CN105833790A - Fluorine-containing phosphate surfactant and preparation method thereof - Google Patents
Fluorine-containing phosphate surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-containing phosphate surfactant and a preparation method thereof. The preparation method comprises that 4-perfluoroalkenoxybenzene sulfonyl chloride and 2-methylaminoethanol as raw materials undergo a reaction in an organic solvent in the presence of an acid binding agent at a temperature of 0-150 DEG C for 2-12h, the product is treated to form N-ethoxy-N-methyl-4-perfluoroalkenoxybenzsulfamide, the N-ethoxy-N-methyl-4-perfluoroalkenoxybenzsulfamide and an inorganic phosphorus compound are mixed and undergo a reaction at a temperature of 30-200 DEG C for 2-24h, an alkali liquid is added into the reaction product and undergoes a reaction, the reaction solution is separated and the precipitates are subjected to dewatering and drying so that the fluorine-containing phosphate surfactant is obtained. The preparation method has simple processes. The fluorine-containing phosphate surfactant has excellent performances, a high reaction yield, low surface tension, high activity, good water and oil resistance, wettability, emulsibility and good environmental friendliness and can be used as an emulsifier and a wetting agent in an actual life.
Description
Technical field
The present invention relates to surfactant field, be specifically related to a kind of fluorine-containing phosphate ester surfactant and preparation method thereof.
Background technology
Fluorine surfactant is the property of " three-hypers, two hate " owing to having, and is increasingly subject to the concern of people, is table in current all surface activating agent
The class that face activity is the highest, the technology that is mainly used in requires that higher extraordinary occasion or general conventional surfactants are difficult to be competent at, apply effect poor
Field, its fluorine-containing alkyl not only hydrophobic but also hate oil [new chemical materials, 2004,32 (8): 46].Enter 21 century fluorine-containing surfactant progressively to environment
Friendly, high surfactant, low cost direction are developed.External and China develops fluorine-containing surfactant mainly with the perfluoro capryl class of 8 carbon
For the various fluorine surfactant of Material synthesis.And various experimentation shows perfluoro capryl sulphonyl compounds (PFOS) and perfluoro caprylic acid and its esters
(PFOA) compound, occur hardly under various physico chemical factors any it is observed that degraded, for being most difficult at present having of degraded the most in the world
One of organic pollutants, has the highest bioconcentration and human body multi viscera toxicity.Therefore, in the end of the year 2006, European Union has formally issued PFOS
Sale and use limit instruction.According to international environmental science scholarly forecast, surfactant and finishing agent containing PFOS/PFOA will be in recent years
Limit use in the world, until disabling completely.
Now, our task of top priority is the succedaneum of research and development PFOS and PFOA.And the branched chain type fluorine with hexafluoropropylene trimer as development of raw materials
Carbon surface active agent, easily degrades under various physico chemical factors, and bioaccumulation is little, is the ideal substitute of PFOS/PFOA, Dupont
Company reports ethylene in patent US8049040 B2, tetrafluoroethene, perfluoroalkyl iodides telomerize, then through series reaction step prepare ethylene-
The technological process of tetrafluoroethene phosphate composition fluorine carboanion surfactant, this patent gained surfactant surface property is excellent, but ethylene,
Tetrafluoroethene, perfluoroalkyl iodides telomerize complex process, and yield is low, cause with high costs, it is difficult to industrialization, and patent US20110092410A1 is reported
The new technology of perfluoralkyl phosphate fluorine carboanion surfactant is prepared in road with hexafluoropropylene dimmer for raw material, but this technological reaction step mistake
Many, complex process, and have employed cesium fluoride, the expensive reagent such as bromopropene, production cost is higher, patent WO 9104978 (JP 3123786 A)
Report the preparation method of a kind of phosplate fluorine carboanion surfactant, but raw material non-ω-H fluorinated alkyl alcohol, the more difficult acquisition of raw material, produce
Cost is high.
Summary of the invention
In order to overcome defect and the deficiency of above-mentioned prior art, the invention provides a kind of fluorine-containing phosphate ester surfactant, and provide a kind of raw material
Convenient sources, synthetic method is simple, the preparation method of the phosphate fluorosurfactants containing perfluor that reaction yield is high.
On the one hand technical scheme provides a kind of fluorine-containing phosphate ester surfactant, it is characterised in that described fluorine-containing phosphate ester surface activity
The general structure of agent such as Formulas I:
Wherein n=2 or 3, M are Na, K, Mg, Ca or NH4。
On the other hand technical scheme provides a kind of fluorine-containing phosphate ester surfactant, including following reactions steps:
1) with 4-perfluoro alkene oxygen base benzene sulfonyl chloride and 2-methylaminoethanol as raw material, in the presence of acid binding agent, in organic solvent after reaction, through after
Process obtains product N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide；
2) by after above-mentioned N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and inorganic phosphorous compound hybrid reaction, add alkali liquor and continue reaction,
Gained reactant liquor is separated, after dehydrate fluorine-containing phosphate ester surfactant.
