CN112266343A - Synthetic method of perfluorohexyl sodium ethyl sulfonate - Google Patents
Synthetic method of perfluorohexyl sodium ethyl sulfonate Download PDFInfo
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- CN112266343A CN112266343A CN202011391336.7A CN202011391336A CN112266343A CN 112266343 A CN112266343 A CN 112266343A CN 202011391336 A CN202011391336 A CN 202011391336A CN 112266343 A CN112266343 A CN 112266343A
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- perfluorohexyl
- sodium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
Abstract
The invention belongs to the technical field of fluorocarbon surfactant application, and particularly discloses a synthetic method of sodium perfluorohexylethyl sulfonate, which comprises the following steps: (1) adding water into perfluorohexylethyl iodide, potassium thiocyanate and a phase transfer catalyst under the protection of nitrogen, heating, stirring, reacting, separating an organic layer, and performing rotary evaporation to obtain perfluorohexylethyl thiocyanate; (2) adding perfluorohexyl ethyl thiocyanate into water, heating, continuously introducing chlorine gas, stirring for reaction, filtering and separating to obtain perfluorohexyl ethyl sulfonyl chloride; (3) and (3) dropwise adding perfluorohexyl ethyl sulfonyl chloride into the sodium hydroxide aqueous solution, stirring for reaction, filtering, washing with water, recrystallizing and drying to obtain the perfluorohexyl sodium ethyl sulfonate. The invention has the beneficial effects that: the perfluorohexyl sodium ethyl sulfonate has high yield, high purity, excellent surface activity, excellent compounding performance with hydrocarbon surfactant, excellent heat stability, excellent salt resistance and excellent chemical stability, and meets the requirement of environmental protection.
Description
Technical Field
The invention belongs to the technical field of application of fluorocarbon surfactants, and particularly relates to a synthesis method of perfluorohexyl sodium ethylsulfonate.
Background
The fluorocarbon surfactant is a surfactant with hydrophobic and oleophobic fluorocarbon chain segment formed by replacing all or part of oxygen atoms in a nonpolar group carbon-oxygen chain with fluorine atoms, is the surfactant with the most excellent surface activity at present, has high chemical activity, high thermal stability, high chemical stability and hydrophobic and oleophobic properties, and is widely applied to the fields of detergents, foods, cosmetics, petrochemical industry, coatings, plastics, rubber, fire fighting, photosensitive materials, medical appliances and the like.
The fluorocarbon surfactant widely used at present is perfluorooctyl sulfonate and perfluorocaprylic acid salt, which are widely applied to various fields of textiles, carpets, paper, coatings, fire-fighting foams, image materials, aviation hydraulic oil and the like, but the two salts are one of the most difficult-to-degrade organic pollutants at present, have high biological accumulation capacity and bring environmental pollution problems, and a suitable substitute needs to be found.
Therefore, based on the above problems, the present invention provides a method for synthesizing perfluorohexylethyl sodium sulfonate.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a method for synthesizing perfluorohexylethyl sodium sulfonate, which has high yield, the synthesized perfluorohexylethyl sodium sulfonate is used as an anionic fluorocarbon surfactant, the product performance is excellent and meets the current environmental protection requirement, and the method can replace the existing perfluorooctyl sulfonate and perfluorocaprylate fluorocarbon surfactant.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a synthetic method of perfluorohexyl sodium ethyl sulfonate comprises the following steps:
(1) under the protection of nitrogen, adding metered perfluorohexyl ethyl iodide, potassium thiocyanate and a phase transfer catalyst into a reaction flask, adding deionized water, heating, stirring and reacting for 5-6h, then separating an organic layer, washing with the deionized water, separating for 4-5 times, and placing in a rotary evaporator to remove water to obtain perfluorohexyl ethyl thiocyanate;
(2) adding the perfluorohexyl ethyl thiocyanate obtained in the step (1) into a high-pressure reaction kettle after oxygen removal, adding deionized water, heating to 90-100 ℃, continuously introducing chlorine for 10h, continuing stirring to react for 3-4 h after the addition is finished, cooling and discharging;
(3) washing the product obtained in the step (2) with deionized water, separating an organic layer by using a separating funnel, repeating the washing for 4-5 times, adding a toluene solvent to dissolve the product, washing with deionized water, separating the organic layer, repeating the washing for 2-3 times, and then removing the solvent by rotary evaporation to obtain a product, namely perfluorohexyl ethyl sulfonyl chloride;
(4) adding a metered sodium hydroxide aqueous solution into a round-bottom flask, dropwise adding the perfluorohexyl ethyl sulfonyl chloride obtained in the step (3) into an ice-water bath reaction system, keeping the dropwise adding time at 2 h, stirring and reacting for 20 h after the dropwise adding is finished, filtering to obtain a filtrate, cooling and filtering the filtrate to obtain a filter cake, and washing, recrystallizing and drying the filter cake to obtain the perfluorohexyl ethyl sodium sulfonate.
