CN103657512A - Perfluoroolefine type anionic gemini surfactant and preparation method thereof - Google Patents
Perfluoroolefine type anionic gemini surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN103657512A CN103657512A CN201310662220.6A CN201310662220A CN103657512A CN 103657512 A CN103657512 A CN 103657512A CN 201310662220 A CN201310662220 A CN 201310662220A CN 103657512 A CN103657512 A CN 103657512A
- Authority
- CN
- China
- Prior art keywords
- perfluorinated
- perfluor
- sodium
- condensation
- alkene
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a sulfonic acid type anionic gemini surfactant based on perfluorinated nonene and perfluorinated hexane, and a preparation method thereof. According to the preparation method, perfluorinated nonene or perfluorinated hexane is taken as a raw material; perfluorinated alkene oxyl benzoyl chloride is obtained via condensation of the raw material with p-hydroxybenzoic acid, and chlorination; perfluorinated alkene oxyl benzamide is obtained via direct condensation of perfluorinated alkene oxyl benzoyl chloride with diamine without separation; and at last the sulfonic acid type anionic gemini fluorinated surfactant is obtained via condensation of perfluorinated alkene oxyl benzamide with a sulfonated alkylation agent, wherein perfluorinated alkene oxyl phenyl groups are taken as lipophilic groups, amide bonds are taken as conjugation bridges, and sulfonates are taken as hydrophilic groups. The anionic gemini surfactant based on hexafluoropropene trimer or perfluoro(4-methylpent-2-ene) is high in surface activity, simple in synthesis, and low in cost, and possesses a promising application prospect.
Description
Technical field
The present invention relates to a class fluorine surfactant, particularly a class contains the anion Gemini surface active agent of perfluorinated nonene oxygen base or perfluor hexene oxygen base, and preparation method thereof.
Background technology
Fluorine surfactant is the special surfactant of a class, and it has and typical three high two hate (high thermal stability, high chemical stability, high surface, not only hate oil but also hydrophobic) characteristic, therefore at aspects such as fire-fighting, oil recoveries, has important application.The most widely used fluorine surfactant is perfluoro caprylic acid (PFOA) and perfluoro octyl sulfonic acid (PFOS) and derivative thereof all the time, but PFOA and PFOS compounds exist produce pollute large, can not biodegradation, can long-distance migration etc. shortcoming, be faced with and limit the use of and forbid.Hexafluoropropene oligomers particularly hexafluoropropylene dimmer and the derivative fluorine surfactant of hexafluoropropylene trimer is the potential PFOA of a class and PFOS substitute.But hexafluoropropene oligomers has branched structure, the surface-active of its derivative does not reach the level of PFOA and PFOS and derivative thereof, and the application of such substitute has been produced to very large restriction.
Gemini surface active agent is the special surface activating agent being formed by connecting in chemical bond mode by special linking group by two traditional surfactant molecules, contains two hydrophilic radicals and two oleophylic chains in molecule.Compare with traditional surfactant, it is strong that Gemini surface active agent has the micella of formation ability, and critical micelle concentration is low, reduce surface tension efficiency high, Kraft point is low, good water solubility, with the advantage such as other surfactant compatibility is good, be called as surfactant of new generation.The existing bibliographical information of Shuangzi fluorine surfactant based on straight chain type perfluor carbochain, as Chinese patent CN 101502771, CN 101293844, CN 102166494, CN 101309899 etc., but Shuangzi fluorine surfactant based on branched chain type perfluor carbochains such as hexafluoropropylene trimer or hexafluoropropylene dimmers there is no any bibliographical information.
Summary of the invention
In order to overcome the defect of existing hexafluoropropene oligomers derivative class surfactant surface-active deficiency, the present invention has prepared the double type fluorine surfactant of a class based on perfluorinated nonene and perfluor hexene, and its general formula is
Compound, R wherein
ffor perfluorinated nonene base or perfluor hexenyl, n be 2 or 3, M be sodium or potassium, R is (CH
2)
2or (CH
2)
3or (CH
2)
4or (CH
2)
5or (CH
2)
2o (CH
2)
2.
