CN114315564A - Novel anionic fluorocarbon surfactant and preparation method and application thereof - Google Patents
Novel anionic fluorocarbon surfactant and preparation method and application thereof Download PDFInfo
- Publication number
- CN114315564A CN114315564A CN202111560085.5A CN202111560085A CN114315564A CN 114315564 A CN114315564 A CN 114315564A CN 202111560085 A CN202111560085 A CN 202111560085A CN 114315564 A CN114315564 A CN 114315564A
- Authority
- CN
- China
- Prior art keywords
- surfactant
- fluorocarbon surfactant
- anionic fluorocarbon
- fluoride
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Disclosed is an anionic fluorocarbon surfactant selected from compounds of the general formula (1). The surfactant has low critical micelle concentration and low surface tension. The corresponding preparation method can overcome the defects of the prior art, has higher yield and purity, and simultaneously reduces the cost and the wastewater discharge. When the emulsifier is applied to the fluorine-containing olefin polymerization, the emulsifier has good emulsifying property.
Description
Technical Field
The invention relates to the field of surfactants, in particular to a novel anionic fluorocarbon surfactant and a preparation method and application thereof.
Background
The fluorocarbon surfactant has high surface activity, high heat-resistant stability, high chemical stability and excellent compatibility, is hydrophobic and oleophobic, is antifouling, and can obviously improve the wettability, permeability, emulsification and leveling properties of a medium. At present, the method is widely applied to the industries of chemical industry, textile industry, coating industry, papermaking industry and the like. Among the most widely used fluorocarbon surfactants include: perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and derivatives thereof. The fluorocarbon surfactant has low cost and high chemical stability.
Studies have shown that PFOA/PFOS-type surfactants are one of the most difficult to degrade organic contaminants found in nature and have the essential characteristics of persistent bioaccumulation and long-range migration. After the organism takes in PFOA/PFOS, it is difficult to decompose the PFOA/PFOS by the organism's metabolism. Although the effect on humans is not well defined, high doses of ammonium perfluorooctanoate have been shown in animal experiments to cause carcinogenesis in the animal body, and to present a threat to human health. PFOS has been reported to have a half-life in humans of up to 8.7 years.
The Environmental Protection Agency (EPA) issued a voluntary 2010-2015 environmental program for perfluorooctanoic acid and its salts to target trace residues. In 2017, the european union published (EU)2017/1000 in official gazette, new REACH regulation annex XVII 68 restriction terms on perfluorooctanoic acid (PFOA), and officially incorporated PFOA, salts thereof, and other related substances into REACH regulation restriction lists.
In order to solve the problem of pollution caused by PFOA/PFOS, environmental-friendly fluorocarbon surfactants are researched, and short fluorocarbon chain compounds (C) are found in the long-term research processnF2n+1N is less than or equal to 6) has lower toxicity and bioaccumulation than long fluorocarbon chain compounds. Accordingly, researchers have proposed strategies for developing environmentally friendly fluorocarbon surfactants, including: shortening the length of the fluorocarbon chain; introducing heteroatoms such as oxygen, nitrogen, sulfur and the like into the fluorocarbon chain; introducing a branched chain on the fluorocarbon chain. These strategies introduce a certain amount of fluorine into the fluorocarbon chainThe degradable sites of (2) make the fluorocarbon chain more easily degraded under natural environmental conditions, and reduce the toxicity, environmental durability and biological accumulation of the fluorocarbon chain. The short fluorocarbon chain environment-friendly fluorocarbon surfactant developed by the strategy is used as a substitute of the long fluorocarbon chain fluorocarbon surfactant, and has extremely important significance for sustainable development of human society.
JP-A-61-76439A discloses a perfluorohexylbenzoic acid surfactant. The surface tension of the surfactant at 25 ℃ is 18.9 mN/m; however, the Critical Micelle Concentration (CMC) of this surfactant is high, only 5X 10-3mol/L。
It is well known that the smaller the critical micelle concentration, the lower the concentration of surfactant required to form micelles, and the lower the concentration required to achieve surface saturation adsorption. The lower the concentration required for the change in surface properties, which acts as wetting, emulsifying, solubilizing, foaming, etc.
On the other hand, as the fluorocarbon surfactant, the existing preparation methods have some defects. For example, some synthetic processes require the use of highly corrosive, highly toxic oxidants, and generate large amounts of wastewater; some synthesis processes require the use of a large amount of expensive catalysts, and have high cost and low yield.