In the technical scheme, the phase transfer catalyst is methyl trioctyl ammonium chloride.
According to the technical scheme, the molar ratio of the perfluorohexyl ethyl iodide, the potassium thiocyanate and the phase transfer catalyst in the step (1) is 1:1-3: 0.05-0.1.
In the technical scheme, the temperature rise temperature in the step (1) is 135-145 ℃.
In the technical scheme, the temperature of the ice water bath in the step (4) is-5 ℃ to-10 ℃.
Compared with the prior art, the synthetic method of the perfluorohexyl sodium ethylsulfonate has the beneficial effects that: the perfluorohexyl sodium ethyl sulfonate prepared by the method has high yield, high purity, excellent surface activity, excellent compounding performance with a hydrocarbon surfactant, and very good thermal stability, salt resistance and chemical stability, can replace perfluorooctyl sulfonate and perfluorocaprylate fluorocarbon surfactant, and meets the requirement of environmental protection.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The invention relates to a synthesis method of perfluorohexyl sodium ethyl sulfonate, which comprises the following steps:
(1) under the protection of nitrogen, adding 47.5g of perfluorohexylethyl iodide, 9.7g of potassium thiocyanate and 4.1g of methyltrioctylammonium chloride into a reaction flask, adding deionized water, heating to 135 ℃ and 145 ℃, stirring for reaction for 5 hours, separating an organic layer, washing with the deionized water, separating for 4-5 times, and placing in a rotary evaporator to remove moisture to obtain perfluorohexylethyl thiocyanate;
(2) adding the perfluorohexyl ethyl thiocyanate obtained in the step (1) into a high-pressure reaction kettle after oxygen removal, adding deionized water, heating to 90 ℃, continuously introducing chlorine for 10 hours, continuing stirring for reaction for 4 hours after the addition is finished, cooling and discharging;
(3) washing the product obtained in the step (2) with deionized water, separating an organic layer by using a separating funnel, repeating the washing for 4 times, adding a toluene solvent to dissolve the product, washing with deionized water, separating the organic layer, repeating the washing for 3 times, and removing the solvent by rotary evaporation to obtain a product, namely perfluorohexyl ethyl sulfonyl chloride;
(4) adding a metered sodium hydroxide aqueous solution into a round-bottom flask, dropwise adding the perfluorohexyl ethyl sulfonyl chloride obtained in the step (3) into an ice-water bath reaction system at the temperature of between 5 ℃ below zero and 10 ℃ below zero, keeping the dropwise adding time for 2 hours, stirring and reacting for 20 hours after the dropwise adding is finished, filtering to obtain a filtrate, cooling and filtering the filtrate to obtain a filter cake, washing the filter cake with water, recrystallizing and drying to obtain the perfluorohexyl ethyl sodium sulfonate, wherein the yield is 89.9%.
Example 2
The invention relates to a synthesis method of perfluorohexyl sodium ethyl sulfonate, which comprises the following steps:
(1) under the protection of nitrogen, adding 47.5g of perfluorohexylethyl iodide, 19.4 g of potassium thiocyanate and 2.1g of methyltrioctylammonium chloride into a reaction flask, adding deionized water, heating to 135 ℃ and 145 ℃, stirring for reaction for 6 hours, then separating an organic layer, washing with the deionized water, separating for 4-5 times, and placing in a rotary evaporator to remove moisture to obtain perfluorohexylethyl thiocyanate;
(2) adding the perfluorohexyl ethyl thiocyanate obtained in the step (1) into a high-pressure reaction kettle after oxygen removal, adding deionized water, heating to 95 ℃, continuously introducing chlorine for 10 hours, continuing stirring for reaction for 3 hours after the addition is finished, cooling and discharging;
(3) washing the product obtained in the step (2) with deionized water, separating an organic layer by using a separating funnel, repeating the washing for 4 times, adding a toluene solvent to dissolve the product, washing with deionized water, separating the organic layer, repeating the washing for 3 times, and removing the solvent by rotary evaporation to obtain a product, namely perfluorohexyl ethyl sulfonyl chloride;
(4) adding a metered sodium hydroxide aqueous solution into a round-bottom flask, dropwise adding the perfluorohexylethylsulfonyl chloride obtained in the step (3) into an ice-water bath reaction system at the temperature of between 5 ℃ below zero and 10 ℃ below zero, keeping the dropwise adding time for 2 hours, stirring and reacting for 20 hours after the dropwise adding is finished, filtering to obtain a filtrate, cooling and filtering the filtrate to obtain a filter cake, washing the filter cake with water, recrystallizing and drying to obtain the perfluorohexylethylsulfonic acid sodium salt, wherein the yield is 90.2%.
Example 3
The invention relates to a synthesis method of perfluorohexyl sodium ethyl sulfonate, which comprises the following steps:
(1) under the protection of nitrogen, adding 47.5g of perfluorohexylethyl iodide, 29.1g of potassium thiocyanate and 3.3g of methyltrioctylammonium chloride into a reaction flask, adding deionized water, heating to 135 ℃ and 145 ℃, stirring for reaction for 5-6h, separating an organic layer, washing with the deionized water, separating for 4-5 times, and placing in a rotary evaporator to remove moisture to obtain perfluorohexylethyl thiocyanate;
(2) adding the perfluorohexyl ethyl thiocyanate obtained in the step (1) into a high-pressure reaction kettle after oxygen removal, adding deionized water, heating to 100 ℃, continuously introducing chlorine for 10 hours, continuing stirring for reaction for 3 hours after the addition is finished, cooling and discharging;
(3) washing the product obtained in the step (2) with deionized water, separating an organic layer by using a separating funnel, repeating the washing for 5 times, adding a toluene solvent to dissolve the product, washing with deionized water, separating the organic layer, repeating the washing for 2 times, and removing the solvent by rotary evaporation to obtain a product, namely perfluorohexyl ethyl sulfonyl chloride;
(4) adding a metered sodium hydroxide aqueous solution into a round-bottom flask, dropwise adding the perfluorohexylethylsulfonyl chloride obtained in the step (3) into an ice-water bath reaction system at the temperature of between 5 ℃ below zero and 10 ℃ below zero, keeping the dropwise adding time for 2 hours, stirring and reacting for 20 hours after the dropwise adding is finished, filtering to obtain a filtrate, cooling and filtering the filtrate to obtain a filter cake, washing the filter cake with water, recrystallizing and drying to obtain the perfluorohexylethylsulfonic acid sodium salt, wherein the yield is 90.4%.
The synthesis method of the perfluorohexyl sodium ethylsulfonate in the first embodiment or the second embodiment or the third embodiment of the invention has the advantages of high yield and purity of the perfluorohexyl sodium ethylsulfonate, excellent surface activity, excellent compounding performance with hydrocarbon surfactant, and very good thermal stability, salt resistance and chemical stability, and can replace perfluorooctyl sulfonate and perfluorocaprylate fluorocarbon surfactant to meet the requirement of environmental protection.
The foregoing is considered as illustrative of the preferred embodiments of the invention, but is made merely for the purpose of providing an understanding of the principles of the embodiments; meanwhile, for a person skilled in the art, according to the present embodiment, there may be a change in the specific implementation and application scope, and in summary, the present disclosure should not be construed as a limitation to the present invention.
Claims (5)
1. A synthetic method of perfluorohexyl sodium ethyl sulfonate is characterized in that: the method comprises the following steps:
(1) under the protection of nitrogen, adding metered perfluorohexyl ethyl iodide, potassium thiocyanate and a phase transfer catalyst into a reaction flask, adding deionized water, heating, stirring and reacting for 5-6h, then separating an organic layer, washing with the deionized water, separating for 4-5 times, and placing in a rotary evaporator to remove water to obtain perfluorohexyl ethyl thiocyanate;
(2) adding the perfluorohexyl ethyl thiocyanate obtained in the step (1) into a high-pressure reaction kettle after oxygen removal, adding deionized water, heating to 90-100 ℃, continuously introducing chlorine for 10h, continuing stirring to react for 3-4 h after the addition is finished, cooling and discharging;
(3) washing the product obtained in the step (2) with deionized water, separating an organic layer by using a separating funnel, repeating the washing for 4-5 times, adding a toluene solvent to dissolve the product, washing with deionized water, separating the organic layer, repeating the washing for 2-3 times, and then removing the solvent by rotary evaporation to obtain a product, namely perfluorohexyl ethyl sulfonyl chloride;
(4) adding a metered sodium hydroxide aqueous solution into a round-bottom flask, dropwise adding the perfluorohexyl ethyl sulfonyl chloride obtained in the step (3) into an ice-water bath reaction system, keeping the dropwise adding time at 2 h, stirring and reacting for 20 h after the dropwise adding is finished, filtering to obtain a filtrate, cooling and filtering the filtrate to obtain a filter cake, and washing, recrystallizing and drying the filter cake to obtain the perfluorohexyl ethyl sodium sulfonate.