It is oleophilic moiety that above-claimed cpd be take perfluorinated nonene oxygen base phenyl or perfluor hexene oxygen base phenyl, take sulfonate as hydrophilic segment, and sodium ion or potassium ion are cation, between two surfactants with methene chain (CH
2)
2or (CH
2)
3or (CH
2)
4or (CH
2)
5or 3-oxa-pentylidene chain-(CH
2)
2o (CH
2)
2-for connecting bridge, oleophilic moiety is connected by amido link with hydrophilic segment.Owing to having possessed said structure feature, make described compound there is very high surface-active, surface tension, between 15.8mN/m and 21.0mN/m, approaches the level of PFOA and PFOS; Critical micelle concentration is lower, between 6.0x10
-5mol/L and 4.6x10
-4between mol/L.
It is raw material that sulfoacid gemini fluorine surfactant prepared by the present invention be take perfluorinated nonene or perfluor hexene, obtains perfluoro alkene oxygen base chlorobenzoyl chloride with P-hydroxybenzoic acid condensation, thionyl chloride chlorination
(A), the direct and ethylenediamine, 1 without separation, 3-propane diamine, Putriscine, 1,5-pentanediamine or 3-oxa--1, the condensation of 5-pentanediamine obtains corresponding perfluoro alkene oxygen yl-benzamide
(B), last and vinyl sulfonic acid sodium, chloroethyl sodium sulfonate, bromoethyl sodium sulfonate or the condensation of 1,3-propane sultone obtain a class perfluor alkene type sulfoacid gemini surfactant
(C).Synthetic route of the present invention is as follows:
In preparation method of the present invention, by perfluorinated nonene and perfluor hexene, prepare key intermediate perfluoro alkene oxygen base chlorobenzoyl chloride
(A)technique open in the literature.Such as US Patent No. 4788321, Shi Hongxin etc. (fine chemistry industry 2009,26(3), 239-242,247).
Amidation process in preparation method of the present invention, due to perfluoro alkene oxygen base chlorobenzoyl chloride
(A)more vivaciously be easy to decompose, therefore prepare
(A)without separation, direct and diamine compounds condensation makes perfluoro alkene oxygen yl-benzamide
(B).The hydrogen chloride that reaction produces is generally by adding tertiary amine acid binding agent to neutralize as triethylamine, pyridine etc., also can select sodium carbonate, potash, sodium acid carbonate, saleratus, tetraethylethylenediamine etc. is acid binding agent, boiling point is compared with low and be solvent to the ketone of this reactionlessness, ethers, nitrile, amide-type, sulfoxide type etc., as butanone, acetonitrile, oxolane, DMF and dimethyl sulfoxide (DMSO).
Final step reaction in preparation method of the present invention, by perfluoro alkene oxygen yl-benzamide intermediate (B) and vinyl sulfonic acid sodium, chloroethyl sodium sulfonate, bromoethyl sodium sulfonate or 1, the sulfoalkylation reaction of 3-propane sultone, nucleophilic addition, nucleophilic displacement of fluorine or nucleophilic displacement of fluorine open loop under acid binding agent exists are carried out.Reaction preferred water and with the miscible organic solvent of water be mixed solvent, sodium carbonate, potash, sodium acid carbonate, saleratus, triethylamine etc. are made alkali.The preferably strong polar aprotic solvent of organic solvent, as DMF, acetonitrile, oxolane etc.Also can be by using phase transfer catalyst to promote the carrying out of reaction.Cation in final surfactant can and obtain through ion-exchange by acid binding agent or alkali selected in selected raw material, reaction.
The compound with formula (C) of gained of the present invention, characterizes through the detection means such as infrared spectrum, mass spectrum, elementary analysis, the raw materials used and reaction condition of association reaction etc., with shown in structure conform to.The surface property of product also shows that they have the feature of Shuangzi structure.
The prepared sulfonic acid type anionic of the present invention Shuangzi fluorine surfactant has high surface, adds on a small quantity and can significantly reduce surface tension.Product can improve decontamination and washability, has excellent dispersiveness etc., can be used for fabric post-treatment, washing agent, tertiary oil production in oil field etc.
