CN103127877A - Fluorine-containing surfactant and preparation method thereof - Google Patents

Fluorine-containing surfactant and preparation method thereof Download PDF

Info

Publication number
CN103127877A
CN103127877A CN2013100705455A CN201310070545A CN103127877A CN 103127877 A CN103127877 A CN 103127877A CN 2013100705455 A CN2013100705455 A CN 2013100705455A CN 201310070545 A CN201310070545 A CN 201310070545A CN 103127877 A CN103127877 A CN 103127877A
Authority
CN
China
Prior art keywords
chf
coo
fluorine
containing surfactant
partially
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
Application number
CN2013100705455A
Other languages
Chinese (zh)
Other versions
CN103127877B (en
Inventor
夏俊
魏文涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
Original Assignee
Shandong Dongyue Polymer Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong Dongyue Polymer Material Co Ltd filed Critical Shandong Dongyue Polymer Material Co Ltd
Priority to CN201310070545.5A priority Critical patent/CN103127877B/en
Publication of CN103127877A publication Critical patent/CN103127877A/en
Application granted granted Critical
Publication of CN103127877B publication Critical patent/CN103127877B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a fluorine-containing surfactant and a preparation method thereof. The fluorine-containing surfactant has the following formula: [Rf-(O)m-CHF-Rf'-COO]nAn+, wherein Rf refers to partially or completely fluorinated linear or branched alkyl, or partially or completely fluorinated linear or branched alkyl with 1-6 inserted ether oxygen atoms; m refers to 0 or 1; Rf' refers to partially or completely fluorinated linear or branched alkyl with a main chain containing more than two carbon atoms; and An+ refers to n-valence cation, wherein n is 1, 2 or 3. The preparation method of the fluorine-containing surfactant provided by the invention is simple and is low in cost; and the prepared fluorine-containing surfactant has high surface activity, and has a wide application prospect.