2. The method for synthesizing sodium perfluorohexylethyl sulfonate according to claim 1, characterized in that: the phase transfer catalyst is methyl trioctyl ammonium chloride.
3. The method for synthesizing sodium perfluorohexylethyl sulfonate according to claim 1, characterized in that: the molar ratio of the perfluorohexylethyl iodide, the potassium thiocyanate and the phase transfer catalyst in the step (1) is 1:1-3: 0.05-0.1.
4. The method for synthesizing sodium perfluorohexylethyl sulfonate according to claim 1, characterized in that: the temperature rise temperature in the step (1) is 135-145 ℃.
5. The method for synthesizing sodium perfluorohexylethyl sulfonate according to claim 1, characterized in that: the temperature of the ice water bath in the step (4) is-5 ℃ to-10 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003300A (en) * | 2022-12-15 | 2023-04-25 | 三明市海斯福化工有限责任公司 | Preparation method of chromium fog inhibitor |
| CN116003300B (en) * | 2022-12-15 | 2024-04-26 | 三明市海斯福化工有限责任公司 | Preparation method of chromium fog inhibitor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239948A (en) * | 1996-12-13 | 1999-12-29 | 纳幕尔杜邦公司 | Fluorinated alkylthiocyanate process |
| CN101759613A (en) * | 2010-01-29 | 2010-06-30 | 湖北恒新化工有限公司 | Preparation method for perfluoroalkyl vikane |
| CN102216345A (en) * | 2008-11-13 | 2011-10-12 | 纳幕尔杜邦公司 | Fluorosulfonates |
| CN104844483A (en) * | 2015-04-24 | 2015-08-19 | 巨化集团技术中心 | Preparation method for perfluorohexylethyl sulfonate |
| EP2940049A1 (en) * | 2012-12-28 | 2015-11-04 | Daikin Industries, Ltd. | Production method for polyvinylidene fluoride aqueous dispersion liquid, and polyvinylidene fluoride aqueous dispersion liquid |
| CN105683140A (en) * | 2013-09-04 | 2016-06-15 | 霍尼韦尔国际公司 | Fluorosurfactants having improved biodegradability |
-
2020
- 2020-12-02 CN CN202011391336.7A patent/CN112266343A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239948A (en) * | 1996-12-13 | 1999-12-29 | 纳幕尔杜邦公司 | Fluorinated alkylthiocyanate process |
| CN102216345A (en) * | 2008-11-13 | 2011-10-12 | 纳幕尔杜邦公司 | Fluorosulfonates |
| CN101759613A (en) * | 2010-01-29 | 2010-06-30 | 湖北恒新化工有限公司 | Preparation method for perfluoroalkyl vikane |
| EP2940049A1 (en) * | 2012-12-28 | 2015-11-04 | Daikin Industries, Ltd. | Production method for polyvinylidene fluoride aqueous dispersion liquid, and polyvinylidene fluoride aqueous dispersion liquid |
| CN105683140A (en) * | 2013-09-04 | 2016-06-15 | 霍尼韦尔国际公司 | Fluorosurfactants having improved biodegradability |
| CN104844483A (en) * | 2015-04-24 | 2015-08-19 | 巨化集团技术中心 | Preparation method for perfluorohexylethyl sulfonate |
Non-Patent Citations (3)
| Title |
|---|
| SHENG PENG等: "Fluorinated sulfonate surfactants", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
| 王载结著: "《阴离子表面活性剂》", 30 June 1983, 轻工业出版社 * |
| 范春雷等: "氟碳表面活性剂全氟己基磺酸钾的合成研究", 《有机氟工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003300A (en) * | 2022-12-15 | 2023-04-25 | 三明市海斯福化工有限责任公司 | Preparation method of chromium fog inhibitor |
| CN116003300B (en) * | 2022-12-15 | 2024-04-26 | 三明市海斯福化工有限责任公司 | Preparation method of chromium fog inhibitor |
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Inventor after: Dong Jingfei Inventor after: Pan Deshun Inventor after: Li Jing Inventor after: Wang Junqi Inventor after: Huang Dunyi Inventor before: Dong Jingfei Inventor before: Zhang Quanling Inventor before: Pan Deshun Inventor before: Chen Fang Inventor before: Yu Wei Inventor before: Li Jing Inventor before: Wang Junqi Inventor before: Huang Dunyi |