Therefore, in order to overcome the above defects in the prior art, a new anionic fluorocarbon surfactant with better surface activity, and a preparation method and application thereof are urgently needed to be found.
Disclosure of Invention
The invention aims to provide a novel anionic fluorocarbon surfactant. The fluorocarbon surfactant not only has lower Critical Micelle Concentration (CMC), but also has lower surface tension.
It is a second object of the present invention to further provide a process for the preparation of the novel anionic fluorocarbon surfactants described above and below. The preparation method can overcome the defects of the prior art, has higher yield and purity, and simultaneously reduces the cost and the wastewater discharge.
It is a further object of the present invention to provide the use of the novel anionic fluorocarbon surfactants described above and below. When applied to fluorine-containing olefin polymerization, the novel anionic fluorocarbon surfactant has low surface tension and good emulsifying property.
In order to achieve the above object, in one aspect, the present invention provides an anionic fluorocarbon surfactant characterized in that the surfactant is selected from compounds of the general formula (1),
wherein M is selected from hydrogen and NH4Or an alkali metal; n is an integer from 1 to 6.
The surfactant according to the present invention, wherein the surfactant is selected from the compounds of formula (2),
in another aspect, the present invention provides a method for preparing the anionic fluorocarbon surfactant of the present invention, comprising:
1) mixing hexafluoropropylene dimer, tetrabutylammonium fluoride (TBAF), an organic solvent and alkali metal fluoride, then dropwise adding the compound of the formula (3),
wherein R represents an alkyl group of 1 to 4 carbon atoms, X represents a leaving group, and n is selected from integers of 1 to 6; carrying out heat preservation reaction, and cooling the obtained reaction system after the reaction is finished;
2) pulping the obtained reaction system, and filtering to obtain an esterified substance;
3) and adding alkali into the obtained ester for hydrolysis to obtain the corresponding salt of the anionic fluorocarbon surfactant.
The preparation method according to the invention further comprises the following steps: and adding acid into the obtained salt solution for acidification to obtain the corresponding anionic fluorocarbon surfactant.
The production process according to the present invention, wherein the hexafluoropropylene dimer is selected from the compounds of formula (4),
the preparation method of the invention, wherein X represents bromine or iodine.
The preparation method provided by the invention is characterized in that n is selected from 2.
The preparation method of the invention is characterized in that R represents CH3Or C2H5。
The production method according to the present invention, wherein the alkali metal fluoride is selected from potassium fluoride, sodium fluoride or cesium fluoride.
In another aspect, the invention provides a use of the anionic fluorocarbon surfactant of the invention, which is characterized in that the anionic fluorocarbon surfactant is used for fluorine-containing olefin polymerization.
Compared with the prior art, the novel anionic fluorocarbon surfactant disclosed by the invention is not only low in Critical Micelle Concentration (CMC), but also reduced in surface tension. The corresponding preparation method can overcome the defects of the prior art, has higher yield and purity, and simultaneously reduces the cost and the wastewater discharge. When the anionic fluorocarbon surfactant is applied to fluorine-containing olefin polymerization, the novel anionic fluorocarbon surfactant has lower surface tension and good emulsifying property.
Drawings
FIG. 1 is a schematic representation of an anionic fluorocarbon surfactant according to an embodiment of the present invention19F NMR chart.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the invention. Unless otherwise indicated, percentages in the examples are uniformly percentages by mass.
In a particular embodiment of the present invention, there is provided an anionic fluorocarbon surfactant according to the present invention, selected from compounds of general formula (1),
wherein M is selected from hydrogen and NH4Or an alkali metal; n is an integer from 1 to 6.
In a particular embodiment of the invention, the alkali metal is selected from lithium, sodium, potassium, rubidium, cesium.
Further, n is selected from an integer of 1 to 4, preferably an integer of 1 to 3.
In a specific embodiment of the present invention, there is provided a method for preparing the anionic fluorocarbon surfactant according to the present invention, comprising:
1) mixing hexafluoropropylene dimer, tetrabutylammonium fluoride (TBAF), an organic solvent and alkali metal fluoride, then dropwise adding the compound of the formula (3),
wherein R represents an alkyl group of 1 to 4 carbon atoms, X represents a leaving group, and n is selected from integers of 1 to 6; carrying out heat preservation reaction, and cooling the obtained reaction system after the reaction is finished;
2) pulping the obtained reaction system, and filtering to obtain an esterified substance;
3) and adding alkali into the obtained ester for hydrolysis to obtain the corresponding salt of the anionic fluorocarbon surfactant.
