CN102068937A - Method for preparing fluorocarbon surfactant - Google Patents
Method for preparing fluorocarbon surfactant Download PDFInfo
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- CN102068937A CN102068937A CN2011100075540A CN201110007554A CN102068937A CN 102068937 A CN102068937 A CN 102068937A CN 2011100075540 A CN2011100075540 A CN 2011100075540A CN 201110007554 A CN201110007554 A CN 201110007554A CN 102068937 A CN102068937 A CN 102068937A
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- fluorine
- potassium permanganate
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Abstract
The invention relates to a method for preparing a fluorocarbon surfactant, in particular to an anionic fluorine-containing surfactant which is expressed by the follow general formula: C6F13CH2COOX, wherein X represents Na<+> or NH<4+>. The method comprises the following steps of: generating perfluorohexyl acetic acid from perfluorohexyl ethanol in the presence of an oxidizer; and neutralizing with an alkali to prepare a corresponding salt. The anionic fluorine-containing surfactant has a simple and convenient preparation method and superior surface performance; and the surfactant has six fluorocarbon atoms; and the environmental protection requirement of the surfactant is met at present. The surfactant can be used for emulsion polymerization of a fluorine-containing monomer.
Description
Technical field
The present invention relates to a kind of general structure is C
6F
13CH
2(wherein X represents Na to COOX
+Or NH
4 +) the preparation method of fluorine-containing surfactant.
Background technology
Fluorine-containing surfactant has high surface, high thermal stability and high chemical stability, not only hydrophobic but also hate the characteristics of oil, is widely used in a plurality of fields such as chemistry, chemical industry, weaving, leather, building, oil, fire-fighting.The fluorine-containing surfactant of extensive use at present is perfluorooctanoic acid salt (PFOA) and perfluorinated sulfonate (PFOS).Wherein PFOA is widely used in the preparation of fluororesin and fluorubber.
Studies show that PFOA is difficult to degrade in natural environment, have the essential characteristic of persistence environmental organic pollutant, human body is had adverse effect.Therefore 2006 under the advocating of Environmental Protection Agency; the main fluorine manufacture of materials producer in the 8 tame worlds that comprises Du Pont, 3M, Da Jin, A Kema etc. has signed PFOA reduction of discharging agreement; promise to undertake and to stop using PFOA stage by stage, all will ban use of PFOA in all products in 2015 and can derive the compound of PFOA.In the end of the year 2006, European Parliament has also issued the instruction of using PFOS about restriction, also points out that PFOA is under a cloud simultaneously to have similar harmfulness to PFOS, also needs carry out risk assessment to it, and quilt is summoned to court relevant substitute.Therefore, to be used for substituting PFOA very urgent for the fluorine-containing surfactant of the new compliance with environmental protection requirements of exploitation.
Studies show that the source of PFOA environmental problem is to come to contain C8(eight carbon perfluor segments in this type of surfactant), it can water and oil repellant, has bioaccumulation, extremely difficult the decomposition.Except PFOA and PFOS, as long as all there is similar problem in other compound that can produce C8 perfluor segment.
One of main thought of PFOA substitute exploitation at present is the carbon number that reduces the perfluor chain, thereby it can be excreted along with human body metabolism, reduces deposition conditions.Fluorine-containing surfactant provided by the invention adopts this thinking design just, and (PFOA, molecular formula is C with perfluoro caprylic acid
6F
13CF
2COOX) near carboxyl-CF
2-unit changes into-CH
2-, prepare perfluoro hexyl acetate salt surfactant (C
6F
13CH2COOX), thereby fluorine-containing carbon atom number is reduced to 6, satisfies current environmental requirement, the while has better surface property than the surfactant of perfluor short chain again.
Precursor about this surfactant---perfluoro hexyl acetate, document (1.Tetrahedron, 65 (27), 5271-5277,2009; 2.Tetrahedron Letters, 49 (49), 6955-6958,2008; 3.Tetrahedron, 64 (3), 522-528,2008; 4.Journal of Fluorine Chemistry, 70 (1), 19-26,1995) reported by with perfluoro hexyl ethanol CrO
3/ H
2SO
4(Jones reagent) carries out the preparation method of oxidation; United States Patent (USP) (U.S. Pat. 2008/0064900) has been reported the preparation method who carries out oxidation by periodic acid (HIO4).Above-mentioned two kinds of methods all come with some shortcomings, the CrO that uses in the method 1
3/ H
2SO
4In (Jones reagent), the reagent that contains chromium is poisonous and carcinogenic, and human body and environment are had bigger harm; The periodic acid that uses in the method 2 also has strong impulse and corrosivity, and price is expensive, is unfavorable for carrying out suitability for industrialized production.
Above-mentioned in addition document and patent are also not mentioned with perfluoro hexyl acetate conversion salify and as fluorine-containing surfactant.
Given this, the fluorine-containing surfactant preparation method who a kind of easy economy, excellent product performance is provided and meets current environmental requirement becomes this patent technical issues that need to address.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of fluorine-containing surfactant of easy economy, make it both have excellent surface property, can meet current environmental requirement again.
