CN1692974A - Synthetic method and use of perfluoro-amphoteric surfactant - Google Patents
Synthetic method and use of perfluoro-amphoteric surfactant Download PDFInfo
- Publication number
- CN1692974A CN1692974A CN200510024463.2A CN200510024463A CN1692974A CN 1692974 A CN1692974 A CN 1692974A CN 200510024463 A CN200510024463 A CN 200510024463A CN 1692974 A CN1692974 A CN 1692974A
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- Prior art keywords
- perfluoro
- amphoteric surfactant
- reaction
- synthetic method
- perfluor aliphatic
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Abstract
A process for synthesizing the ampholytic perfluoro surfactant is prepared through the reaction between perfluoro aliphatic carboxylate and hydroxyalkyl diamine compound under the protection of N2 to generate perfluoro aliphatic amide, and reacting on chloroacetic acid to generate quaternary ammonium salt type surfactant while using the solution of sodium hydroxide to absorb the generated hydrogen chloride.
Description
[technical field]
The present invention relates to the amphoteric surfactant technical field, specifically a kind of perfluoro-amphoteric surfactant and preparation method and use thereof.
[background technology]
Amphoteric surfactant is because it has special nature, in acid medium, be cationic, in alkaline medium, be anionic, pH value 6～8 o'clock apparent both sexes, thereby can be well composite with the surfactant of other ionics and nonionic in pH scope comparatively widely, and be widely used in various fields.
Fluorocarbon surfactant is owing to its high surface, high thermal stability, high chemical stability; Do not decompose serviceability temperature and can reach more than 260 ℃ under the condition that strong acid, highly basic, strong oxidizer exist, not only hydrophobic but also hate the wet goods good characteristic had purposes widely.Require many that fluorocarbon surfactant has irreplaceable effect in the special field.
But at present, the two part that also comes with some shortcomings of amphoteric surfactant and fluorocarbon surfactant, as the advantage of amphoteric surfactant, fluorocarbon surfactant does not have; The advantage of fluorocarbon surfactant, amphoteric surfactant does not have yet.Thereby both can not be employed more widely.
[summary of the invention]
Purpose of the present invention is exactly will solve above-mentioned deficiency and a kind of perfluoro-amphoteric surfactant is provided, and combines the two excellent properties of amphoteric surfactant and fluorocarbon surfactant.It has the surface of good activity in the aqueous solution, the surface tension of the aqueous solution can be reduced to 12～15mN/m, is a kind of good surfactant.This compounds dissolves in various solvent, in acid medium, be cationic, in alkaline medium, be anionic, pH value 6～8 o'clock apparent both sexes, can reduce the surface tension of system effectively, thereby the needs that adapt to various different field can be widely used in fields such as chemical industry, printing ink, coating, adhesive, machinery, weaving, papermaking, glass, metallurgy, fuel, sensitization, building, leather, fire-fighting, household supplies.
For achieving the above object, the invention provides a kind of perfluoro-amphoteric surfactant, this compound has following general formula:
R wherein
fBe meant that the carbochain number is more than or equal to 6 perfluoroalkyl or perfluoroalkyl ethers; M=0,1,2,3; N=2,3,4,5; P=1,2,3,4,5;
This compound can make by the following method:
Wherein Rf is meant that the carbochain number is more than or equal to 6 perfluoroalkyl or perfluoroalkyl ethers; M=0,1,2,3; N=2,3,4,5; P=1,2,3,4,5;
First step reaction; perfluor aliphatic carboxylic acid esters, and hydroxy alkyl diamine compounds carry out the monoamides reaction under nitrogen protection; generate the perfluor aliphatic amide; the molar ratio of reactant is: the perfluor aliphatic carboxylic acid esters: hydroxy alkyl diamines=1: 1.0～2.0; reaction temperature is 60～150 ℃, and the reaction time is 1～30 hour.Send out and should finish, excessive hydroxy alkyl diamines is removed in decompression distillation, and the cut of 140 ℃～200 ℃/20mmHg is collected in decompression distillation then, promptly gets intermediate perfluor aliphatic amide.