In a particular embodiment of the invention, the hexafluoropropylene dimer is selected from compounds of formula (4),
those skilled in the art know that hexafluoropropylene dimer has both the structures D1 and D2, the latter being a compound of formula (4). D1 was converted to D2 by isomerization under high or normal pressure conditions.
Under normal pressure conditions, the isomerization reaction is advantageously carried out in the presence of KF and acetonitrile at a temperature of about 50 ℃ and at a conversion of greater than 99% over 8 h.
In some embodiments, said step 1) specifically comprises: mixing hexafluoropropylene dimer D2, TBAF and an organic solvent, and adding alkali metal fluoride; heating the mixture to 50-70 ℃, and dropwise adding the compound of the formula (3); wherein R represents CH3Or C2H5X represents bromine or iodine, and n is an integer selected from 1 to 3.
Advantageously, after the dropwise addition is completed within 1-4 h, the reaction system is heated to 75-95 ℃ for heat preservation reaction.
In some more specific embodiments, the compound of formula (3) is further selected from compounds of formula (3-1),
in some more specific embodiments, hexafluoropropylene dimer, TBAF, and organic solvent are put into an esterification reaction device, alkali metal fluoride is added, stirring is started, a hot water valve is opened, the temperature is raised to 60 ℃, and dropwise addition of the compound of formula (3-1) is started, wherein R represents C2H5And dripping the solution in 1-4 h, heating the reaction system to 75-95 ℃, preserving the temperature for 2h, and finally opening a jacket to cool the water to room temperature.
Further, in the step 1), the mass ratio of the hexafluoropropylene dimer, the TBAF, the organic solvent, the alkali metal fluoride and the compound of the formula (3) is 2.5-3.5: 0.1-0.2: 1.5-2.5: 0.2-1.2: 1.5-2.5.
Further, the alkali metal fluoride is selected from potassium fluoride, sodium fluoride, cesium fluoride.
Further, the organic solvent is selected from DMF, DMAc, NMP.
In some preferred embodiments, said step 2) specifically comprises: cooling the reaction mixed system obtained in the step 1) to room temperature, pulping for 2h, and filtering to remove filtrate to obtain white solid, namely esterified substance.
In some specific embodiments, the pulping time is 1-3 hours, the pulping temperature is 10-30 ℃, and the esterified substance is obtained by filtering.
In some preferred embodiments, said step 3) specifically comprises: and adding the obtained ester into an alkaline water solution, finishing dropwise adding within 20-50 min, and keeping the hydrolysis temperature at 70-85 ℃ to obtain the salt.
For example, in some more specific embodiments, the ester obtained in step 2) is added into an aqueous alkali solution, the concentration of the aqueous alkali is 10 wt%, and the dropwise addition is completed within 30min, and the hydrolysis temperature is kept at 70-85 ℃, so as to obtain the salt of the anionic fluorocarbon surfactant.
Further, the base is selected from NaOH or KOH.
In some preferred embodiments, said step 4) specifically comprises: adding excessive acid into the salt solution obtained in the step 3), controlling the reaction temperature to be 60-70 ℃ during dropwise adding, keeping the temperature to be 70-85 ℃ for 1h after dropwise adding is finished, finally cooling to room temperature, filtering, and washing with water to obtain the anionic fluorocarbon surfactant.
For example, in some specific embodiments, hydrochloric acid is pumped into an acidification reaction device, the temperature of the reaction liquid is controlled to be 60-70 ℃, hydrochloric acid is started to be dripped, heat preservation is carried out for 1 hour at 70-85 ℃ after dripping is finished, circulating water is started to cool, pulping is carried out for 1 hour after cooling to room temperature, filtering is carried out, and washing is carried out once again to obtain the anionic fluorocarbon surfactant.
Example 1:
(1) esterification reaction
Adding 250g of hexafluoropropylene dimer D2, 150g of DMF and 10g of TBAF into an esterification reaction device, starting stirring, adding 100g of potassium fluoride after stirring for 10min, heating to 60 ℃, dropwise adding 200g of a compound shown in the following formula,
and (5) finishing the dropwise addition within 2h, carrying out heat preservation reaction at 80 ℃ for 2h, starting cold water to cool to room temperature after finishing the heat preservation.
(2) Filtration
Cooling the mixed system obtained in the last step to 20 ℃, stirring and pulping for 2h, and filtering to remove filtrate to obtain the esterified substance.
(3) Hydrolysis reaction
Adding the ester into 200g of 10 wt% potassium hydroxide aqueous solution, heating to 80 ℃ for hydrolysis, and reacting for 1h to obtain a potassium salt solution.
(4) Acidification reaction
Pumping hydrochloric acid into an acidification reaction device, controlling the temperature of the reaction liquid to be 60-70 ℃, starting to dropwise add the hydrochloric acid, preserving the heat at 80 ℃ for 1h after the dropwise addition is finished, starting circulating water to cool, pulping for 1h after the temperature is reduced to room temperature, filtering, and washing with water once to obtain the finished product of the anionic fluorocarbon surfactant.
(5) Drying by baking
And drying the filtered finished product at the temperature of 60 ℃ for 24h to obtain the anionic fluorocarbon surfactant. The total yield is 98 percent, and the purity reaches 99 percent.
FIG. 1 is a schematic representation of the anionic fluorocarbon surfactant of example 1 of the present invention19F NMR chart.
When the anionic fluorocarbon surfactant of example 1 was measured for surface tension of the fluorocarbon surfactant obtained at different concentrations at pH 7.0 (adjusted using KOH solution), the specific results were as follows: the concentration is 2.07 x 10-3When M is used, the surface tension is 16.7 mN/M; CMC 4.38 × 10-5M is superior to most of the prior similar products. The preparation method can overcome the defects of the prior art, has higher yield and purity, and simultaneously reduces the cost and the wastewater discharge. When the anionic fluorocarbon surfactant is applied to fluorine-containing olefin polymerization, the novel anionic fluorocarbon surfactant has lower surface tension and good emulsifying property.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (10)
1. An anionic fluorocarbon surfactant characterised in that the surfactant is selected from compounds of formula (1),
wherein M is selected from hydrogen and NH4Or an alkali metal; n is an integer from 1 to 6.
2. The surfactant according to claim 1, wherein the surfactant is selected from compounds of formula (2),
3. a process for the preparation of an anionic fluorocarbon surfactant as claimed in claim 1 or claim 2 comprising:
1) mixing hexafluoropropylene dimer, tetrabutylammonium fluoride (TBAF), an organic solvent and alkali metal fluoride, then dropwise adding the compound of the formula (3),
wherein R represents an alkyl group of 1 to 4 carbon atoms, X represents a leaving group, and n is selected from integers of 1 to 6; carrying out heat preservation reaction, and cooling the obtained reaction system after the reaction is finished;
2) pulping the obtained reaction system, and filtering to obtain an esterified substance;
3) and adding alkali into the obtained ester for hydrolysis to obtain the corresponding salt of the anionic fluorocarbon surfactant.
4. The production method according to claim 3, further comprising: and adding acid into the obtained salt solution for acidification to obtain the corresponding anionic fluorocarbon surfactant.
5. The production process according to claim 3 or 4, wherein the hexafluoropropylene dimer is selected from a compound of formula (4),
6. the process according to claim 5, wherein X represents bromine or iodine.
7. The method according to claim 5, wherein n is 2.
8. The process according to claim 5, wherein R represents CH3Or C2H5。
9. A production method according to claim 5, wherein the alkali metal fluoride is selected from potassium fluoride, sodium fluoride or cesium fluoride.
