CN103007812A - Preparation method of sulfate surfactant containing fluoride anion and use thereof - Google Patents
Preparation method of sulfate surfactant containing fluoride anion and use thereof Download PDFInfo
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Abstract
The invention discloses synthesis of sulfate surfactant [N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butylene ether) benzene sulfonamido] sodium ethylsulfate containing fluoride anion and use thereof, and discloses a preparation method thereof. The surface properties such as surface tension, interfacial tension, contact angle, water repellency, oil repellency, oil displacement efficiency, wettability, foamability and emulsibility are researched so as to find out the low surface tension and interfacial tension, and excellent water repellency, oil repellency, wettability, foamability and emulsibility; and the sulfate surfactant has certain oil displacement efficiency after a hydrocarbon surfactant is compounded.
Description
Technical field
The present invention relates to preparation of a kind of sulfate type anionic fluorochemical surfactant [N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] SES and uses thereof.
Background technology
Fluorine-containing surfactant is owing to have a characteristic of " three height, two are hated ", along with demand international, the domestic market increases day by day, the fluorine-containing surfactant excellent performance, with high content of technology, added value is large, causes domestic and international researcher's very big interest.Its fluorine-containing alkyl has the water of refusing, refuses oil [new chemical materials, 2004,32 (8): 46], is widely used in industry and the agriculture fields [household chemicals, 2011,41 (4): 40-43] such as oil, coal, mining and metallurgy, machinery, weaving, medicine.
Anion surfactant is as one of wherein important kind, mainly contain carboxylic acid type, sulfonate type, sulfate type and phosphate type etc. [fluorocarbon surfactant [M]. Beijing, Chemical Industry Press, 2001,6; Surfactant Chemistry [M]. Beijing, publishing house of Beijing University of Science ﹠ Engineering, 2009,8]; Have good foaminess, soil release characteristics, dispersiveness, emulsibility and stability in hard water, its aqueous solution is neutral or faint alkalescence, is widely used as washing agent, foaming agent, wetting agent, emulsifying agent and dispersant, and output accounts for the first place of surfactant.
In the sulfate type anionic fluorochemical surfactant molecule, hydrophobic group generally also has common hydrocarbon chain except containing fluorocarbon chain; Containing the fluorocarbon chain major part is the straight chain of 6-10 carbon atom; Its hydrophilic group is the sulfate radical anion.
The developed countries such as the U.S., West Europe, Japan develop this series products in succession, as: Dupont, Britain ICI, French Atochem, German Hoechst and Bayer, Switzerland Ciba-Geigy and the companies such as Japan AGC, Da Jin and Neos have the international market more than 80%.With abroad compare, China's fluorine-containing surfactant, all relatively weaker no matter on production capacity, or in study on the synthesis, application study.
In recent years, the research report for the straight chain fluorine-containing surfactant is a lot.The perfluor sulfonyl fluorine, the perfluoroacyl fluoride that obtain with the electrofluorination method are perhaps with perfluoroalkyl iodide (R
FI) be raw material, the fluoro-containing intermediate by telomerization method obtains further synthesizes straight chain fluorine-containing surfactant [Langmuir, 2009,25 (16): 8919-8926; J. Fluorine Chem. 2012 (138) 3-23].Such surfactant has higher surface-active, but has the shortcomings such as energy consumption is large, expensive.
Take the Fluorine containing olefine that obtains by the oligomerisation method as raw material, overcome the shortcomings such as electrofluorination method, telomerization method energy consumption are large, expensive, can for the preparation of branch type fluorine-containing surfactant, have synthetic simple, low, the cost performance high of cost.At present, there is no this sulfate type anionic fluorochemical surfactant of bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of sulfate type anionic fluorochemical surfactant [N-methyl-(4-perfluor-(1, the 3-dimethyl-2-isopropyl)-and the 1-butenyloxy) benzene sulfonamido] preparation and uses thereof of SES, the present invention has excellent surface-active.
Structural formula of the present invention is as follows:
I
The preparation method of above-mentioned sulfate type anionic fluorochemical surfactant comprises the steps: take fluorine-containing benzene sulfonyl chloride as raw material, obtains fluorine-containing hydroxyethylbenzene sulfonamide intermediate with the reaction of N-methylethanolamine; Further obtain target product with the sulfur acidizing reagent reaction: [N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] SES.
The reaction equation of described reaction is:
The compounds of this invention II reaction that is fluorine-containing phenyl ether and sulfonylation agent under the temperature that is fit to, solvent, catalyst and certain molar ratio and preparation.
Substantive distinguishing features of the present invention can be achieved from following examples of implementation, but these examples of implementation only as an illustration, rather than limits the invention.
Description of drawings
Fig. 1 is aqueous solution surface tension and the concentration logarithmic curve chart of embodiment
Fig. 2 is the foam stability change curve of embodiment
Specific implementation method
Example 1:N-methyl-N-ethoxy-4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzsulfamide
In 100 mL four-hole boiling flasks with reflux condenser, 4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzene sulfonyl chloride (3.11 g, 0.005 mol) is dissolved in the 20 mL acetonitriles, stir and make its dissolving.Room temperature drips 2-methylaminoethanol (0.75 g, 0.01 mol), about 0.5 h.Dropwise, stirring at room is reacted 3.0 h.React complete, removal of solvent under reduced pressure, with 3 * 10mL washing that gained white opacity thick liquid is dry, get white solid powder, about 3.01 g, yield 92 % behind the recrystallization.IR(cm
?1):?υ(O-H)?3497.1,υ(C-H)2963.2,υ(C=C)?1592.0,1491.4,?υ(S=O)?1012.1,υ(C-F)1287.2,1185.0,1127.1,980.1;
1H-NMR?((CD
3)
2SO)δ:?7.92(d,2H,ArH),7.37?(d,2H,ArH),3.51(t,2H,CH
2),3.03(t,2H,CH
2),2.74(s,3H,?CH
3);ESI-MS:?661.02。
Example 2:[N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] preparation of SES
In the four-hole boiling flask of 100 mL, add N-methyl-N-ethoxy-4-perfluor-(1, the 3-dimethyl-2-isopropyl)-1-butenyloxy benzsulfamide (3.30 g, 0.005mol), be dissolved in the 40 mL carbon tetrachloride, stir and be warming up to backflow, slowly drip chlorosulfonic acid (1.16 g, 0.01mol), about 30 min continue reaction 6 h.Reaction is left standstill and is cooled to room temperature after finishing, removal of solvent under reduced pressure after the decolouring, join 10 % NaOH solution, stir, neutralization obtains white viscous liquid, add the 50mL saturated aqueous common salt, separate out white solid, filter, oven dry obtains [N-methyl-(4-perfluor-(1, the 3-dimethyl-2-isopropyl)-and the 1-butenyloxy) benzene sulfonamido] SES, yield 80 %.IR(cm
-1):?υ(N-H)3446.3,υ(C=C)1626.6,1590.9,1491.5,υ(C-O)1241.8;υ(S=O)1014.2,υ(C-F)1240.8,979.50,742.06;?
1H-NMR(DMSO-d6)δ:?7.93(d,2H,ArH),?7.38(d,2H,?ArH),3.83(t,2H,CH
2),3.19(t,2H,CH
2),2.73(s,3H,CH
3);?ESI-MS:?726.96。
Example 3 surface tension tests (Wilhelmy method)
Hang the sheet method, claim again the Wilhelmy method, adopt cover glass, mica sheet, filter paper, platinum foil, the perpendicular dull and stereotyped test liquid that inserts makes its base contact with liquid level, measures when hanging sheet to break away from the required maximum pull F that contends with surface tension of liquid.The method has, and is intuitive and reliable, do not need correction factor, and this and other spin off method is different, can also measure liquid-liquid interface tension force.By accompanying drawing 1, can draw its critical micelle concentration is 4.8 * 10
-4Mol/L, the at this moment surface tension (γ of its aqueous solution
CMC) be 19.5mN/m(pure water surface tension 71.0 mN/m).
Example 4 interfacial tensions tests (adopting platinum plate method)
Interfacial tension refers to vertically act on along interface between immiscible two-phase (liquid-solid, liquid-liquid, liquid-gas) the surperficial convergent force on the unit length liquid surface.Its unit is mN/m.Liquid contacts with another kind of not miscible liquid, and the power of its generation of interfaces is the interfacial tension between liquid phase and liquid phase.Different from surface tension, be in the molecule of boundary layer, be subject on the one hand the effect of body phase internal layer same substance molecule, another that is subject on the other hand different in kind mutually in effect of material molecule, its active force may not necessarily be cancelled out each other.Therefore interfacial tension wants specific surface tension much smaller usually.The sulfate type anion surfactant 1 % aqueous solution, its pH is 7.8, can be fully water-soluble.0.1% solution interface tension force is: 0.19 mN/m.
The test of example 5 contact angles
When a drop of liquid dropped on the fabric face, possible complete wetting fabric formed water membrane on the surface, might form drops, and drop edge and the surface of solids form an angle theta, and this angle just is called contact angle.When 0 °＜θ＜90 °, liquid part wet fabric, and within the extremely short time, drop to around diffusion and infiltrating in the fabric, in the time of 90 °＜θ＜180 °, liquid can not the wet fabric surface and form the liquid pearl, drop tumbles during inclination.Reach the purpose of refusing water, contact angle θ will be the bigger the better.According to famous Young equation: γ S=γ SL+γ Lcos θ, the contact angle that liquid forms at the surface of solids and the relation between the interfacial tension are as can be known, because surface tension of liquid is constant, reach the purpose of refusing water, just must reduce solid surface tension or make the solid-liquid surface tension become large, the results are shown in Table 1.
Table 1 arrangement rear surface water contact angle
| Sample | Water contact angle (°) |
| Synthetic leather | 99.2 |
| Cotton | 98.0 |
| Glass | 108.5 |
Example 6 is refused water, oil repellent test
Refuse oily principle and to refuse the water principle very similar, all be to change fabric, fiber surface performance that its critical surface tension is reduced, and the contact angle that water and oil are larger with its generation reaches the purpose of water and oil repellant, and don't affects the gas permeability of fabric.
In the detection, the water rank of refusing of fabric is tested, generally use the trickle performance test methods.Carry out according to the sampling, operation sequence, the evaluation that require among the GB/T4745-1997 " textile fabric surface moisture resistance is measured to get wet and pressed test ", the warp-wise of fabric is parallel with water (flow) direction, test respectively wash front, wash rear sample refuse the water rank; Refuse the test of wet goods level and adopt method in GB/T19977-2005 " the anti-hydrocarbon test of the textile oil repellent " standard.At first be the experimental liquid with lowest number, carefully drip on fabric with 0.05 mL liquid, if in 30 s without infiltration and wetting phenomena generation, then and then drip on fabric with the experimental liquid of higher number.Experiment is carried out continuously, until experimental liquid is in 30 s till the fountain solution side of dripping and on every side the fabric.The wet goods level of refusing of fabric represents with the experimental liquid of high numbering that can not wet fabric in 30 s.The results are shown in Table 2.
Table 2 fabric is refused water, oil repellent test
| Sample | Solvent | Refuse the water rank | Refuse oily rank | The clear situation of spot | |
| Synthetic leather | Acetone | 5 | 1.5 | Easy cleaning | |
| Synthetic | Isopropyl alcohol | 6 | 2 | Easy | |
| Cotton | Acetone | ||||
| 6 | 1.5 | Easy cleaning | |||
| Cotton | Isopropyl alcohol | 5 | 1.5 | Easy cleaning |
Example 7 foams can be tested
Adopt succusion to measure foam volume and foam stability.Prepare the aqueous solution of sulfate type anionic fluorochemical surfactant (FS) of the variable concentrations of 20 mL, pour in the tool plug graduated cylinder, behind 3 min that vibrate, the record foam volume is V, and liquid volume is N.Time T when the record liquid level reaches (20+N)/2 volume
1/2(lather collapse half-life), experimental temperature is 25 ± 2 ℃.Take foam volume V as ordinate, mass concentration is abscissa, gets all kinds of material foam bubbles power change curves, with lather collapse half-life T
1/2Be ordinate, mass concentration is abscissa, gets the foam stability change curve, as shown in Figure 2:
Example 8 displacement of reservoir oil property testings
In alkylbenzenesulfonate, add a certain amount of sulfate type anionic fluorochemical surfactant, interfacial tension is studied discovery, such as table 3.
Table 3 FS and alkylbenzenesulfonate are composite
Because the adding of anionic fluorochemical surfactant improves the interfacial activity of alkylbenzenesulfonate, working concentration is low, can make oil water interfacial tension reach ultralow (10 in the concentration range of wider and lower alkali
-3The mN/m order of magnitude), has good Oil Displacing Capacity.
The test of example 9 emulsifiabilities
Adopt minute emulsifiability of water Time Method test product, get 40 mL mass concentrations and be the aqueous solution of product of 1.0 g/L in 100 mL tool plug graduated cylinders, add 40 mL benzene, fierce vibration 5 times, leave standstill 1 min, repeat aforesaid operations 5 times, rear startup stopwatch is left standstill in the 5th vibration, and the time of 10 mL water told in record.Emulsifying ability and interfacial tension are closely related, and interfacial tension is lower, easier emulsification.The aqueous solution of sulfate type anionic fluorochemical surfactant (FS) and the emulsifying ability of benzene relation are as shown in table 4.Experiment shows that the sulfate type anion surfactant has excellent emulsifiability.
The table 4 FS aqueous solution is on the impact of benzene/water emulsification system
| № | Product | Emulsifying ability/s |
| 1 | FS | 513.2 |
| 2 | Lauryl sodium sulfate | 305.2 |
| 3 | OP-10 | 285.3 |
The test of example 10 wettabilities
Adopt the canvas sedimentation to survey sinking time, measure the wetting power of solution.Be that the canvas of 4cm is parallel to liquid level to place mass concentration be the aqueous solution of the product of 1.0 g/L with diameter, open stopwatch when canvas begins to immerse solution, stop stopwatch when canvas begins to descend, this time is the sinking time T of solution, can characterize wetting power.Wherein the sinking time of canvas in pure water is about 135.65 s.Solubility and canvas the sinking time in the aqueous solution of 1.0 g/L sulfate type anionic fluorochemical surfactants (FS) of product in water is as shown in table 5:
The different products of table 5 are on the impact of aqueous solution wetting power
| № | Product | Solubility | T/s |
| 0 | Blank | —— | 135.65 |
| 1 | FS | 0.47 | 13.38 |
Claims (6)
1. one kind suc as formula a kind of sulfate type anionic fluorochemical surfactant shown in the I [N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] SES:
I。
2. the preparation method suc as formula [N-methyl-(4-perfluor-(1,3-the dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] SES shown in the I as claimed in claim 1 is characterized in that described method is:
Be raw material with 4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzene sulfonyl chloride, at organic solvent
1In ,-10 ~ 100 ℃, with alkanolamine derivative reaction 1 ~ 10 h, reaction is removed organic phase after finishing, and recrystallization obtains N-methyl-N-ethoxy-4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzsulfamide; At solvent
2In, add sulfur acidizing reagent, in-20 ~ 100 ℃ of reactions, after the removal of solvent under reduced pressure, obtain [N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] SES with the alkaline matter neutralization after finishing:
Described solvent
1For one of following: acetonitrile, DMF, benzene,toluene,xylene, carrene, chloroform, carbon tetrachloride, ethyl acetate, benzinum, dimethyl sulfoxide (DMSO), pyridine, triethylamine, piperidines, cyclohexanone, acetone, butanone, methyl alcohol, ethanol;
Described solvent
2For one of following: carrene, chloroform, carbon tetrachloride, acetonitrile, dichloroethanes;
Described sulfonated reagent is one of following: chlorosulfonic acid, the concentrated sulfuric acid, sulfur trioxide, oleum;
Described alkali compounds is one of following: 1% ~ 30% sodium carbonate, potash, sodium acid carbonate, NaOH, potassium hydroxide aqueous solution.
3. method as claimed in claim 2 is characterized in that the molar ratio of described 4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzene sulfonyl chloride, methylethanolamine, chlorosulfonic acid is: 1:1.0 ~ 3.0:1.0 ~ 3.0:1 ~ 3.0.
4. method as claimed in claim 2 is characterized in that described amidation process temperature-10 ~ 100 ℃, reaction time 1 ~ 10 h.
5. the method for claim 1 is characterized in that described sulfating reaction temperature-20 ~ 100 ℃, reaction time 3 ~ 10 h.
6. application as claimed in claim 5, it is characterized in that [N-methyl-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] SES is as surface property research and the application of sulfate type anionic fluorochemical surfactant.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349870A (en) * | 2017-06-22 | 2017-11-17 | 华中师范大学 | The fluorine-containing extinguishing chemical of oil fire and liquid hydrocarbon evaporation inhibitor and preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57164198A (en) * | 1982-03-15 | 1982-10-08 | Neos Kk | Fluorine-containing surfactant and manufacture |
| CN101293860A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Quaternary ammonium salt fluorine surfactant preparing method |
| CN101406816A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for producing sulfuric acid fluorinated surfactants |
-
2012
- 2012-12-04 CN CN2012105118829A patent/CN103007812A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57164198A (en) * | 1982-03-15 | 1982-10-08 | Neos Kk | Fluorine-containing surfactant and manufacture |
| CN101293860A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Quaternary ammonium salt fluorine surfactant preparing method |
| CN101406816A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for producing sulfuric acid fluorinated surfactants |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349870A (en) * | 2017-06-22 | 2017-11-17 | 华中师范大学 | The fluorine-containing extinguishing chemical of oil fire and liquid hydrocarbon evaporation inhibitor and preparation method and application |
| CN107349870B (en) * | 2017-06-22 | 2019-01-04 | 华中师范大学 | The fluorine-containing extinguishing chemical of oil fire and liquid hydrocarbon evaporation inhibitor and the preparation method and application thereof |
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