Description

A kind of fluorine-containing surfactant and preparation method thereof
Technical field
The present invention relates to a kind of fluorine-containing surfactant and preparation method thereof, belong to the fluorine chemical technical field.
Background technology
Fluorine-containing surfactant is most important kind in special surfactant, and its special performance often is summarized as " three height ", " two hate ", i.e. high surface, high heat-resistant stability and high chemical stability.Fluorine-containing surfactant is widely used in all conglomeraties such as synthetic detergent, cosmetics, food, rubber, plastics, printing ink.In addition, fluorine-containing surfactant can also as additive, the easer of fire-extinguishing chemical, be used for oil exploitation, textile printing and dyeing, the processing of paper leather, environment-protection pesticide, synthetic resin, high-grade paint.
In the production process of fluoropolymer, fluorine-containing surfactant usually uses as dispersant, all can use fluorine-containing surfactant in the dispersin polymerization system such as the various monomer homopolymerizations such as tetrafluoroethene, vinylidene, trifluoro-ethylene, hexafluoropropene, CTFE, perfluoroalkyl vinyl ether and copolymerization.
The fluorine-containing surfactant that dispersion method production fluoropolymer polymer field is most widely used is perfluoro caprylic acid, i.e. C 7F 15COOH and derivative thereof, or be called " C8 ", be a kind of artificial synthesizing but not the naturally occurring raw material of industry.The molecular structure of PFOA also has been doomed its persistence and cumulative bad in environment when giving its excellent surface properties.Because contain full-fluorine group in the PFOA molecule, and interconnective carbochain is long, finally causes PFOA to have strong heat endurance and dynamic stability, has increased the persistence of PFOA molecule in environment.Show after deliberation, PFOA is standing under heat-flash, illumination, chemical action, microbial action and high vertebrate metabolism all to be difficult to degraded, and PFOA is one of organic pollution of the difficult degradation found in the world at present.At present some developed countries and non-government organization pay close attention to the harm that environment and health may cause PFOA as focus.
At present domestic and international many fluorine chemical manufacturer is all in the substitute of active development PFOA, and carried out extensive work.For example: morning twilight chemical research institute is at Chinese patent literature CN101648122A(application number 200910092202.2) in mention and adopt Fluorine containing olefine to be contained at low temperatures the surfactant of ether segment by the dioxygen oxidation preparation, the surfactant that this method obtains contains a large amount of side chains, and is dispersed bad in polymerization process.Hugeization group is at Chinese patent literature CN102504063A(application number 201110338501) in adopt the surfactant of the fluorine-containing ether segment of chloride atom, but the toxicity of this surfactant is larger, can not satisfy eco-friendly requirement fully.United States Patent (USP) 5789508,4025709, the surfactant that 5688884,5763552 grades are mentioned due to the relation of molecular structure, can affect the product quality of polymer in polymerization process.
Search out a kind of suitable substitute of perfluoro caprylic acid, this substitute should possess raw material and be easy to get, and synthetic route is simple, safety, cost are low, and has the characteristics of good dispersive property and stability, becomes the focus of present research.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of fluorine-containing surfactant and preparation method thereof is provided, the substitute that this fluorine-containing surfactant can be used as perfluoro caprylic acid is used for the process that dispersion method is produced fluoropolymer.
A kind of fluorine-containing surfactant, described fluorine-containing surfactant has following general formula:
[Rf-(O) m-CHF-Rf’-COO] nA n+
Wherein, straight chain or the branched alkyl of Rf for partially or completely fluoridizing perhaps, inserts the straight chain of partially or completely fluoridizing or the branched alkyl of 1～6 ether oxygens atom; M is 0 or 1; Rf ' is for partially or completely fluoridizing, and main chain contains two carbon atoms above straight chain or branched alkyl; A n+The cation of expression n valency, n is 1,2 or 3.
Preferred according to the present invention, described partially fluorinated non-fluorine atom is H, Cl, Br atom.
Preferred according to the present invention, Rf is the backbone c atoms number less than the partially fluorinated or fluoridized alkyl of 8, and perhaps, Rf is for containing ether oxygen atom, and the alkyl that connects of ether oxygen atom two ends is carbon number less than the partially fluorinated or fluoridized alkyl of 8 arbitrarily.
Further preferred according to the present invention, described fluorine-containing surfactant general formula is as follows:
[CF 3-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF(CF 3)-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF(CF 3)-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF 2-O-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-O-CF 2-O-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-CF 2-O-CHF-CF2-CF2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF(CF 3)-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF(CF 3)-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF(CF 3)-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+。
Preferred according to the present invention, described A n+Be H +, Li +, K +, Na +Or NH 4 +Cation.
The preparation method of above-mentioned fluorine-containing surfactant, step is as follows:
get and contain fluoroalkyl vinyl ether and fluorine-containing iodo acid esters 1:(0.1～10 in molar ratio) ratio mix, add copper powder, the mol ratio that contains fluoroalkyl vinyl ether and copper powder is 1:(0.005～1), in confined conditions, be warming up to 50～200 ℃, reacted 4～20 hours, cold filtration, obtain containing the addition compound product of fluoroalkyl vinyl ether and fluorine-containing iodo acid esters after filtrate rectifying, the addition compound product that makes is joined in tributyl hydrogen tin, addition compound product and tributyl hydrogen tin mol ratio are 1:(0.1～10), 20～100 ℃ of reactions 2～4 hours, after rectification and purification, add NaOH, stirring reaction is 1～2 hour under 20～80 ℃ of conditions, then transfer pH to 0.5～1.5, after layering, get oil phase, through cleaning, after drying, and get final product.
Preferred according to the present invention, described rectifying pressure is 0.1kPa～100kPa.
Beneficial effect
The preparation method of fluorine-containing surfactant of the present invention is simple, cost is low, and the surface-active of the fluorine-containing surfactant that makes is high, is with a wide range of applications.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further elaborated, but the protection domain that the present invention protects is not limited to this.
The raw material explanation
CF 3-O-CF=CF 2(perfluoro methyl vinyl ether PMVE) is available from Shandong Huaxia Shenzhou New Material Co., Ltd.;
CF 3-CF 2-O-CF=CF 2(perfluoroethylvinyl ether PEVE) is available from Shandong Huaxia Shenzhou New Material Co., Ltd.;
CF 3-CF 2-CF 2-O-CF=CF 2(perfluoro propyl vinyl ether PPVE) is available from Shandong Huaxia Shenzhou New Material Co., Ltd.;
The difluoro ethyl iodoacetate is available from lark prestige Science and Technology Ltd.;
Tetrafluoro 2-iodopropionic acid ethyl ester is according to the 4th page of embodiment 4(EXAMPLE4 of specification in European patent EP 0842160) middle preparation method's preparation of putting down in writing;
Tri-butyl tin hydride is available from the triumphant auspicious chemical Science and Technology Ltd. in Changzhou.
Embodiment 1:CF 3-O-CHF-CF 2-CF 2The preparation of-COOH
In the stainless steel cauldron of 1L, add CF 3-O-CF=CF 2Compound 170g, difluoro ethyl iodoacetate 250g, copper powder 4g.After the reactor sealing, stir, be warmed up to 140 ℃ of afterreactions 8 hours.Cooling reactor is to room temperature, and after still internal reaction thing was filtered, filtrate obtained CF after 10kPa rectifying 3-O-CFI-CF 2-CF 2-COOC 2H 5Amount to 262.3g.Get 100gCF 3-O-CFI-CF 2-CF 2-COOC 2H 5Slowly join in 70g tributyl hydrogen tin, control reaction temperature 30～50 ℃ of reactions 3 hours, obtaining CF after rectification and purification under the 10kPa condition 3-O-CFH-CF 2-CF 2-COOC 2H 5Be total to 61.4g.With CF 3-O-CFH-CF 2-CF 2-COOC 2H 5Mix with the sodium hydrate aqueous solution of 1L20%, stirred 1 hour under 50 ℃.Adding the salt acid for adjusting pH value is 1, is divided into oil phase and water after system layering, gets oil phase through cleaning, drying, obtains target product 46.8g.
Product is tested through infrared spectrometer: at 970cm -1The vicinity has-the C-O-C-characteristic absorption, at 2370cm -1Near have-CF 2-characteristic absorption is at 1000～1300cm -1The continuous characteristic absorption of a plurality of CF keys appears, at 1807cm -1The place has-the COOH characteristic absorption peak.By H atom chemistry displacement 5.18 in 1H NMR detection-CHF-.
Product is tested through elementary analysis:
? C H F O
Theoretical value (%) 22.90 0.76 58.02 18.32
Actual value (%) 22.95 0.78 57.98 18.29
It is 22.7mN/m according to its surface tension of ASTMD971 standard test that product is configured to ammonium salt solution.
Embodiment 2:CF 3-CF 2-O-CHF-CF 2-CF 2The preparation of-COOH
In the stainless steel cauldron of 1L, add CF 3-CF 2-O-CF=CF 2Compound 172g, difluoro ethyl iodoacetate 200g, copper powder 2.5g.After the reactor sealing, stir, be warmed up to 142 ℃ of afterreactions 8.5 hours.Cooling reactor is to room temperature, and after still internal reaction thing was filtered, filtrate obtained CF after 2kPa rectifying 3-CF 2-O-CFI-CF 2-CF 2-COOC 2H 5Amount to 219.6g.Get 100g CF 3-CF 2-O-CFI-CF 2-CF 2-COOC 2H 5Slowly join in 65g tributyl hydrogen tin, control reaction temperature 25～55 ℃ of reactions 4 hours, obtaining CF after rectification and purification under the 2kPa condition 3-CF 2-O-CFH-CF 2-CF 2-COOC 2H 5Be total to 55.5g.With CF 3-CF 2-O-CFH-CF 2-CF 2-COOC 2H 5Mix with the sodium hydrate aqueous solution of 1L20%, stirred 1 hour under 50 ℃.Adding the salt acid for adjusting pH value is 1, is divided into oil phase and water after system layering, gets oil phase through cleaning, drying, obtains target product 35.7g.
Product is tested through infrared spectrometer: at 968cm -1The vicinity has-the C-O-C-characteristic absorption, at 2373cm -1Near have-CF 2-characteristic absorption is at 1000～1300cm -1The continuous characteristic absorption of a plurality of CF keys appears, at 1805cm -1The place has-the COOH characteristic absorption peak.By H atom chemistry displacement 5.17 in 1H NMR detection-CHF-.
Product is tested through elementary analysis:
? C H F O
Theoretical value (%) 23.08 0.64 60.90 15.39
Actual value (%) 23.04 0.67 60.88 15.41
It is 19.3mN/m according to its surface tension of ASTMD971 standard test that product is configured to ammonium salt solution.
Embodiment 3:CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2The preparation of-COOH
In the stainless steel cauldron of 1L, add CF 3-CF 2-CF 2-O-CF=CF 2Compound 180g, difluoro ethyl iodoacetate 170g, copper powder 5g.After the reactor sealing, open and stir, be warmed up to 155 ℃ of afterreactions 9 hours.Cooling reactor is to room temperature, and after still internal reaction thing was filtered, filtrate obtained CF after 0.5kPa rectifying 3-CF 2-CF 2-O-CFI-CF 2-CF 2-COOC 2H 5Amount to 279.6g.Get 100g CF 3-CF 2-CF 2-O-CFI-CF 2-CF 2-COOC 2H 5Slowly join in 56g tributyl hydrogen tin, control reaction temperature 35～50 ℃ of reactions 4 hours, obtaining CF after rectification and purification under the 0.5kPa condition 3-CF 2-CF 2-O-CFH-CF 2-CF 2-COOC 2H 5Be total to 63.5g.With CF 3-CF 2-CF 2-O-CFH-CF 2-CF 2-COOC 2H 5Mix with the sodium hydrate aqueous solution of 1L20%, stirred 1 hour under 48 ℃.Adding the salt acid for adjusting pH value is 1.Be divided into oil phase and water after system layering, get oil phase and obtain target product 47.4g through cleaning, drying.
Product is tested through infrared spectrometer: at 970cm -1The vicinity has-the C-O-C-characteristic absorption, at 2371cm -1Near have-CF 2-characteristic absorption is at 1000～1300cm -1The continuous characteristic absorption of a plurality of CF keys appears, at 1808cm -1The place has-the COOH characteristic absorption peak.By H atom chemistry displacement 5.17 in 1H NMR detection-CHF-.
Product is tested through elementary analysis:
? C H F O
Theoretical value (%) 23.20 0.55 62.98 13.26
Actual value (%) 23.22 0.57 62.95 13.26
It is 14.4mN/m according to its surface tension of ASTMD971 standard test that product is configured to ammonium salt solution.
Embodiment 4:CF 3-O-CHF-CF 2-CF 2-CF 2The preparation of-COOH
In the stainless steel cauldron of 1L, add CF 3-O-CF=CF 2Compound 168g, tetrafluoro 2-iodopropionic acid ethyl ester 300g, copper powder 4g.After the reactor sealing, stir, be warmed up to 140 ℃ of afterreactions 8 hours.Cooling reactor is to room temperature, and after still internal reaction thing was filtered, filtrate obtained CF after 3kPa rectifying 3-O-CFI-CF 2-CF 2-CF 2-COOC 2H 5Amount to 259.4g.Get 100gCF 3-O-CFI-CF 2-CF 2-CF 2-COOC 2H 5Slowly join in 63g tributyl hydrogen tin, control reaction temperature 30～60 ℃ of reactions 3 hours, obtaining CF after rectification and purification under the 3kPa condition 3-O-CHF-CF 2-CF 2-CF 2-COOC 2H 5Be total to 51.4g.With CF 3-O-CHF-CF 2-CF 2-CF 2-COOC 2H 5Mix with the sodium hydrate aqueous solution of 1L20%, stirred 1 hour under 50 ℃.Adding the salt acid for adjusting pH value is 1, is divided into oil phase and water after system layering, gets oil phase through cleaning, drying, obtains target product 34.9g.
Product is tested through infrared spectrometer: at 971cm -1The vicinity has-the C-O-C-characteristic absorption, at 2374cm -1Near have-CF 2-characteristic absorption is at 1000～1300cm -1The continuous characteristic absorption of a plurality of CF keys appears, at 1803cm -1The place has-the COOH characteristic absorption peak.By H atom chemistry displacement 5.16 in 1H NMR detection-CHF-.
Product is tested through elementary analysis:
? C H F O
Theoretical value (%) 23.08 0.64 60.90 15.39
Actual value (%) 23.07 0.63 60.94 15.36
It is 20.8mN/m according to its surface tension of ASTMD971 standard test that product is configured to ammonium salt solution.
Embodiment 5:CF 3-CF 2-O-CHF-CF 2-CF 2-CF 2The preparation of-COOH
In the stainless steel cauldron of 1L, add CF 3-CF 2-O-CF=CF 2Compound 200g, tetrafluoro 2-iodopropionic acid ethyl ester 280g, copper powder 6g.After the reactor sealing, open and stir, be warmed up to 138 ℃ of afterreactions 10 hours.Cooling reactor is to room temperature, and after still internal reaction thing was filtered, filtrate obtained CF after 0.4kPa rectifying 3-CF 2-O-CFI-CF 2-CF 2-CF 2-COOC 2H 5Amount to 323.5g.Get 100g CF 3-CF 2-O-CFI-CF 2-CF 2-CF 2-COOC 2H 5Slowly join in 58g tributyl hydrogen tin, control reaction temperature 40～60 ℃ of reactions 4 hours, obtaining CF after rectification and purification under the 0.4kPa condition 3-CF 2-O-CFH-CF 2-CF 2-CF 2-COOC 2H 5Be total to 52.7g.With CF 3-CF 2-O-CFH-CF 2-CF 2-CF 2-COOC 2H 5Mix with the sodium hydrate aqueous solution of 1L20%, stirred 2 hours under 55 ℃.Adding the salt acid for adjusting pH value is 1.Be divided into oil phase and water after system layering, get oil phase through cleaning, drying, obtain target product 35.1g.
Product is tested through infrared spectrometer: at 970cm -1The vicinity has-the C-O-C-characteristic absorption, at 2372cm -1Near have-CF 2-characteristic absorption is at 1000～1300cm -1The continuous characteristic absorption of a plurality of CF keys appears, at 1802cm -1The place has-the COOH characteristic absorption peak.By H atom chemistry displacement 5.15 in 1H NMR detection-CHF-.
Product is tested through elementary analysis:
? C H F O
Theoretical value (%) 23.20 0.55 62.98 13.26
Actual value (%) 23.19 0.56 62.96 13.28
It is 15.1mN/m according to its surface tension of ASTMD971 standard test that product is configured to ammonium salt solution.
Embodiment 6:CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2The preparation of-COOH
In the stainless steel cauldron of 1L, add CF 3-CF 2-CF 2-O-CF=CF 2Compound 185g, tetrafluoro 2-iodopropionic acid ethyl ester 210g, copper powder 4.5g.After the reactor sealing, open and stir, be warmed up to 158 ℃ of afterreactions 10 hours.Cooling reactor is to room temperature, and after still internal reaction thing was filtered, filtrate obtained CF after 0.1kPa rectifying 3-CF 2-CF 2-O-CFI-CF 2-CF 2-CF 2-COOC 2H 5Amount to 238.3g.Get 100gCF 3-CF 2-CF 2-O-CFI-CF 2-CF 2-CF 2-COOC 2H 5Slowly join in 52g tributyl hydrogen tin, control reaction temperature 35～60 ℃ of reactions 6 hours, obtaining CF after rectification and purification under the 0.1kPa condition 3-CF 2-CF 2-O-CFH-CF 2-CF 2-CF 2-COOC 2H 5Be total to 60.6g.With CF 3-CF 2-CF 2-O-CFH-CF 2-CF 2-CF 2-COOC 2H 5Mix with the sodium hydrate aqueous solution of 1L20%, stirred 1 hour under 55 ℃.Adding the salt acid for adjusting pH value is 1.Be divided into oil phase and water after system layering, get oil phase through cleaning, drying, obtain target product 48.8g.
Product is tested through infrared spectrometer: at 968cm -1The vicinity has-the C-O-C-characteristic absorption, at 2372cm -1Near have-CF 2-characteristic absorption is at 1000～1300cm -1The continuous characteristic absorption of a plurality of CF keys appears, at 1806cm -1The place has-the COOH characteristic absorption peak.By H atom chemistry displacement 5.14 in 1H NMR detection-CHF-.
Product is tested through elementary analysis:
? C H F O
Theoretical value (%) 23.30 0.49 64.56 11.65
Actual value (%) 23.32 0.50 64.55 11.63
It is 13.7mN/m according to its surface tension of ASTMD971 standard test that product is configured to ammonium salt solution.
Comparative Examples 1
According to Chinese patent CN101331105A(application number 200680047620.4) described in the preparation method prepare CF 3-CF 2-CF 2It is 22.9mN/m according to its surface tension of ASTMD971 standard test that-O-CHF-COOH, product are configured to ammonium salt solution.
Compare with embodiment 3, the product surface tension that Comparative Examples 1 makes is obviously higher, prepare in the process of fluoropolymer in dispersion method, embodiment 3 can reduce addition, reduce production costs, and less addition can make polymer particle reach dispersing morphology preferably, is conducive to following process.
Comparative Examples 2
According to Chinese patent CN101331105A(application number 200680047620.4) described in the preparation method prepare CF 3-CF 2-CF 2-O-CHF-CF 2It is 19.5mN/m according to its surface tension of ASTMD971 standard test that-COOH, product are configured to ammonium salt solution.
Compare with embodiment 6, the product surface tension that Comparative Examples 2 makes is higher, prepares in the process of fluoropolymer in dispersion method, embodiment 6 can reduce addition, reduce production costs, and less addition can make polymer particle reach dispersing morphology preferably, be conducive to following process.