10. Use of the anionic fluorocarbon surfactant of claim 1 or 2 in the polymerization of fluoroolefins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111560085.5A CN114315564B (en) | 2021-12-20 | 2021-12-20 | Novel anionic fluorocarbon surfactant, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111560085.5A CN114315564B (en) | 2021-12-20 | 2021-12-20 | Novel anionic fluorocarbon surfactant, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114315564A true CN114315564A (en) | 2022-04-12 |
| CN114315564B CN114315564B (en) | 2023-09-29 |
Family
ID=81053007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111560085.5A Active CN114315564B (en) | 2021-12-20 | 2021-12-20 | Novel anionic fluorocarbon surfactant, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114315564B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176439A (en) * | 1984-09-21 | 1986-04-18 | Neos Co Ltd | Perfluorohexylbenzylcarboxylic acid and its salt |
| CN1182437A (en) * | 1995-03-24 | 1998-05-20 | 查珀尔希尔北卡罗来纳大学 | Multi-phase polymerization process |
| CN109851529A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院上海有机化学研究所 | A kind of amphoteric fluorine-containing surfactant and the preparation method and application thereof |
| CN113750435A (en) * | 2020-06-03 | 2021-12-07 | 南京理工大学 | Efficient and environment-friendly aqueous film-forming foam extinguishing agent and preparation method thereof |
-
2021
- 2021-12-20 CN CN202111560085.5A patent/CN114315564B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176439A (en) * | 1984-09-21 | 1986-04-18 | Neos Co Ltd | Perfluorohexylbenzylcarboxylic acid and its salt |
| CN1182437A (en) * | 1995-03-24 | 1998-05-20 | 查珀尔希尔北卡罗来纳大学 | Multi-phase polymerization process |
| CN109851529A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院上海有机化学研究所 | A kind of amphoteric fluorine-containing surfactant and the preparation method and application thereof |
| CN113750435A (en) * | 2020-06-03 | 2021-12-07 | 南京理工大学 | Efficient and environment-friendly aqueous film-forming foam extinguishing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114315564B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US1881172A (en) | The-main | |
| CN103831057A (en) | Fluorocarbon surface active agent and preparation method thereof | |
| CN105017097A (en) | Preparation method for surfactant N-carboxyethyl, N-3-dimethylaminopropyl-perfluoro hexyl sulfonamide | |
| CN111499550B (en) | Fluorine-containing surfactant and preparation method and application thereof | |
| CN108911983A (en) | A kind of environment-friendly preparation method of fluorinated acrylate | |
| CN114315564A (en) | Novel anionic fluorocarbon surfactant and preparation method and application thereof | |
| CN110354755A (en) | Novel fluorine-containing betaine surfactant and preparation method and application thereof | |
| US8633328B2 (en) | Method of making fluorinated alkoxy carboxylic acids and precursors thereof | |
| CN100500737C (en) | Method of synthesizing polyethylene glycol perfluoroolefin ether | |
| JPS5846043A (en) | Manufacture of quaternary ammonium compound, softening and antistatic method and expulsion of gonococcus | |
| US4658052A (en) | Salts, containing fluoroalkyl groups, of β-alkylamino-propionic acid esters, a process for their synthesis and their use for the production of aqueous polyacrylate dispersions containing fluoroalkyl groups | |
| CN101433813B (en) | Hexafluoropropylene-based quaternary ammonium salt cationic surfactant, synthesizing method and use | |
| CN102766065B (en) | Synthetic method of fluorocarbon surfactant N-2 hydroxyethyl perfluorocarbon symplectic amide | |
| CN105924573A (en) | Perfluoroalkyl polyene ester waterproof agent, preparation method and application | |
| JP2014037355A (en) | Novel fluorocarbon chain-containing compound, production method and use of the same | |
| CN1692974A (en) | Synthetic method and use of perfluoro-amphoteric surfactant | |
| CN109762132B (en) | Preparation method of polymerizable nonionic fluorine-containing short-chain surfactant | |
| CN101863739A (en) | Preparation method of perfluoroalkyl ethyl alcohol | |
| CN113563192A (en) | Preparation method of low-toxicity fluorine-containing acrylate | |
| KR101530606B1 (en) | Surfactants of Sulfate and Phosphate-Based Perfluorinated Alkyl Esters and Chromium Etchant and Low Temperature Process Soaping Agent Comprising the Same | |
| KR100721220B1 (en) | Manufacturing method of 4,6-bis (substituted) phenyl azo resorcinol | |
| CN109912468A (en) | A kind of preparation method of acrylic acid (1- chloromethyl, 2-N- methyl perfluoro hexyl sulfoamido) ethyl ester | |
| JPS6233222B2 (en) | ||
| KR101401045B1 (en) | Surfactants of sulfate and phosphate-based perfluorinated alkyl esters and chromium etchant and low temperature process soaping agent comprising the same | |
| JPH029845A (en) | Production of n,n-disubstituted aniline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230421 Address after: 709-711, 715-717, 716-718, Building D, No. 606 Ningliu Road, Jiangbei New District, Nanjing City, Jiangsu Province, 210047 Applicant after: Jiangsu Tongfu High tech Materials Co.,Ltd. Address before: 210047 room 1101, building D, No. 606, ningliu Road, Changlu street, Jiangbei new area, Nanjing, Jiangsu Province Applicant before: Nanjing Xinfu New Material Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |