfluoro hexyl sulfonamide, and structural formula is:
2. method for preparing fluorine-containing surfactant comprises:
(1) alkylamine, triethylamine and isopropyl ether is miscible, ice bath splashes into the perfluoro hexyl sulfuryl fluoride, and 60-70 ℃ is reacted 3-4h down and get N-propyl group perfluoro hexyl sulfonamide;
(2) the N-propyl group perfluoro hexyl sulfonamide that said step (1) is obtained is dissolved in ethanol and adds potassium hydroxide, and 40-50 ℃ is reacted 1-3h down, adds ethylene chlorhydrin then, 70-80 ℃ of reaction 12-24h, and products therefrom is said fluorine-containing surfactant.
3. a kind of method for preparing fluorine-containing surfactant according to claim 2; It is characterized in that: the mol ratio of the alkylamine in the said step (1), triethylamine, perfluoro hexyl sulfuryl fluoride is 1:1.1～1.3:1.3～1.5, and the concentration range of alkylamine in isopropyl ether is that 0.04～0.08g/mL, the triethylamine concentration range in isopropyl ether is 0.06～0.15g/mL.
4. a kind of method for preparing fluorine-containing surfactant according to claim 2 is characterized in that: the alkylamine in the said step (1) is one or more in methylamine, ethamine, propylamine, the butylamine.
5. a kind of method for preparing fluorine-containing surfactant according to claim 3 is characterized in that: said alkylamine is a n-propylamine.
6. a kind of method for preparing fluorine-containing surfactant according to claim 2 is characterized in that: the N-propyl group perfluoro hexyl sulfonamide in the said step (1) is got by following purification procedures:
After step (1) reaction finishes, at first in reaction system, add distilled water, remove water behind the standing demix; Using mass concentration is that 0.5% salt acid elution is to neutral; Use the saturated common salt water washing again, isolate product, use anhydrous magnesium sulfate drying; Filter, obtain N-propyl group perfluoro hexyl sulfonamide after the decompression distillation.
7. a kind of method for preparing fluorine-containing surfactant according to claim 2; It is characterized in that: the mol ratio of the N-propyl group perfluoro hexyl sulfonamide in the said step (2), potassium hydroxide, ethylene chlorhydrin is 1:1～3:1～3, and the concentration range of N-propyl group perfluoro hexyl sulfonamide in ethanol is 0.25～0.5g/mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408695A (en) * | 2013-07-11 | 2013-11-27 | 东华大学 | Preparation and application of perfluoro-short-carbon-chain-containing water-repellent oil-repellent finishing agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020731A (en) * | 2007-03-12 | 2007-08-22 | 安徽大学 | Process of preparing solvent type fluoric acrylate copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020731A (en) * | 2007-03-12 | 2007-08-22 | 安徽大学 | Process of preparing solvent type fluoric acrylate copolymer |
Non-Patent Citations (2)
| Title |
|---|
| 杨彬彬: "新型含氟聚丙烯酸酯的合成及其在棉织物上的应用", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
| 潘阳等: "氟表面活性剂C8F17SO2N(C2H5)C2H4(OC2H4)NOH的合成与性能", 《材料开发与应用》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408695A (en) * | 2013-07-11 | 2013-11-27 | 东华大学 | Preparation and application of perfluoro-short-carbon-chain-containing water-repellent oil-repellent finishing agent |
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Application publication date: 20121121 |