Claims (7)

1. a fluorine-containing surfactant, is characterized in that, described fluorine-containing surfactant has following general formula:
[Rf-(O) m-CHF-Rf’-COO] nA n+
Wherein, straight chain or the branched alkyl of Rf for partially or completely fluoridizing perhaps, inserts the straight chain of partially or completely fluoridizing or the branched alkyl of 1～6 ether oxygens atom; M is 0 or 1; Rf ' is for partially or completely fluoridizing, and main chain contains two carbon atoms above straight chain or branched alkyl; A n+The cation of expression n valency, n is 1,2 or 3.
2. fluorine-containing surfactant as claimed in claim 1, it is characterized in that, Rf is the backbone c atoms number less than the partially fluorinated or fluoridized alkyl of 8, perhaps, Rf is for containing ether oxygen atom, and the alkyl that connects of ether oxygen atom two ends is carbon number less than the partially fluorinated or fluoridized alkyl of 8 arbitrarily.
3. fluorine-containing surfactant as claimed in claim 2, is characterized in that, described fluorine-containing surfactant general formula is as follows:
[CF 3-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF(CF 3)-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF(CF 3)-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF 2-O-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-O-CF 2-O-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-CF 2-O-CHF-CF2-CF2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF(CF 3)-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-COO] nA n+
[CF 3-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF(CF 3)-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-O-CF(CF 3)-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF(CF 3)-COO] nA n+
[CF 3-CF(CF 3)-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+
[CF 3-CF 2-CF 2-O-CF 2-CF 2-CF 2-O-CHF-CF 2-CF 2-CF 2-COO] nA n+。
4. fluorine-containing surfactant as described in claim 1～2 any one, is characterized in that, described partially fluorinated non-fluorine atom is H, Cl, Br atom.
5. fluorine-containing surfactant as described in claim 1～3 any one, is characterized in that, described A n+Be H +, Li +, K +, Na +Or NH 4 +Cation.
6. the preparation method of the described fluorine-containing surfactant of claim 1, is characterized in that, step is as follows:
get and contain fluoroalkyl vinyl ether and fluorine-containing iodo acid esters 1:(0.1～10 in molar ratio) ratio mix, add copper powder, the mol ratio that contains fluoroalkyl vinyl ether and copper powder is 1:(0.005～1), in confined conditions, be warming up to 50～200 ℃, reacted 4～20 hours, cold filtration, obtain containing the addition compound product of fluoroalkyl vinyl ether and fluorine-containing iodo acid esters after filtrate rectifying, the addition compound product that makes is joined in tributyl hydrogen tin, addition compound product and tributyl hydrogen tin mol ratio are 1:(0.1～10), 20～100 ℃ of reactions 2～4 hours, after rectification and purification, add NaOH, stirring reaction is 1～2 hour under 20～80 ℃ of conditions, then transfer pH to 0.5～1.5, after layering, get oil phase, through cleaning, after drying, and get final product.
7. preparation method as claimed in claim 6, is characterized in that, described rectifying pressure is 0.1kPa～100kPa.
CN201310070545.5A 2013-03-05 2013-03-05 A kind of fluorine-containing surfactant and preparation method thereof Active CN103127877B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310070545.5A CN103127877B (en) 2013-03-05 2013-03-05 A kind of fluorine-containing surfactant and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310070545.5A CN103127877B (en) 2013-03-05 2013-03-05 A kind of fluorine-containing surfactant and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103127877A true CN103127877A (en) 2013-06-05
CN103127877B CN103127877B (en) 2015-09-09