The reaction of second step, intermediate perfluor aliphatic amide are carried out quaternary amine salinization reaction with chloride aliphatic carboxylic acid again, with the hydrogen chloride of sodium hydroxide solution absorption reaction generation.The molar ratio of reactant is: the perfluor aliphatic amide: chloride aliphatic carboxylic acid: NaOH=1: 2.0～3.0: 2.0～3.0, reaction temperature are 50～120 ℃, and the reaction time is 0.5～24 hour.After reaction finishes, wash the accessory substance sodium chloride of removing excessive chloride aliphatic carboxylic acid and NaOH and reaction generation with low amounts of water, vacuum gets corresponding perfluoro-amphoteric surfactant after dry 10 hours down for 50 ℃; The present invention is an initiation material with the perfluor aliphatic carboxylic acid esters,, carries out with the hydroxy alkyl diamines that monoamides is combined to; Perfluor aliphatic amide and monoxone carry out quaternary amine salinization reaction, with the hydrogen chloride of sodium hydroxide solution absorption reaction generation.
The present invention compares with prior art, have the surface of good activity, in acid medium, be cationic, in alkaline medium, be anionic, pH value 6～8 o'clock apparent both sexes, can reduce the surface tension of system effectively, and simple synthetic method, be easy to control, the reaction yield height, can be widely used in many fields, be fit to suitability for industrialized production, be worthy of promotion and application.
[specific embodiment]
Embodiment one:
With C
7F
15COOCH
3(42.8g, 0.10mol) and H
2NCH
2CH
2NHCH
2CH
2(12.5g 0.12mol) adds in the reaction bulb OH, is heated to 90～120 ℃ of reactions under stirring, and reaction distillation simultaneously removes the methyl alcohol that dereaction generates, and excessive hydroxyl diamine compounds H is removed in decompression distillation
2NCH
2CH
2NHCH
2CH
2OH promptly gets corresponding amide C
7F
15CONHCH
2CH
2NHCH
2CH
2The OH crude product.Crude product is collected the cut of 140～175 ℃/20mmHg scope through decompression distillation, promptly gets acid amides C
7F
15CONHCH
2CH
2NHCH
2CH
2OH elaboration 46.5g, productive rate 93.0%.
With ClCH
2COOH (20.8g, 0.22mol) be dissolved in the 20ml water, under the ice bath cooling condition, keep reaction temperature between-5 ℃～+ 5 ℃, slowly add (8.8g, 0.22mol) NaOH is dissolved in the aqueous solution of 20ml, about the pH=7 of regulator solution, be heated to 40 ℃～70 ℃ then, slowly add the acid amides C that above-mentioned reaction generates
7F
15CONHCH
2CH
2NHCH
2CH
2(20.8g 0.10mol), is heated to 80 ℃～100 ℃ and continues reaction 5～6 hours OH after adding, after reaction finishes, remove excessive ClCH with the low amounts of water washing
2The accessory substance NaCl that COOH and NaOH and reaction generate, vacuum gets corresponding perfluoro-amphoteric surfactant 60.1g, productive rate 94.2% after dry 10 hours down for 50 ℃.Product is consistent with target compound through identifying; This manufacturing technology concerning those skilled in the art still more clearly.
Claims (5)
1. perfluoro-amphoteric surfactant is characterized in that this compounds has following general structure:
R wherein
fBe meant that the carbochain number is more than or equal to 6 perfluoroalkyl or perfluoroalkyl ethers, m=0,1,2,3; N=2,3,4,5; P=1,2,3,4,5;
2. the synthetic method of a perfluoro-amphoteric surfactant is characterized in that the synthetic method of such compound may further comprise the steps:
(1) perfluor aliphatic carboxylic acid esters, and hydroxy alkyl diamine compounds carry out the monoamides reaction under nitrogen protection, generate the perfluor aliphatic amide;
(2) the perfluor aliphatic amide carries out quaternary amine salinization reaction with monoxone again, with the hydrogen chloride of sodium hydroxide solution absorption reaction generation.