The specific embodiment
For the present invention is further illustrated, below in conjunction with specific embodiment, be illustrated.
embodiment 1 perfluorinated nonene oxygen base chlorobenzoyl chloride and 3-oxa--1, intermediate (B) is prepared in the condensation of 5-pentanediamine
The perfluorinated nonene oxygen base chlorobenzoyl chloride that 11.47g (20.2mmol) perfluorinated nonene p-methoxybenzoic acid obtains through thionyl chloride chlorination is dissolved in acetonitrile 30mL, splash into 3-oxa--1, the mixed liquor of 5-pentanediamine 1.04g (10.0mmol), triethylamine 2.07g (20.5mmol) and acetonitrile 30mL, 50 ℃ of insulation reaction 8h, decompression and solvent recovery, adds water and stirs, filter, washing, vacuum drying obtains faint yellow solid 11.4g, yield 94.5%.
embodiment 2 N, N '-bis-(perfluorinated nonene oxygen base benzoyl)-3-oxa--1, fluorine surfactant is prepared in 5-pentanediamine and the condensation of 1,3-propane sultone
Get embodiment 1 products therefrom 6.02g (5.0mmol), 1,3-propane sultone 1.34g (11.0mmol), DMF 10mL and water 20mL mix, and add potassium hydroxide to regulate pH to 10,60 ℃ of reaction 22h.Cooling, filter, washing, vacuum drying obtains amber solid product 7.1g, yield 93.4%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1643(C=O), 1596(phenyl ring C=C), 1493(phenyl ring C=C), 1243(S=O), 1235(aryl-O), 1185(C-F), 1134(C-F), 1129(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
42h
28f
34k
2n
2o
11s
2theoretical value C 33.07%, and H 1.84%, and F 42.39%; Measured value C 32.90%, H 1.74%, and F 42.18%.Mass spectrum: molecular weight 1524.
intermediate (B) is prepared in embodiment 3 perfluor hexene oxygen base chlorobenzoyl chlorides and Putriscine condensation
In perfluor hexene oxygen base chlorobenzoyl chloride, Anhydrous potassium carbonate 2.79g (20.2mmol) and the oxolane 40mL obtaining through thionyl chloride chlorination to 8.44g (20.2mmol) perfluor hexene p-methoxybenzoic acid, splash into 1, the mixed liquor of 4-butanediamine 0.88g (10.0mmol) and oxolane 30mL, back flow reaction 8h, decompression and solvent recovery, add water and stir, filter, washing, vacuum drying obtains faint yellow solid 7.9g, yield 88.9%.
embodiment 4 N, fluorine surfactant is prepared in N '-bis-(perfluor hexene oxygen base benzoyl)-Putriscine and the condensation of vinyl sulfonic acid sodium
Get embodiment 3 products therefrom 4.44g (5.0mmol), vinyl sulfonic acid sodium 1.43g (11.0mmol), acetonitrile 20mL and water 20mL and mix, add NaOH to regulate pH to 10,60 ℃ of reaction 22h.Cooling, filter, washing, vacuum drying obtains amber solid product 5.2g, yield 90.6%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1644(C=O), 1600(phenyl ring C=C), 1495(phenyl ring C=C), 1244(S=O), 1233(aryl-O), 1185(C-F), 1133(C-F), 1128(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
34h
24f
22n
2na
2o
10s
2theoretical value C 35.54%, and H 2.09%, and F 36.41%; Measured value C 35.38%, H 2.00%, and F 36.26%.Mass spectrum: molecular weight 1148.
intermediate (B) is prepared in embodiment 5 perfluorinated nonene oxygen base chlorobenzoyl chlorides and the condensation of 1,5-pentanediamine
The perfluorinated nonene oxygen base chlorobenzoyl chloride that 11.47g (20.2mmol) perfluorinated nonene p-methoxybenzoic acid obtains through thionyl chloride chlorination is dissolved in acetonitrile 30mL, splash into 1, the mixed liquor of 5-pentanediamine 1.02g (10.0mmol), triethylamine 2.07g (20.5mmol) and acetonitrile 30mL, 50 ℃ of insulation reaction 8h, decompression and solvent recovery, adds water and stirs, filter, washing, vacuum drying obtains faint yellow solid 11.0g, yield 91.6%.
embodiment 6 N, N '-bis-(perfluorinated nonene oxygen base benzoyl)-1, fluorine surfactant is prepared in 5-pentanediamine and the condensation of bromoethyl sodium sulfonate
Get embodiment 5 products therefrom 6.01g (5.0mmol), bromoethyl sodium sulfonate 3.16g (15.0mmol) and water 25mL, N, dinethylformamide 15mL mixes, add NaOH to regulate pH to 10,60 ℃ of reaction 16h, add NaOH and keep pH substantially constant in course of reaction.Cooling, filter, washing, vacuum drying obtains amber solid product 6.7g, yield 91.6%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1643(C=O), 1598(phenyl ring C=C), 1493(phenyl ring C=C), 1242(S=O), 1234(aryl-O), 1186(C-F), 1133(C-F), 1130(S=O), 1041(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
41h
26f
34n
2na
2o
10s
2theoretical value C 33.65%, and H 1.78%, and F 44.19%; Measured value C 33.48%, H 1.65%, and F 44.04%.Mass spectrum: molecular weight 1462.