Family

ID=48488704

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310070545.5A Active CN103127877B (en) 2013-03-05 2013-03-05 A kind of fluorine-containing surfactant and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103127877B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2721284C2 (en) * 2015-12-30 2020-05-18 Нойборон Медтех Лтд. NEUTRON CAPTURE THERAPY SYSTEM FOR ELIMINATING AMYLOID β-PROTEIN

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070142541A1 (en) * 2005-12-21 2007-06-21 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US20090163653A1 (en) * 2006-08-31 2009-06-25 Asahi Glass Company, Limited Perfluorocarboxylic acid salt and process for producing it
WO2009157416A1 (en) * 2008-06-24 2009-12-30 旭硝子株式会社 Fluorine-containing compound purification method
US20100152379A1 (en) * 2006-11-09 2010-06-17 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using Polymerization Agent Comprising Fluoropolyether Acid or Salt and Short Chain Fluorosurfactant
JP2011503097A (en) * 2007-11-09 2011-01-27 デュポン パフォーマンス エラストマーズ エルエルシー Fluoroolefin monomers and copolymers thereof
CN102068937A (en) * 2011-01-14 2011-05-25 上海三爱富新材料股份有限公司 Method for preparing fluorocarbon surfactant
CN102145268A (en) * 2011-01-20 2011-08-10 上海三爱富新材料股份有限公司 Surfactant composition and application of surfactant composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070142541A1 (en) * 2005-12-21 2007-06-21 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US20090163653A1 (en) * 2006-08-31 2009-06-25 Asahi Glass Company, Limited Perfluorocarboxylic acid salt and process for producing it
US20100152379A1 (en) * 2006-11-09 2010-06-17 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using Polymerization Agent Comprising Fluoropolyether Acid or Salt and Short Chain Fluorosurfactant
JP2011503097A (en) * 2007-11-09 2011-01-27 デュポン パフォーマンス エラストマーズ エルエルシー Fluoroolefin monomers and copolymers thereof
WO2009157416A1 (en) * 2008-06-24 2009-12-30 旭硝子株式会社 Fluorine-containing compound purification method
CN102068937A (en) * 2011-01-14 2011-05-25 上海三爱富新材料股份有限公司 Method for preparing fluorocarbon surfactant
CN102145268A (en) * 2011-01-20 2011-08-10 上海三爱富新材料股份有限公司 Surfactant composition and application of surfactant composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2721284C2 (en) * 2015-12-30 2020-05-18 Нойборон Медтех Лтд. NEUTRON CAPTURE THERAPY SYSTEM FOR ELIMINATING AMYLOID β-PROTEIN

Also Published As

Publication number Publication date
CN103127877B (en) 2015-09-09

Similar Documents

Publication Publication Date Title
US7671112B2 (en) Method of making fluoropolymer dispersion
CN104370743B (en) The preparation method of plasticizer triethylene glycol two tricaprylates
CN101215225B (en) Method for producing perfluoroalkyl vinyl ether
CN103127877B (en) A kind of fluorine-containing surfactant and preparation method thereof
CN104803827B (en) One prepares 2 by ionic liquid-catalyzed ortho-chlorotolu'ene, the method for 6 – toluene dichloride
CN104861116A (en) Preparation method of fluorine-containing soap-free emulsion repellent
CN103145969A (en) Perfluorinated polyether diol and polyester-polyether segmented copolymer
CN103193904B (en) A kind of dispersion method prepares the method for fluoropolymer
CN106748713B (en) A method of the solid acid catalysis ester exchange reaction based on UIO-66 synthesizes (R) -2- chloropropionic acid
CN104231136A (en) Method for preparing fluorine-containing polymer by dispersion process
CN102068937A (en) Method for preparing fluorocarbon surfactant
CN104788608A (en) Fluorine-containing polymer for low-energy surface coating and preparation method of fluorine-containing polymer
CN101433813B (en) Hexafluoropropylene-based quaternary ammonium salt cationic surfactant, synthesizing method and use
CN104326862A (en) Preparation method of 2,4-dichloro-1,1,1-trifluorobutane derivative
CN102153473A (en) Method for preparing perfluor alkyl ethyl acrylate
CN108911947A (en) A kind of preparation method of the fluoro- 2- butylene of 1,1,1,2,4,4,4- seven
CN112374982B (en) Perfluorocarboxylic acid and preparation method thereof
CN105753661A (en) Polyether-type hydrofluoroether and preparation method thereof
CN110003003B (en) Fluorine-containing acrylate monomer and preparation method thereof
CN105439856A (en) Method for preparing didodecyl carbonate by taking oxometallate ion liquid as catalyst
CN104211840B (en) A kind of hypotoxicity emulsifying agent of fluoropolymer reaction and the preparation method of fluoropolymer
CN103025689A (en) Producing short chain perfluoroalkyl iodides
CN104861091B (en) Emulsifier for fluorine-containing polymerization reaction and preparation method of fluorine-containing polymer
CN103923243A (en) Rotatory polyacetylene infrared low-transmission material and preparation method thereof
CN104016848A (en) Preparation method of pentafluoropropionyl fluoride

Legal Events

Date Code Title Description
C06 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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201204

Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park

Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd

Address before: 256401 Shandong Dongyue Huantai high polymer material Co., Ltd., Tangshan County, Zibo, Shandong

Patentee before: SHANDONG DONGYUE POLYMER MATERIAL Co.,Ltd.