The preparation method of fluorine-containing surfactant of the present invention comprises following two steps:
(1) fluorine alcohol is dissolved in an amount of solvent, under 50～70 ℃, described fluorine alcohol is oxidized to fluorine-containing organic acid by oxidant;
(2) with described fluorine-containing organic acid at room temperature with in the alkali and after prepare corresponding salt, promptly obtain described fluorocarbon surfactant;
The structure of described fluorocarbon surfactant is represented by following general formula: C
6F
13CH
2COOX, wherein X represents Na
+Or NH
4 +
Described solvent (can be with water miscible and not with reactant reaction) be a kind of in acetone, oxolane, the dioxane or several.
Described oxidant is a potassium permanganate.
Described potassium permanganate uses in acidity or alkaline aqueous solution.
Described acidic aqueous solution is an aqueous sulfuric acid, dissolves to form behind the described potassium permanganate saturated or near saturated solution.
The concentration of described aqueous sulfuric acid is 10～50%, preferred 20～30%.
Described alkaline aqueous solution is a sodium hydrate aqueous solution, dissolves to form behind the described potassium permanganate saturated or near saturated solution.
The concentration of described sodium hydrate aqueous solution is 3～40%, preferred 5～20%.
Described alkali is sodium hydrate aqueous solution or ammoniacal liquor.
Described sodium hydrate aqueous solution concentration is 2～52%, preferred 5～20%
The reaction equation of above-mentioned steps (1) is as follows:
The reaction equation of above-mentioned steps (2) is as follows:
Wherein X is Na
+Or NH
4 +
Said N-process is that solution with alkali under agitation is added drop-wise in the solution of perfluoro hexyl acetate gradually in the above-mentioned steps 2, reaches between 7.5～8.5 until the pH of solution value.
Our prepared surfactant sees from structure and meets current environmental requirement, and its surface property also obviously is better than the PFOA class surfactant that uses at present, and comparing result is seen Fig. 1.
Description of drawings
Fig. 1 is the prepared surfactant precursor perfluoro hexyl acetate of the present invention
19F NMR;
Fig. 2 is the prepared perfluoro hexyl sodium acetate of the present invention, perfluoro hexyl ammonium acetate with the surface tension of Sodium perfluorooctanoate and perfluorooctanoic acid to concentration curve.
The specific embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this; following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention, some nonessential improvement and adjustment that the professional and technical personnel in this field content according to the present invention is made still belong to protection scope of the present invention.
In the glass reaction still of 10L, 100g perfluoro hexyl ethanol is dissolved in the 400mL acetone, being heated to acetone under stirring refluxes, in 50～70 ℃ of downhill reaction systems, drip the 7L acid permanganate soln gradually and (wherein contain 550 gram potassium permanganate, the sulfuric acid of 1750 grams 98%), the color of potassium permanganate is no longer taken off in system, stops reaction, with reacting liquid filtering, and with acetone rinsing filter cake 2～3 times.Filtrate and wash solution are merged, drip oxalic acid solution, until the system bleach.Under 70 ℃ the acetone in the system is steamed, occur precipitation in the system, filter, drying promptly gets perfluoro hexyl acetate 78 grams, and productive rate is 75%, product
19F NMR sees Fig. 1.
20 gram perfluoro hexyl acetate are scattered in 200mL water and the 10mL acetone, under the stirring at room in system dropping ammonia, reach 8 until the pH value, promptly get the perfluoro hexyl ammonium acetate.
Use prepared perfluoro hexyl acetate among the embodiment 1, it is scattered in the mixed solution of water and acetone, the sodium hydrate aqueous solution neutralization with 10% is 8 until the pH value, promptly gets the perfluoro hexyl sodium acetate.
Use prepared perfluoro hexyl acetate among the embodiment 1, do not add any solvent, directly under agitation slowly to the sodium hydrate aqueous solution of Dropwise 5 % wherein, dissolve fully to sample, regulation system pH value to 8 promptly gets product.
In the glass reaction still of 10L, 100g perfluoro hexyl ethanol is dissolved in the 400mL acetone, being heated to acetone under stirring refluxes, in reaction system, drip the 7L alkaline permanganate solution gradually and (wherein contain 550 gram potassium permanganate, 400 gram NaOH), the color of potassium permanganate is no longer taken off in system, stops reaction, with reacting liquid filtering, and with acetone rinsing filter cake 2～3 times.Filtrate and wash solution are merged, drip oxalic acid solution, until the system bleach.Under 70 ℃ the acetone in the system is steamed, add hydrochloric acid and carry out acidifying in system, a large amount of precipitations occur in system, filter, drying promptly gets perfluoro hexyl acetate 85 grams, and productive rate is 82%.
According to the method for embodiment 1 and 2, product is changed into perfluoro hexyl ammonium acetate and perfluoro hexyl sodium acetate.
Claims (10)
1. the preparation method of a fluorocarbon surfactant is characterized in that, comprises the steps:
(1) fluorine alcohol is dissolved in an amount of solvent, under 50～70 ℃, described fluorine alcohol is oxidized to fluorine-containing organic acid by oxidant;
(2) with described fluorine-containing organic acid at room temperature with in the alkali and after prepare corresponding salt, promptly obtain described fluorocarbon surfactant;
The structure of described fluorocarbon surfactant is represented by following general formula: C
6F
13CH
2COOX, wherein X represents Na
+Or NH
4 +
2. preparation method according to claim 1 is characterized in that, described solvent is a kind of in acetone, oxolane, the dioxane or several.
3. preparation method according to claim 1 is characterized in that, described oxidant is a potassium permanganate.
4. preparation method according to claim 3 is characterized in that described potassium permanganate uses in acidity or alkaline aqueous solution.
5. preparation method according to claim 4 is characterized in that described acidic aqueous solution is an aqueous sulfuric acid, dissolves to form behind the described potassium permanganate saturated or near saturated solution.
6. preparation method according to claim 5 is characterized in that, the concentration of described aqueous sulfuric acid is 10～50%, preferred 20～30%.
7. preparation method according to claim 4 is characterized in that described alkaline aqueous solution is a sodium hydrate aqueous solution, dissolves to form behind the described potassium permanganate saturated or near saturated solution.
8. preparation method according to claim 7 is characterized in that, the concentration of described sodium hydrate aqueous solution is 3～40%, preferred 5～20%.
9. preparation method according to claim 1 is characterized in that, described alkali is sodium hydrate aqueous solution or ammoniacal liquor.
10. preparation method according to claim 9 is characterized in that, described sodium hydrate aqueous solution concentration is 2～52%, preferred 5～20%.
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|---|---|---|---|
| CN2011100075540A CN102068937A (en) | 2011-01-14 | 2011-01-14 | Method for preparing fluorocarbon surfactant |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127877A (en) * | 2013-03-05 | 2013-06-05 | 山东东岳高分子材料有限公司 | Fluorine-containing surfactant and preparation method thereof |
| CN105198729A (en) * | 2015-09-17 | 2015-12-30 | 海门德思行药业科技有限公司 | Preparation method of perfluoroalkyl acetic acid |
| WO2019159707A1 (en) * | 2018-02-15 | 2019-08-22 | 富士フイルム株式会社 | Binder composition, binder layer, optical laminate and image display device |
| CN112341364A (en) * | 2020-09-29 | 2021-02-09 | 陈力群 | Preparation method and application of surfactant |
| CN112852475A (en) * | 2020-12-25 | 2021-05-28 | 天津长芦新材料研究院有限公司 | Fluorine-containing demulsifying compound and demulsifying agent for oil field |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279217A (en) * | 2008-01-04 | 2008-10-08 | 上海亚孚化工科技有限公司 | Fluorine-carbon surfactant and method of producing the same |
-
2011
- 2011-01-14 CN CN2011100075540A patent/CN102068937A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279217A (en) * | 2008-01-04 | 2008-10-08 | 上海亚孚化工科技有限公司 | Fluorine-carbon surfactant and method of producing the same |
Non-Patent Citations (1)
| Title |
|---|
| SAMUEL ACHILEFU，ET AL.，: "Synthesis of 2H,2H-perfluoroalkyl and 2H-perfluoroalkenyl carboxylic acids and amides", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127877A (en) * | 2013-03-05 | 2013-06-05 | 山东东岳高分子材料有限公司 | Fluorine-containing surfactant and preparation method thereof |
| CN103127877B (en) * | 2013-03-05 | 2015-09-09 | 山东东岳高分子材料有限公司 | A kind of fluorine-containing surfactant and preparation method thereof |
| CN105198729A (en) * | 2015-09-17 | 2015-12-30 | 海门德思行药业科技有限公司 | Preparation method of perfluoroalkyl acetic acid |
| CN105198729B (en) * | 2015-09-17 | 2017-07-11 | 海门德思行药业科技有限公司 | The preparation method of perfluoroalkyl acetic acid |
| WO2019159707A1 (en) * | 2018-02-15 | 2019-08-22 | 富士フイルム株式会社 | Binder composition, binder layer, optical laminate and image display device |
| JPWO2019159707A1 (en) * | 2018-02-15 | 2021-02-25 | 富士フイルム株式会社 | Binder composition, binder layer, optical laminate and image display device |
| US11180661B2 (en) | 2018-02-15 | 2021-11-23 | Fujifilm Corporation | Binder composition, binder layer, optical laminate, and image display device |
| CN112341364A (en) * | 2020-09-29 | 2021-02-09 | 陈力群 | Preparation method and application of surfactant |
| CN112852475A (en) * | 2020-12-25 | 2021-05-28 | 天津长芦新材料研究院有限公司 | Fluorine-containing demulsifying compound and demulsifying agent for oil field |
| CN112852475B (en) * | 2020-12-25 | 2023-02-28 | 天津长芦新材料研究院有限公司 | Fluorine-containing demulsifying compound and demulsifier for oil field |
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Application publication date: 20110525 |