intermediate (B) is prepared in embodiment 7 perfluorinated nonene oxygen base chlorobenzoyl chlorides and ethylenediamine condensation
The perfluorinated nonene oxygen base chlorobenzoyl chloride that 11.47g (20.2mmol) perfluorinated nonene p-methoxybenzoic acid obtains through thionyl chloride chlorination is dissolved in acetonitrile 30mL, splash into the mixed liquor of ethylenediamine 0.60g (10.0mmol), triethylamine 2.07g (20.5mmol) and acetonitrile 30mL, 60 ℃ of insulation reaction 12h, decompression and solvent recovery, add water and stir, filter, washing, vacuum drying obtains faint yellow solid 11.0g, yield 94.8%.
embodiment 8 N, fluorine surfactant is prepared in N '-bis-(perfluorinated nonene oxygen base benzoyl) ethylenediamine and the condensation of chloroethyl sodium sulfonate
Getting embodiment 7 products therefrom 5.80g (5.0mmol), chloroethyl sodium sulfonate 2.50g (15.0mmol) and water 25mL, dimethyl sulfoxide (DMSO) 10mL mixes, add NaOH to regulate pH to 10,60 ℃ of reaction 16h, add NaOH and keep pH substantially constant in course of reaction.Cooling, filter, washing, vacuum drying obtains amber solid product 6.6g, yield 92.9%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1644(C=O), 1598(phenyl ring C=C), 1494(phenyl ring C=C), 1241(S=O), 1235(aryl-O), 1185(C-F), 1132(C-F), 1128(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
38h
20f
34n
2na
2o
10s
2theoretical value C 32.11%, and H 1.41%, and F 45.49%; Measured value C 31.98%, H 1.35%, and F 45.34%.Mass spectrum: molecular weight 1420.
intermediate (B) is prepared in embodiment 9 perfluor hexene oxygen base chlorobenzoyl chlorides and the condensation of 1,3-propane diamine
In perfluor hexene oxygen base chlorobenzoyl chloride, Anhydrous potassium carbonate 2.79g (20.2mmol) and the oxolane 40mL obtaining through thionyl chloride chlorination to 8.44g (20.2mmol) perfluor hexene p-methoxybenzoic acid, splash into 1, the mixed liquor of 3-propane diamine 0.74g (10.0mmol) and oxolane 30mL, back flow reaction 8h, decompression and solvent recovery, add water and stir, filter, washing, vacuum drying obtains faint yellow solid 7.9g, yield 90.4%.
embodiment 10 N, N '-bis-(perfluor hexene oxygen base benzoyl)-1, fluorine surfactant is prepared in 3-propane diamine and the condensation of 1,3-propane sultone
Get embodiment 9 products therefrom 4.37g (5.0mmol), 1,3-propane sultone 1.34g (11.0mmol), DMF 15mL and water 20mL mix, and add potassium hydroxide to regulate pH to 10,60 ℃ of reaction 22h.Cooling, filter, washing, vacuum drying obtains amber solid product 5.4g, yield 91.3%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1643(C=O), 1598(phenyl ring C=C), 1493(phenyl ring C=C), 1242(S=O), 1234(aryl-O), 1186(C-F), 1133(C-F), 1130(S=O), 1041(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
35h
26f
22k
2n
2o
10s
2theoretical value C 35.18%, and H 2.18%, and F 35.01%; Measured value C 35.00%, H 2.05%, and F 34.89%.Mass spectrum: molecular weight 1194.
Above example chemical raw material used, solvent etc. are technical grade.Surface tension records by surface tension instrument, and critical micelle concentration is tried to achieve by measuring the relation curve of surface tension and concentration.Be below surface tension and the critical micelle concentration data of the part surface activating agent of synthesized of the present invention.
| Compound | n, M | R f, R | Minimum surface is opened (mN/m) | Critical micelle concentration (mol/L) |
| 1 | 2, Na | C 6F 11, (CH 2) 2 | 20.0 | 4.2x10 -4 |
| 2 | 3, K | C 6F 11, (CH 2) 2 | 19.9 | 2.6x10 -4 |
| 3(embodiment 10 preparations) | 3, K | C 6F 11, (CH 2) 3 | 18.3 | 2.5x10 -4 |
| 4 | 2, Na | C 6F 11, (CH 2) 3 | 19.0 | 2.2x10 -4 |
| 5(embodiment 4 preparations) | 2, Na | C 6F 11, (CH 2) 4 | 20.2 | 1.2x10 -4 |
| 6 | 3, K | C 6F 11, (CH 2) 4 | 20.4 | 1.0x10 -4 |
| 7 | 3, Na | C 6F 11, (CH 2) 5 | 20.6 | 3.6x10 -4 |
| 8 | 2, K | C 6F 11, (CH 2) 5 | 21.0 | 4.4x10 -4 |
| 9 | 2, K | C 6F 11, (CH 2) 2O(CH 2) 2 | 20.6 | 3.2x10 -5 |
| 10 | 3, Na | C 6F 11, (CH 2) 2O(CH 2) 2 | 20.4 | 3.2x10 -4 |
| 11 | 3, K | C 9F 17, (CH 2) 2 | 16.6 | 8.8x10 -5 |
| 12(embodiment 8 preparations) | 2, Na | C 9F 17, (CH 2) 2 | 16.2 | 8.2x10 -5 |
| 13 | 2, K | C 9F 17, (CH 2) 3 | 16.2 | 6.0x10 -5 |
| 14 | 3, Na | C 9F 17, (CH 2) 3 | 15.8 | 6.2x10 -5 |
| 15 | 3, K | C 9F 17, (CH 2) 3 | 16.4 | 6.2x10 -5 |
| 16 | 2, Na | C 9F 17, (CH 2) 4 | 16.6 | 6.8x10 -5 |
| 17 | 3, K | C 9F 17, (CH 2) 4 | 17.2 | 7.7x10 -5 |
| 18(embodiment 6 preparations) | 2, Na | C 9F 17, (CH 2) 5 | 18.8 | 1.2x10 -4 |
| 19 | 3, K | C 9F 17, (CH 2) 5 | 19.6 | 1.3x10 -4 |
| 20(embodiment 2 preparations) | 3, K | C 9F 17, (CH 2) 2O(CH 2) 2 | 17.8 | 9.0x10 -5 |
| 21 | 2, Na | C 9F 17, (CH 2) 2O(CH 2) 2 | 18.2 | 9.4x10 -5 |
The lowest surface tension of all compounds prepared by the present invention all below 21.0mN/m, minimum only 15.8mN/m, close with the lowest surface tension (≤16.0mN/m) of PFOA and PFOS analog derivative.Comparatively speaking, similar structures but non-double type kind as the lowest surface tension of N-methyl perfluorinated nonene oxygen base benzene sulfonamido SES be 23.1mN/m, the lowest surface tension of N-methyl perfluorinated nonene oxygen base benzene sulfonamido sodium acetate is 22.8mN/m etc.Visible, by the Shuangzi of perfluor alkene type surfactant, can effectively improve surface-active.
The technical staff of the industry should be appreciated that, the present invention is not restricted to the described embodiments, in above-described embodiment and description, describe just for principle of the present invention is described.Without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these all fall in the scope of protection of present invention.
Claims (4)
1. a class perfluor alkene type anion Gemini surface active agent, general formula is
Compound, R wherein
ffor perfluorinated nonene base or perfluor hexenyl, n be 2 or 3, M be sodium or potassium, R is (CH
2)
2or (CH
2)
3or (CH
2)
4or (CH
2)
5or (CH
2)
2o (CH
2)
2; It is oleophilic moiety that these compounds be take perfluorinated nonene oxygen base phenyl or perfluor hexene oxygen base phenyl, take sodium sulfonate or potassium sulfonate as hydrophilic segment, between two surfactants with methene chain (CH
2)
2or (CH
2)
3or (CH
2)
4or (CH
2)
5or 3-oxa-pentylidene chain-(CH
2)
2o (CH
2)
2-for connecting bridge, oleophilic moiety is connected by amido link with hydrophilic segment.
2. prepare the method for perfluor alkene type anion Gemini surface active agent as claimed in claim 1 for one kind, it is characterized in that: take perfluorinated nonene or perfluor hexene is raw material, with P-hydroxybenzoic acid condensation, chlorination makes perfluoro alkene oxygen base chlorobenzoyl chloride, direct and the ethylenediamine without separation, 1, 3-propane diamine, 1, 4-butanediamine, 1, 5-pentanediamine, 3-oxa--1, the condensation of 5-pentanediamine obtains corresponding perfluoro alkene oxygen yl-benzamide, again with vinyl sulfonic acid sodium, chloroethyl sodium sulfonate, bromoethyl sodium sulfonate or 1, the condensation of 3-propane sultone obtains a class perfluor alkene type anion Gemini surface active agent.
3. the preparation method of perfluor alkene type anion Gemini surface active agent as claimed in claim 2, it is characterized in that: perfluoro alkene oxygen yl-benzamide and vinyl sulfonic acid sodium, chloroethyl sodium sulfonate, bromoethyl sodium sulfonate or 1, the sulfoalkylation reaction of 3-propane sultone condensation is that nucleophilic addition, nucleophilic displacement of fluorine or the nucleophilic ring opening under acid binding agent exists carries out.
4. the preparation method of perfluor alkene type anion Gemini surface active agent as claimed in claim 3, it is characterized in that: the solvent that sulfoalkylation reacts used is water and N, any one mixture in dinethylformamide, acetonitrile, oxolane, makes alkali with sodium carbonate, potash, sodium acid carbonate, saleratus, triethylamine etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310662220.6A CN103657512B (en) | 2013-12-10 | 2013-12-10 | One class perfluor ene-type anionic gemini surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310662220.6A CN103657512B (en) | 2013-12-10 | 2013-12-10 | One class perfluor ene-type anionic gemini surfactant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103657512A true CN103657512A (en) | 2014-03-26 |
| CN103657512B CN103657512B (en) | 2016-08-31 |
Family
ID=50297002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310662220.6A Expired - Fee Related CN103657512B (en) | 2013-12-10 | 2013-12-10 | One class perfluor ene-type anionic gemini surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103657512B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173869A (en) * | 2021-04-19 | 2021-07-27 | 三明学院 | Preparation method of fluorosulfonate-containing gemini surfactant |
| CN113684014A (en) * | 2021-09-23 | 2021-11-23 | 扬州润达油田化学剂有限公司 | Fluorocarbon gemini anti-oil-foam discharging agent and preparation method thereof |
| CN114634818A (en) * | 2022-03-21 | 2022-06-17 | 福州大学 | Benzyl Gemini surfactant and preparation method thereof |
| TWI768009B (en) * | 2017-03-21 | 2022-06-21 | 美商3M新設資產公司 | Heat transfer fluids and methods of using same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129508A (en) * | 1997-07-08 | 1999-02-02 | Neos Co Ltd | Electrically sensitive compound, electrically sensitive composition and use thereof |
| WO2000058277A1 (en) * | 1999-03-31 | 2000-10-05 | American Home Products Corporation | Aryl sulfonic acids and derivatives as fsh antagonists |
| CN101293853A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Cation fluorine surfactant and preparation method thereof |
| CN102872751A (en) * | 2012-09-12 | 2013-01-16 | 衢州学院 | Sulfonic acid dimeric surfactant based on perfluoroolefine and preparation method thereof |
| CN102908937A (en) * | 2012-09-12 | 2013-02-06 | 衢州学院 | Cationic type gemini fluorinated surfactant based on perfluorinated nonene and perfluorinated hexene and preparation method of cationic type gemini fluorinated surfactant |
| CN102921345A (en) * | 2012-10-11 | 2013-02-13 | 浙江工业大学 | Preparation method and application of novel branch-type fluorine-contained quaternary ammonium salt cationic surfactant |
-
2013
- 2013-12-10 CN CN201310662220.6A patent/CN103657512B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129508A (en) * | 1997-07-08 | 1999-02-02 | Neos Co Ltd | Electrically sensitive compound, electrically sensitive composition and use thereof |
| WO2000058277A1 (en) * | 1999-03-31 | 2000-10-05 | American Home Products Corporation | Aryl sulfonic acids and derivatives as fsh antagonists |
| CN101293853A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Cation fluorine surfactant and preparation method thereof |