3. the synthetic method of a kind of perfluoro-amphoteric surfactant as claimed in claim 2, the molar ratio that it is characterized in that reactant is: the perfluor aliphatic carboxylic acid esters: hydroxy alkyl diamines=1: 1.0～2.0, reaction temperature is 60～150 ℃, and the reaction time is 1～30 hour.
4. the synthetic method of a kind of perfluoro-amphoteric surfactant as claimed in claim 2, the molar ratio that it is characterized in that reactant is: perfluor aliphatic amide: monoxone: NaOH=1: 2.0～3.0: 2.0～3.0, reaction temperature is 50～120 ℃, and the reaction time is 0.5～24 hour.
5. a kind of perfluoro-amphoteric surfactant as claimed in claim 1 is characterized in that being widely used in chemical industry, printing ink, coating, adhesive, machinery, weaving, papermaking, glass, metallurgy, fuel, sensitization, building, leather, fire-fighting, household supplies field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100244632A CN1323747C (en) | 2005-03-18 | 2005-03-18 | Synthetic method and use of perfluoro-amphoteric surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100244632A CN1323747C (en) | 2005-03-18 | 2005-03-18 | Synthetic method and use of perfluoro-amphoteric surfactant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1692974A true CN1692974A (en) | 2005-11-09 |
| CN1323747C CN1323747C (en) | 2007-07-04 |
Family
ID=35352211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100244632A Expired - Fee Related CN1323747C (en) | 2005-03-18 | 2005-03-18 | Synthetic method and use of perfluoro-amphoteric surfactant |
Country Status (1)
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|---|---|
| CN (1) | CN1323747C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396369C (en) * | 2006-03-02 | 2008-06-25 | 翟健 | A novel hybridized non-ion fluorin surfactant and synthesis method thereof |
| US7638650B2 (en) | 2007-08-06 | 2009-12-29 | E.I. Du Pont De Nemours And Company | Fluoroalkyl surfactants |
| CN102574783A (en) * | 2009-10-15 | 2012-07-11 | 纳幕尔杜邦公司 | Fluorinated amphoteric surfactants |
| CN106268494A (en) * | 2016-07-20 | 2017-01-04 | 江苏理文化工有限公司 | A kind of efficient zwitterionic ionic surface active agent and synthetic method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE765255A (en) * | 1970-04-22 | 1971-08-30 | Ugine Kuhlmann | AMPHOLYTIC CARBOXYL FLUORINE COMPOUNDS |
| BE795386A (en) * | 1972-02-15 | 1973-08-13 | Philips Nv | CIRCUIT ALLOWING THE REPRODUCTION OF INFORMATION AT A PACE WHICH DIFFERS FROM THAT AT WHICH THE RECORDING OF THIS INFORMATION TAKEN PLACE |
| US4388212A (en) * | 1979-11-09 | 1983-06-14 | E. I. Du Pont De Nemours & Co. | Reducing surface tension with N-type betaines of 2-hydroxyl-1,1,2,3,3-pentahydroperfluoroalkylamines |
| US4283533A (en) * | 1979-11-09 | 1981-08-11 | E. I. Du Pont De Nemours And Company | N-type betaines of 2-hydroxy-1,1,2,3,3-pentahydroperfluoroalkylamines |
| US4490304A (en) * | 1982-12-29 | 1984-12-25 | Ciba-Geigy Corporation | Perfluoroalkyl thioalkylene amphoteric compounds |
-
2005
- 2005-03-18 CN CNB2005100244632A patent/CN1323747C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396369C (en) * | 2006-03-02 | 2008-06-25 | 翟健 | A novel hybridized non-ion fluorin surfactant and synthesis method thereof |
| US7638650B2 (en) | 2007-08-06 | 2009-12-29 | E.I. Du Pont De Nemours And Company | Fluoroalkyl surfactants |
| CN102574783A (en) * | 2009-10-15 | 2012-07-11 | 纳幕尔杜邦公司 | Fluorinated amphoteric surfactants |
| CN106268494A (en) * | 2016-07-20 | 2017-01-04 | 江苏理文化工有限公司 | A kind of efficient zwitterionic ionic surface active agent and synthetic method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1323747C (en) | 2007-07-04 |
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Granted publication date: 20070704 Termination date: 20100318 |