CN1760178A - Full halothane sulfonic acid salts, preparation method and application - Google Patents
Full halothane sulfonic acid salts, preparation method and application Download PDFInfo
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- CN1760178A CN1760178A CN 200410083656 CN200410083656A CN1760178A CN 1760178 A CN1760178 A CN 1760178A CN 200410083656 CN200410083656 CN 200410083656 CN 200410083656 A CN200410083656 A CN 200410083656A CN 1760178 A CN1760178 A CN 1760178A
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Abstract
A perfluoroalkyl sulfonate [CF3-(CF2) n-1-SO3] NH (CmH2m+1)3, where n=6-10 and m=1-4, is prepared through reaction between perfluoroalkyl sulfonylchloride and the aqueous solution of alamine. Its advantages are high output rate, low cost and no pollution. It can be used as fluouic surfactant, or to prepare the filming foam fire-extinguishing agent.
Description
Technical field
The present invention relates to fluorinated alkyl sulfonate and preparation method thereof and application, particularly a kind of fluorinated alkyl sulfonate and preparation method thereof and its application as the anionic fluorine surfactant.
Background technology
Tensio-active agent is can be adsorbed on table (boundary) face, adds very in a small amount significantly to change the physicochemical property of table (boundary) face, thereby produces a series of materials with application function.Tensio-active agent has almost obtained application at all industrial circles, and it often can greatly improve production technique and product performance as important industrial auxiliary agent, is called as " industrial monosodium glutamate ".
Surfactant molecule one end (polarity part) is hydrophilic, is called hydrophilic group, and the other end (nonpolar part) oleophylic is called oleophilic group or hydrophobic group.The hydrophobic group of general tensio-active agent is hydrocarbon alkyl, is called hc-surfactant, if the hydrogen atom in the hc-surfactant molecule hydrocarbon chain is partly or entirely replaced with fluorine atom, just becomes fluorine surfactant.
Fc-surfactant is a kind of special tensio-active agent, and the special performance that is had often is summarized as " three height ", " two hate ", and " three height " is meant high surface, high heat-resistant stability and high chemical stability; The fluorine-containing alkyl that " two hate " is meant it is hydrophobic but also hate oil not only.
Fc-surfactant is the highest a kind of of surfactivity in all surface promoting agent up to now, and the lowest surface tension of its aqueous solution can reach below the 20mN/m, even to about the 15mN/m.Surfactivity so that its aqueous solution that fc-surfactant is so high can be sprawled on the hydrocarbon ils surface.
Fc-surfactant has very high thermotolerance, as solid-state perfluoro alkyl sulfonic acid potassium, is heated to and just begins more than 420 ℃ to decompose, thereby can use under the high temperature more than 300 ℃.And general hc-surfactant decomposes already in this temperature.
Fc-surfactant also has very high chemical stability, can resist strong oxidizer, strong acid and alkaline effect, and it still can keep the surface of good activity in these three kinds of solution.
Fluorine-containing alkyl in the fc-surfactant molecule, be hydrophobic group be again to hate oil base, thereby it not only can reduce the surface tension of water, if be made into the surface tension that oil soluble surfactant also can reduce organic solvent.
The above-mentioned special performance that fc-surfactant had makes it that purposes widely be arranged.Particularly, play the irreplaceable effect of other tensio-active agent in some special application fields.In early days, it is used as the emulsifying agent of tetrafluoroethylene letex polymerization, progressively as wetting agent, spreading agent, pore forming material, antisticking agent, stain control agent etc., be widely used in a plurality of fields such as fire-fighting, weaving, leather, papermaking, ore dressing, agricultural chemicals, chemical industry later on, demonstrate great vitality.The topic bar overwhelming majority of the topic subfacies of relevant fc-surfactant relates to patent in the U.S. chemical abstract (CA), shows that it has very big range of application.
Because of the aqueous solution of fc-surfactant can be sprawled on pasta, form water membrane, thus oil and air is isolated.Utilize this characteristic to be made into a kind of new and effective fire-fighting medium, be called aqueous film-forming foam extinguishing agent.
But because synthetic difficulty, the more high reason of cost has seriously restricted the application and the development of fc-surfactant.
Three steps of the synthetic branch of fc-surfactant: (1) synthetic fluoroalkyl that contains that contains 6-10 carbon atom; (2) make the fluoro-containing intermediate that is easy to introduce various hydrophilic radicals; (3) introduce various hydrophilic radicals and make all kinds of fc-surfactants.Wherein the most important thing is to contain the production of fluoroalkyl, its industrialized preparing process mainly is electrofluorination method, fluoroolefin telomerization method and fluoroolefin oligomerisation method, wherein the electrofluorination method be industrialization early, method that range of application is the widest.
The fluoroalkyl that contains of electrofluorination gained mainly is divided into perfluoroalkyl sulfonyl fluoride and perfluorocarboxylic acid two big classes.Wherein the productive rate of perfluoroalkyl sulfonyl fluoride is higher, thereby is that the cost of fluorine surfactant of feedstock production is relatively low with the perfluoroalkyl sulfonyl fluoride.
Perfluoroalkyl sulfonyl fluoride alkaline hydrolysis can get fluorinated alkyl sulfonate, and this is an anionoid type fluorine surfactant.Generate perfluoro octyl sulfonic acid potassium as full-fluorine octyl sulfuryl fluoride and potassium hydroxide aqueous solution reaction, it is the main component of chromium fog inhibitor, suppresses the volatilization of chromic anhydride acid mist when being used for electrodeposited chromium.
At present, in the fluorinated alkyl sulfonate anionoid type fluorine surfactant of open report, gegenion is NH
4 +, M
N+(metal ion) or quaternary ammonium ion (N (C
mH
2m+1)
4).But, the surfactivity of these fluorinated alkyl sulfonates is generally relatively poor, the lowest surface tension of its aqueous solution is all more than 20mN/m, respectively up to 34.5mN/m and 40.5mN/m, the lowest surface tension (15mN/m) that can reach with fluorine surfactant differs greatly as the lowest surface tension of perfluoro octyl sulfonic acid potassium and perfluoro octyl sulfonic acid sodium water solution.So high surface tension makes the application of this class fluorine surfactant be subjected to great restriction.A typical example is exactly: the fluorinated alkyl sulfonate anionoid type fluorine surfactant aqueous solution of open report can not be sprawled on pasta at present, thereby can not be directly used in the prescription of aqueous film-forming foam extinguishing agent.
Summary of the invention
The purpose of this invention is to provide a kind of new fluorinated alkyl sulfonate and preparation method thereof.
Fluorinated alkyl sulfonate provided by the present invention (FCTA) is the compound with following molecular formula:
[CF
3-(CF
2)
N-1-SO
3] NH (C
mH
2m+1)
3, n=6-10 wherein, m=1-4.
The method for preparing above-claimed cpd is to add perfluoroalkyl sulfonyl fluoride in the aqueous solution of tertiary amine, and reaction obtains product.
Reaction process of the present invention can be represented by the formula:
In said process, the mol ratio of described perfluoroalkyl sulfonyl fluoride, tertiary amine and water is: 1: 2-6: 1-80.Wherein more preferably the mol ratio of perfluoroalkyl sulfonyl fluoride, tertiary amine and water is: 1: 3: 25.
The used tertiary amine and the purity of perfluoroalkyl sulfonyl fluoride are that technical grade gets final product in the production process, and water is deionized water or industrial soft water.The mode of adding perfluoroalkyl sulfonyl fluoride is for to drip under agitation condition.
Fluorinated alkyl sulfonate of the present invention has the following advantages:
1, raw material is easy to get, and production cost is low;
2, preparation method and equipment are simple, under normal temperature, normal pressure, can be prepared with conventional equipment, and reaction process need not catalyzer, and reaction fast;
3, reaction back mixture need not to separate, and can directly use.And byproduct of reaction [NH (C
mH
2m+1)
3] F also can improve the purpose product C
nF
2n+1SO
3NH (C
mH
2m+1)
3Surfactivity (usually in surfactant soln add ionogen increase surfactivity), in addition, the F in the mixture
-Also can be used as Ca in the hard water
2+Deng the precipitation agent of polyvalent metal ion, thereby the anti-hard water of enhancing fluorine surfactant when it is used, reduces the consumption of sequestrant in hard water;
4, productive rate height: main reaction thing perfluoroalkyl sulfonyl fluoride reaches 100% and transforms;
5, production process toxicological harmless, pollution-free: as not have the discharging of waste gas, waste water in the production process, environment is not had harm substantially.And because the using dosage of fc-surfactant very little (be generally ten thousand/several), thereby can not pollute in the use environment yet;
6, excellent performance: fluorinated alkyl sulfonate of the present invention is the highest class of surfactivity in the fluorinated alkyl sulfonate of having reported in the present document, as having reported the C with fluorine surfactant structural similitude of the present invention in the document
nF
2n+1SO
3N (C
mH
2m+1)
4, it is to be made by perfluoroalkyl sulfonyl fluoride or perfluoro alkyl sulfonic acid and corresponding quaternary ammonium hydroxide reaction.On the one hand the quaternary ammonium hydroxide cost is far above tertiary amine, on the other hand C
nF
2n+1SO
3N (C
mH
2m+1)
4Surfactivity also than C of the present invention
nF
2n+1SO
3NH (C
mH
2m+1)
3Difference is as C
8F
17SO
3NH (C
2H
5)
3The lowest surface tension of the aqueous solution is 16.6mN/m, and C
8F
17SO
3N (C
2H
5)
4The lowest surface tension of the aqueous solution is 22.6mN/m.
With the The compounds of this invention is that activeconstituents can obtain the surfactivity height, the tensio-active agent that cost is low, and, have higher actual application value and vast market prospect because its surfactivity height can be directly used in aqueous film-forming foam extinguishing agent.Adopting fluorinated alkyl sulfonate of the present invention is that " standard of national fixed fire extinguishing system and fire retarding component quality supervision and test " center " identifies that extinguishing property reaches the IA level by GB17427-1998 for the aqueous film-forming foam extinguishing agent of key component preparation.
Description of drawings
Fig. 1 is the surface tension curve of fluorinated alkyl sulfonate of the present invention.
Embodiment
The preparation of embodiment 1, fluorinated alkyl sulfonate
1.2mol tertiary amine and 10mol water are mixed, under stirring condition, slowly drip the 0.4mol perfluoroalkyl sulfonyl fluoride.The solution that reacts completely is the homogeneous phase brown yellow transparent liquid, and is stand-by in the encloses container of packing into.
Products therefrom is the [CF of 0.4mol
3-(CF
2)
N-1-SO
3] NH (C
mH
2m+1)
3And water, n=6-10 wherein, m=1-4 also has by product in addition, is respectively the NH (C of 0.4mol
mH
2m+1)
3NH (the C of F and 0.4mol
mH
2m+1)
3, n=6-10 wherein, m=1-4.Above-mentioned reaction product is carried out ultimate analysis after drying, and the result shows that reaction principal product and by product are correct.
In actual applications, there are same function in two kinds of by products and principal product fluorine surfactant, can increase surfactivity, lathering property and the anti-performance of hard water of fluorine surfactant.Therefore mixture does not need to separate, and can directly use as fluorine surfactant.
The physico-chemical property of embodiment 2, fluorinated alkyl sulfonate of the present invention and performance index:
1, surface tension and critical micelle concentration: C
nF
2n+1SO
3NH (C
mH
2m+1)
3
The surface-active size of tensio-active agent, in actual applications Chang Yiqi critical micelle concentration (cmc) and with the corresponding surface tension γ of cmc
CmcSize weigh, the former presentation surface promoting agent forms the Cmin of micelle (or reaching lowest surface tension), is also referred to as tensio-active agent and reduces capillary efficient, the latter represents to reduce capillary ability.Cmc and γ
CmcValue more little, the surfactivity of tensio-active agent is big more.
Measure the surface tension (γ) of the fc-surfactant (FCTA) of embodiment 1 acquisition with drop-volume method, and (graphic representation (Fig. 1) of γ-lgc), the ordinate zou at weight break point place is represented the lowest surface tension γ of the FCTA aqueous solution among the figure to draw out surface tension (γ)-concentration logarithm
Cmc, the abscissa value at weight break point place is represented critical micelle concentration (cmc).
The surfactivity of FCTA of the present invention and open other perfluoro octyl sulfonic acid salt of reporting is compared (table 1), the lowest surface tension (γ of the FCTA aqueous solution of the present invention
Cmc) be 16.6mN/m, be surfactivity the highest a kind of (weighing) to reduce the capillary ability of the aqueous solution; The critical micelle concentration of FCTA of the present invention is 0.034%.
The surface-active comparison of other perfluoro octyl sulfonic acid salt in table 1 FCTA and the document
| Fluorine surfactant | γ cmc(mN/m) | cmc(％，wt) |
| FCTA | 16.6 | 0.034 |
| C 8F 17SO 3Li | 29.8 | 0.32 |
| C 8F 17SO 3Na | 40.5 | 0.44 |
| C 8F 17SO 3K | 34.5 | 0.43 |
| C 8F 17SO 3NH 4 | 27.8 | 0.28 |
| C 8F 17SO 3NH 3C 2H 4OH | 21.5 | 0.26 |
| C 8F 17SO 3N(CH 4) 4 | 23.1 | |
| C 8F 17SO 3N(C 2H 5) 4 | 22.6 |
2. oil water interfacial tension, spreading coefficient and sprawling on pasta
When a kind of fluid drips is added on the surface of another kind of liquid, three kinds of situations can appear: be sunken to the bottom under (1) drop; As with water droplet on pasta; (2) drop is suspended in pasta, as paraffin is dropped on the water surface; (3) drop spreads out at another fluid surface and forms one deck liquid film, and as long-chain alcohol is dropped on the water surface, this situation is called liquid sprawling on liquid.
Desire to make a kind of liquid to sprawl on another kind of liquid, must satisfy and sprawl condition, promptly spreading coefficient is greater than zero: S
A/b=γ
b-(γ
a+ γ
A/b)＞0, S in the formula
A/bBe spreading coefficient, γ
a, γ
b, γ
A/bBe respectively the surface tension of liquid a, the surface tension of liquid b and the interfacial tension of liquid a, b.
This measuring the interfacial tension of the FCTA aqueous solution with different oil, and calculated its spreading coefficient (S) on pasta, the result is as shown in table 2:
The spreading coefficient of the table 2 compound surfactant aqueous solution on different pastas
| Hexanaphthene | 3.1 |
| Kerosene | 3.8 |
| Gasoline | 2.1 |
The spreading coefficient of FCTA on hexanaphthene, kerosene, gasoline satisfies and sprawls condition all greater than zero, shows that the FCTA aqueous solution all can sprawl the formation moisture film rapidly on hexanaphthene, kerosene, gasoline.Its best is sprawled concentration (residence time of drop on pasta is less than the suitable concentration of 0.5 second required FCTA) and is 0.05-0.1% (wt).
3.FCTA the stability of the aqueous solution
The 0.1%FCTA aqueous solution (surface tension γ=16.6mN/m, 25 ℃) was boiled (backflow) 1-2 hour, be cooled to 25 ℃, survey its surface tension γ=16.5mN/m.
-5 ℃ of the 0.1%FCTA aqueous solution (surface tension γ=16.6mN/m, 25 ℃) were placed 72-100 hour, with temperature retrieval to 25 ℃, surveyed its surface tension γ=16.8mN/m again.
Above-mentioned test-results shows that FCTA solution has satisfactory stability, but long-term storage.
4. lathering property, froth stability and 25% drainage time
The foam expansion of the table 3 FCTA aqueous solution, froth stability and 25% drainage time
| Concentration 0.1% (wt) the deionized water preparation of FCTA | Foam expansion | 6.2 |
| Froth stability | (airtight) be foam completely dissolve not yet after 48 hours | |
| 25% drainage time | 2’42” |
The data of table 3 show, the FCTA aqueous solution adds whipping agent when existing in nothing, promptly has good lathering property.(airtight) be foam completely dissolve not yet after 48 hours, and drainage time is long, shows that it has excellent lathering property and high froth stability.
5. the influence of hard water
Table 4 has been listed the performance of FCTA in different hardness water.
The surfactivity of table 4 FCTA in different water
| The concentration 0.1% (wt) of FCTA | Water quality | Surface tension | Foam expansion | Sprawl on the pasta |
| Deionized water | 16.6 | 6.2 | Sprawl | |
| Tap water | 16.6 | 5.5 | Sprawl | |
| Huangpu river | 16.8 | 4.6 | Sprawl | |
| Common hard water | 16.8 | 3.2 | Sprawl | |
| Artificial seawater | 18.7 | 2.1 | Sprawl hardly |
Annotate: the hardness of common hard water is 5000mg/L
Artificial seawater prescription: MgCl
26H
2O 1.1g, CaCl
22H
2O 0.6g, Na
2SO4 0.4g, NaCl 2.5g is dissolved in 95.84g distilled water
The data of table 4 show that FCTA has excellent anti-performance of hard water, all can well sprawl in pasta in tap water, Huangpu river and common hard water.But in artificial seawater, independent FCTA can not sprawl on pasta.And increase with water hardness, the lathering property of FCTA descends.In the reality prescription, add whipping agent and can remedy this deficiency.
Claims (8)
1, has molecular formula [CF
3-(CF
2)
N-1-SO
3] NH (CmH
2m+1)
3Compound, n=6-10 wherein, m=1-4.
2, a kind of method for preparing the described compound of claim 1 is to add perfluoroalkyl sulfonyl fluoride in the aqueous solution of tertiary amine, and reaction obtains product.
3, preparation method according to claim 2 is characterized in that: described perfluoroalkyl sulfonyl fluoride, tertiary amine, and the mol ratio of water be: 1: 2-6: 1-80.