| CN102872751A (en) * | 2012-09-12 | 2013-01-16 | 衢州学院 | Sulfonic acid dimeric surfactant based on perfluoroolefine and preparation method thereof |
| CN102908937A (en) * | 2012-09-12 | 2013-02-06 | 衢州学院 | Cationic type gemini fluorinated surfactant based on perfluorinated nonene and perfluorinated hexene and preparation method of cationic type gemini fluorinated surfactant |
| CN102921345A (en) * | 2012-10-11 | 2013-02-13 | 浙江工业大学 | Preparation method and application of novel branch-type fluorine-contained quaternary ammonium salt cationic surfactant |
Non-Patent Citations (1)
| Title |
|---|
| 新华书店北京发行所: "《化工辞典》", 31 August 1969, article "酰基", pages: 533 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI768009B (en) * | 2017-03-21 | 2022-06-21 | 美商3M新設資產公司 | Heat transfer fluids and methods of using same |
| CN113173869A (en) * | 2021-04-19 | 2021-07-27 | 三明学院 | Preparation method of fluorosulfonate-containing gemini surfactant |
| CN113684014A (en) * | 2021-09-23 | 2021-11-23 | 扬州润达油田化学剂有限公司 | Fluorocarbon gemini anti-oil-foam discharging agent and preparation method thereof |
| CN114634818A (en) * | 2022-03-21 | 2022-06-17 | 福州大学 | Benzyl Gemini surfactant and preparation method thereof |
| CN114634818B (en) * | 2022-03-21 | 2023-01-10 | 福州大学 | Benzyl Gemini surfactant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103657512B (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865511B (en) | viscoelastic surfactant fracturing fluid and preparation method and application thereof | |
| Cui et al. | Synthesis of didodecylmethylcarboxyl betaine and its application in surfactant–polymer flooding | |
| CN103111229B (en) | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof | |
| CN103657512A (en) | Perfluoroolefine type anionic gemini surfactant and preparation method thereof | |
| CN103113518B (en) | Drilling fluid tackifier and its preparation method | |
| CN102389745A (en) | Preparation method of fluorine-containing double-type cationic surfactant and use thereof | |
| EP3331963B1 (en) | Mixed dimers from alpha-olefin sulfonic acids | |
| US11629283B2 (en) | N,N,N′,N′-tetradodecyl-substituted diphenyl ether sulfonate anionic Gemini surfactant and synthesis method thereof | |
| CN102908937B (en) | Based on the cationic Shuangzi fluorine surfactant and preparation method thereof of perfluorinated nonene and perfluor hexene | |
| CN102380330A (en) | Cathode-non-amphoteric ion type gemini surfactant and synthesis method | |
| CN105037176A (en) | Preparation method for quaternary ammonium salt dimeric surfactant containing hydroxyl group and application of quaternary ammonium salt dimeric surfactant containing hydroxyl group in tertiary oil recovery | |
| CN106362641A (en) | Dendritic polyamide-amine demulsifier and preparation method thereof | |
| CN105622406B (en) | Functionalization column [5] aromatic hydrocarbons trimer preparation method and application | |
| CN103831057A (en) | Fluorocarbon surface active agent and preparation method thereof | |
| CN105017097B (en) | Surfactant N carboxyethyls, the preparation method of 3 dimethylamino-propyl perfluoro hexyl sulfonamide of N | |
| CN102872751B (en) | Sulfonic acid dimeric surfactant based on perfluoroolefine and preparation method thereof | |
| CN102580610B (en) | Lignosulfonate alkylation modified surfactant and preparation method and application thereof | |
| CN102921345A (en) | Preparation method and application of novel branch-type fluorine-contained quaternary ammonium salt cationic surfactant | |
| CN104190314A (en) | Fatty amine polyoxyethylene ether diethyl disulfonate surfactant and preparation method thereof | |
| CN102924345A (en) | Preparation method and application of branched fluorine-containing cationic surfactant | |
| CN102993058A (en) | Preparation method and application of fluorine-containing benzamido sulfate anionic surfactant | |
| CN110746955B (en) | Gemini surfactant for oil displacement, binary composite system, preparation method and application thereof | |
| CN103657513B (en) | Gemini-type ampholytic surfactant based on perfluoroolefine and preparation method thereof | |
| CN102976981A (en) | Preparation method and application of fluorine-containing quaternary ammonium salt type cationic surfactant | |
| CN103816835A (en) | Sulfopropyl betaine type zwitterions fluorocarbon Gemini surfactant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160831 Termination date: 20201210 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |