CN103073410A - Preparation method of fluoro-ether carboxylic acid surfactant - Google Patents
Preparation method of fluoro-ether carboxylic acid surfactant Download PDFInfo
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- CN103073410A CN103073410A CN2012105845715A CN201210584571A CN103073410A CN 103073410 A CN103073410 A CN 103073410A CN 2012105845715 A CN2012105845715 A CN 2012105845715A CN 201210584571 A CN201210584571 A CN 201210584571A CN 103073410 A CN103073410 A CN 103073410A
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Abstract
The invention discloses a preparation method of a fluoro-ether carboxylic acid surfactant. A fluorine-containing olefin monomer, oxygen and a molecular weight regulator are initiated to carry out the photochemical reaction by ultraviolet light to generate fluoro-ether acyl chloride and fluoro-ether acyl fluoride at the temperature of -40 to -80 DEG C, fluoro-ether acyl chloride and fluoro-ether acyl fluoride are hydrolyzed under the radiation of ultraviolet light to generate fluoro-ether carboxylic acid, and the fluoro-ether carboxylic acid is washed and purified to obtain a fluoro-ether carboxylic acid finished product. Through the adoption of the preparation method, the completely nontoxic fluoro-ether carboxylic acid surfactant can be produced, and can serve as a dispersing agent to completely replace perfluoro caprylic acid during the fluorine-containing polymer production process.
Description
Technical field
The present invention relates to a kind of preparation method of fluorine ether carboxylic acid surfactant.
Background technology
Perfluorocaprylic Acid has faced the destiny that bans use of as the good emulsifying agent of synthetic fluoropolymer after environment is caused severe contamination.But the application of the premium properties of fluoropolymer in national economy is but more and more extensive.Therefore, how finding the tensio-active agent that can replace Perfluorocaprylic Acid on performance is the urgent and difficult task of pendulum in face of us.The industry of expert call organic fluorine must be walked the road of cleaner production in Bo'ao forum in 2007, and the surrogate exploitation of PFOA is extremely urgent.Present known energy is used for the Zonyl-TBS(CF3CF2CF2CF2CF2CF2CH2CH2SO3 that E.I.Du Pont Company is arranged of fluoropolymer) and the tripolymer of perfluoro propene oxid sour, but Zonyl-TBS has chain transfer, can not synthesize the fluoropolymer of higher molecular weight and ultra-high molecular weight.And its raw material sources difficulty, there is the HCN generation of severe toxicity that the security of producing is brought very large challenge in the building-up process.The tripolymer acid that another fluorine surfactant that can be used for polymerization is the perfluor epoxy, structural formula is as follows: CF3CF2CF2OCF (CF3) CF2OCF (CF3) COOH, micelle-forming concentration and the surface tension of this tensio-active agent are lower than Perfluorocaprylic Acid, domestic three Ai Fu companies at first used in the polymerization of PFA, had also obtained good effect.But this tensio-active agent only reclaims the tripolymer of paying product in synthetic perfluor n-propyl vinyl ether synthetic just both economical.And the polymer particle that has the investigator to think that this tensio-active agent obtains when polymerizing tetrafluoroethylene is not spherical, impact for some machine-shaping properties.
Summary of the invention
The invention provides a kind of preparation method of fluorine ether carboxylic acid surfactant, it can produce the fluorine ether carboxylic acid surfactant of totally nontoxic, can be used as dispersion agent and replace Perfluorocaprylic Acid fully in fluoropolymer manufacture.
The present invention has adopted following technical scheme: a kind of preparation method's method of fluorine ether carboxylic acid surfactant, fluorinated olefin monomers and oxygen and molecular weight regulator are under-40～-80 ℃ temperature, cause photochmeical reaction through UV-light and generate fluorine ether acyl chlorides and fluorine ether acyl fluorides, fluorine ether acyl chlorides and fluorine ether acyl fluorides are hydrolyzed under UV-irradiation and generate fluorine ether carboxylic acid, obtain fluorine ether carboxylic acid finished product again behind the washing purifying.
Described fluorinated olefin monomers is tetrafluoroethylene monomer or R 1216 monomer.Described molecular weight regulator is trifluorochloroethylene.The pressure of described photochmeical reaction is normal pressure.Described ultraviolet light wavelength is at 300～500nm.Described ultraviolet light intensity is at 10～30Kw.The hydrolysis temperature of described fluorine ether acyl fluorides and fluorine ether acyl chlorides is at 70～150 ℃.The hydrolysis pressure of described fluorine ether acyl fluorides and fluorine ether acyl chlorides is normal pressure.
The present invention has following beneficial effect: the present invention uses the fluorine ether carboxylic acid surfactant of the photooxidation reaction production technique preparation of Fluorine containing olefine to contain Sauerstoffatom owing to this surfactant molecule chain inside, and the introducing of Sauerstoffatom helps the biological degradation of fluorine ether carboxylic acid surfactant, thereby can greatly eliminate residual in organism.
Embodiment
The invention provides a kind of preparation method of fluorine ether carboxylic acid surfactant, fluorinated olefin monomers and oxygen and molecular weight regulator are under-40～-80 ℃ temperature, cause photochmeical reaction through UV-light and generate fluorine ether acyl chlorides and fluorine ether acyl fluorides, the pressure of photochmeical reaction is normal pressure, the ultraviolet light wavelength is at 300～500nm, the ultraviolet light intensity is at 10～30Kw, fluorine ether acyl chlorides and fluorine ether acyl fluorides are hydrolyzed under UV-irradiation and generate fluorine ether carboxylic acid, the hydrolysis temperature of fluorine ether acyl fluorides and fluorine ether acyl chlorides is at 70～150 ℃, the hydrolysis pressure of fluorine ether acyl fluorides and fluorine ether acyl chlorides is normal pressure, behind the washing purifying, obtain fluorine ether carboxylic acid finished product again, fluorinated olefin monomers is tetrafluoroethylene monomer or R 1216 monomer, and molecular weight regulator is trifluorochloroethylene.
Below in conjunction with embodiment, to further detailed explanation of the present invention.
Embodiment 1:
Under the normal pressure, in-40 ℃ reactor, add R 1216 150Kg, open ultraviolet lamp, frequency transfers to 350nm, intensity is 15kw, open and stir, in reactor, pass into oxygen (flow is 12kg/h) and trifluorochloroethylene (flow is 5kg/h), react 3 hours afterreaction still materials and go out to medial launder rising temperature reclamation R 1216.In hydrolysis kettle, add pure water 200kg, open ultraviolet lamp, frequency transfers to 450nm, intensity is 25kw, open to stir, and reclaims material completely in the medial launder and adds in the hydrolysis kettle with the speed of 8kg/min, react stopped reaction after 3 hours, waste water in the hydrolysis kettle is discharged, then add the pure water washing of 100kg, obtain fluorine ether carboxylic acid sterling after washing three times.
Embodiment 2:
Under the normal pressure, in-30 ℃ reactor, add R 1216 450kg, open ultraviolet lamp, frequency transfers to 350nm, intensity is 20kw, open and stir, in reactor, pass into oxygen (flow is 12kg/h) and trifluorochloroethylene (flow is 5kg/h), react 3 hours afterreaction still materials and go out to medial launder rising temperature reclamation R 1216.In hydrolysis kettle, add pure water 200kg, open ultraviolet lamp, frequency transfers to 450nm, intensity is 25kw, open to stir, and reclaims material completely in the medial launder and adds in the hydrolysis kettle with the speed of 8kg/min, react stopped reaction after 3 hours, waste water in the hydrolysis kettle is discharged, then add the pure water washing of 100kg, obtain fluorine ether carboxylic acid sterling after washing three times.
Embodiment 3:
Under the normal pressure, in-78 ℃ reactor, add tetrafluoroethylene 400kg, open ultraviolet lamp, frequency transfers to 350nm, intensity is 10kw, open and stir, in reactor, pass into oxygen (flow is 12kg/h) and trifluorochloroethylene (flow is 5kg/h), react 3 hours afterreaction still materials and go out to medial launder rising temperature reclamation R 1216.In hydrolysis kettle, add pure water 200kg, open ultraviolet lamp, frequency transfers to 450nm, intensity is 25kw, open to stir, and reclaims material completely in the medial launder and adds in the hydrolysis kettle with the speed of 8kg/min, react stopped reaction after 3 hours, waste water in the hydrolysis kettle is discharged, then add the pure water washing of 100kg, obtain fluorine ether carboxylic acid sterling after washing three times.
Embodiment 4:
Under the normal pressure, in-80 ℃ reactor, add tetrafluoroethylene 500kg, open ultraviolet lamp, frequency transfers to 350nm, intensity is 15kw, open and stir, in reactor, pass into oxygen (flow is 12kg/h) and trifluorochloroethylene (flow is 5kg/h), react 3 hours afterreaction still materials and go out to medial launder rising temperature reclamation R 1216.In hydrolysis kettle, add pure water 200kg, open ultraviolet lamp, frequency transfers to 450nm, intensity is 25kw, open to stir, and reclaims material completely in the medial launder and adds in the hydrolysis kettle with the speed of 8kg/min, react stopped reaction after 3 hours, waste water in the hydrolysis kettle is discharged, then add the pure water washing of 100kg, obtain fluorine ether carboxylic acid sterling after washing three times.
Claims (8)
1. the preparation method of a fluorine ether carboxylic acid surfactant, it is characterized in that fluorinated olefin monomers and oxygen and molecular weight regulator are under-40～-80 ℃ temperature, cause photochmeical reaction through UV-light and generate fluorine ether acyl chlorides and fluorine ether acyl fluorides, fluorine ether acyl chlorides and fluorine ether acyl fluorides are hydrolyzed under UV-irradiation and generate fluorine ether carboxylic acid, obtain fluorine ether carboxylic acid finished product again behind the washing purifying.
2. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1 is characterized in that described fluorinated olefin monomers is tetrafluoroethylene monomer or R 1216 monomer.
3. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1 is characterized in that described molecular weight regulator is trifluorochloroethylene.
4. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1, the pressure that it is characterized in that described photochmeical reaction is normal pressure.
5. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1 is characterized in that described ultraviolet light wavelength is at 300～500nm.
6. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1 is characterized in that described ultraviolet light intensity is at 10～30Kw.
7. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1 is characterized in that the hydrolysis temperature of fluorine ether acyl fluorides and fluorine ether acyl chlorides is at 70～150 ℃.
8. the preparation method of fluorine ether carboxylic acid surfactant according to claim 1 is characterized in that the hydrolysis pressure of fluorine ether acyl fluorides and fluorine ether acyl chlorides is normal pressure.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148794A (en) * | 2015-09-30 | 2015-12-16 | 成都晨光博达橡塑有限公司 | Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid |
| CN105170017A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid |
| CN105170018A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant |
| CN105344289A (en) * | 2015-09-30 | 2016-02-24 | 成都晨光博达橡塑有限公司 | Fluorine-containing surfactant free of perfluorooctanoic acid and salts thereof |
| CN105344288A (en) * | 2015-09-30 | 2016-02-24 | 成都晨光博达橡塑有限公司 | Continuous production technology of fluorine-containing surfactant without perfluorocaprylic acid |
| CN109678700A (en) * | 2018-12-24 | 2019-04-26 | 天津市长芦化工新材料有限公司 | The method that comprehensive utilization dioxygen oxidation method prepares the by-product generated in HFPO |
| CN112852475A (en) * | 2020-12-25 | 2021-05-28 | 天津长芦新材料研究院有限公司 | Fluorine-containing demulsifying compound and demulsifying agent for oil field |
| CN114031762A (en) * | 2021-09-30 | 2022-02-11 | 四川弘氟新材料有限公司 | Preparation process of perfluoropolyether surfactant and perfluoropolyether surfactant |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148794A (en) * | 2015-09-30 | 2015-12-16 | 成都晨光博达橡塑有限公司 | Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid |
| CN105170017A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid |
| CN105170018A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant |
| CN105344289A (en) * | 2015-09-30 | 2016-02-24 | 成都晨光博达橡塑有限公司 | Fluorine-containing surfactant free of perfluorooctanoic acid and salts thereof |
| CN105344288A (en) * | 2015-09-30 | 2016-02-24 | 成都晨光博达橡塑有限公司 | Continuous production technology of fluorine-containing surfactant without perfluorocaprylic acid |
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| CN109678700A (en) * | 2018-12-24 | 2019-04-26 | 天津市长芦化工新材料有限公司 | The method that comprehensive utilization dioxygen oxidation method prepares the by-product generated in HFPO |
| CN112852475A (en) * | 2020-12-25 | 2021-05-28 | 天津长芦新材料研究院有限公司 | Fluorine-containing demulsifying compound and demulsifying agent for oil field |
| CN112852475B (en) * | 2020-12-25 | 2023-02-28 | 天津长芦新材料研究院有限公司 | Fluorine-containing demulsifying compound and demulsifier for oil field |
| CN114031762A (en) * | 2021-09-30 | 2022-02-11 | 四川弘氟新材料有限公司 | Preparation process of perfluoropolyether surfactant and perfluoropolyether surfactant |
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Application publication date: 20130501 |