4, preparation method according to claim 3 is characterized in that: the mol ratio of described perfluoroalkyl sulfonyl fluoride, tertiary amine and water is: 1: 3: 25.
5, according to claim 2 or 3 or 4 described preparation methods, it is characterized in that: the purity of described tertiary amine is technical grade; Described water is deionized water or industrial soft water; The purity of described perfluoroalkyl sulfonyl fluoride is technical grade.
6, according to claim 2 or 3 or 4 described preparation methods, it is characterized in that: the mode of described interpolation perfluoroalkyl sulfonyl fluoride is for to drip under agitation condition.
7, the application of the described compound of claim 1 in the preparation tensio-active agent.
8, the application of the described compound of claim 1 in the preparation aqueous film-forming foam extinguishing agent.
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|---|---|---|---|
| CNB2004100836560A CN100376553C (en) | 2004-10-15 | 2004-10-15 | Full halothane sulfonic acid salts, preparation method and application |
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|---|---|---|---|
| CNB2004100836560A CN100376553C (en) | 2004-10-15 | 2004-10-15 | Full halothane sulfonic acid salts, preparation method and application |
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|---|---|
| CN1760178A true CN1760178A (en) | 2006-04-19 |
| CN100376553C CN100376553C (en) | 2008-03-26 |
Family
ID=36706424
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003530B (en) * | 2007-01-19 | 2010-09-08 | 东华大学 | Method for preparing perfluoroalkyl group sulfonyl isoflavone of possessing anticarcinogenesis |
| CN102491923A (en) * | 2011-11-15 | 2012-06-13 | 上海威腾化工科技发展有限公司 | Method for continuous chemosynthesis of perfluoro surfactant with water as solvent |
| CN104860985A (en) * | 2007-08-06 | 2015-08-26 | 纳幕尔杜邦公司 | Mixed Fluoroalkyl-alkyl Surfactants |
| CN105854216A (en) * | 2016-04-01 | 2016-08-17 | 中国民用航空飞行学院 | Aqueous film-forming foam extinguishing agent based on short fluorocarbon chains |
| CN109851531A (en) * | 2019-02-26 | 2019-06-07 | 武汉松石科技股份有限公司 | A kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester |
| CN109912468A (en) * | 2019-02-26 | 2019-06-21 | 武汉松石科技股份有限公司 | A kind of preparation method of acrylic acid (1- chloromethyl, 2-N- methyl perfluoro hexyl sulfoamido) ethyl ester |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55157691A (en) * | 1979-05-29 | 1980-12-08 | Sanyo Chemical Ind Ltd | Fluorine surfactant |
| CN1097191A (en) * | 1993-07-08 | 1995-01-11 | 中国科学院上海有机化学研究所 | A kind of synthetic method of fluorine-containing hydrocarbyl sulfonate |
-
2004
- 2004-10-15 CN CNB2004100836560A patent/CN100376553C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003530B (en) * | 2007-01-19 | 2010-09-08 | 东华大学 | Method for preparing perfluoroalkyl group sulfonyl isoflavone of possessing anticarcinogenesis |
| CN104860985A (en) * | 2007-08-06 | 2015-08-26 | 纳幕尔杜邦公司 | Mixed Fluoroalkyl-alkyl Surfactants |
| CN104860985B (en) * | 2007-08-06 | 2017-08-04 | 纳幕尔杜邦公司 | The fluoro-alkyl alkyl surfactants of mixing |
| CN102491923A (en) * | 2011-11-15 | 2012-06-13 | 上海威腾化工科技发展有限公司 | Method for continuous chemosynthesis of perfluoro surfactant with water as solvent |
| CN105854216A (en) * | 2016-04-01 | 2016-08-17 | 中国民用航空飞行学院 | Aqueous film-forming foam extinguishing agent based on short fluorocarbon chains |
| CN105854216B (en) * | 2016-04-01 | 2019-02-05 | 中国民用航空飞行学院 | Aqueous film-forming foam extinguishing agent based on short carbon fluorine chain |
| CN109851531A (en) * | 2019-02-26 | 2019-06-07 | 武汉松石科技股份有限公司 | A kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester |
| CN109912468A (en) * | 2019-02-26 | 2019-06-21 | 武汉松石科技股份有限公司 | A kind of preparation method of acrylic acid (1- chloromethyl, 2-N- methyl perfluoro hexyl sulfoamido) ethyl ester |
| CN109851531B (en) * | 2019-02-26 | 2021-06-08 | 武汉松石科技股份有限公司 | Preparation method of (N-methyl perfluoroalkyl sulfonamide) ethyl acrylate |
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