According to technique scheme provide method, step 1) in reaction temperature be 0～150 DEG C, the response time is 2～12h；In the present invention one
In a little embodiments, step 1) reaction temperature be 0 DEG C, 30 DEG C, 50 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C
Or 140 DEG C；Response time is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
In certain embodiments of the present invention, step 2) in reaction temperature be 30～200 DEG C, the response time is 2～24h；At another of the present invention
In a little embodiments, step 2) in reaction temperature be 60～150 DEG C, the response time is 3～6h；In some other embodiment of the present invention,
Step 2) in reaction temperature be 30 DEG C, 50 DEG C, 70 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C,
180 DEG C or 190 DEG C, the response time is 2h, 4h, 6h, 8h, 9h, 11h, 12h, 14h, 16h, 18h, 20h, 22h or 24h.
In certain embodiments of the present invention, 4-perfluoro alkene oxygen base benzene sulfonyl chloride (Formulas I), 2-methylaminoethanol (Formula II) and N-ethoxy-N-
The structural formula of methyl-4-perfluoro alkene oxygen base benzsulfamide (formula III) is as follows: wherein n=2 or 3；
In certain embodiments of the present invention, step 1) in 4-perfluoro alkene oxygen base benzene sulfonyl chloride, the amount of material of 2-methylaminoethanol and acid binding agent
Ratio be 1:1～5:1～5；In other embodiments of the present invention, 4-perfluoro alkene oxygen base benzene sulfonyl chloride, 2-methylaminoethanol and the material of acid binding agent
The ratio of amount be 1:2～5:2～5；In some other embodiment of the present invention, 4-perfluoro alkene oxygen base benzene sulfonyl chloride, 2-methylaminoethanol and acid binding agent
The ratio of amount of material be 1:2.5～4.5:2.5～4.5.
In certain embodiments of the present invention, step 1) in organic solvent selected from acetonitrile, ethyl acetate, dichloroethanes, trichloroethane, two
Chloromethanes, chloroform, chlorobenzene, Nitrobenzol, oxolane, N,N-dimethylformamide or dimethyl sulfoxide.
In certain embodiments of the present invention, organic solvent is 1～3:1 with the mass ratio of 4-perfluoro alkene oxygen base benzene sulfonyl chloride；At another of the present invention
In a little embodiments, organic solvent is 1.5～3:1 with the mass ratio of 4-perfluoro alkene oxygen base benzene sulfonyl chloride.
In certain embodiments of the present invention, alkali liquor is selected from KOH solution, NaOH solution or ammonia.
In certain embodiments of the present invention, inorganic phosphorous compound is selected from phosphorus pentoxide or phosphorus oxychloride.
In certain embodiments of the present invention, acid binding agent is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, hydrogen-oxygen
Change potassium, at least one in potassium carbonate, potassium bicarbonate or carbonic acid, triethylamine, diethylamine, ethamine, aniline, phenethylamine or n-butylamine.
In certain embodiments of the present invention, step 1) described in post processing include decompression distillation and recrystallization.
Of the present invention dry, refer to make water or solvent gasification in material by means of energy, and take away the process of generated steam.Some of the present invention
The drying mode that embodiment is used is dried for drying.It should be pointed out that, can reach the drying means of same effect also include but not limited to dry,
Vacuum drying, lyophilization, pneumatic conveying drying, microwave drying, infrared drying and dielectric dry etc..In certain embodiments of the present invention,
Baking temperature≤100 DEG C.
" separation " of the present invention represents the operation separated with nonfluid by fluid under gravity or other External Force Actings, described medium by medium
Including but not limited to filter paper, gauze, filter element, semipermeable membrane, filter screen etc., in theory, the material containing loose structure can become the medium of filtration；
The equipment filtered includes but not limited to vacuum or decompressor, pressue device, centrifugal device etc..
The water used in embodiments of the present invention is deionized water.
The most in contrast, otherwise, all scopes that the present invention quotes include end value.Such as, " step 2) in reaction temperature be
30～200 DEG C ", represent that reaction temperature T is in the range of 30 DEG C≤T≤200 DEG C.
Terminology used in the present invention "or" represents alternative, if appropriate, can they be combined, say, that term "or" includes often
Individual listed independent alternative and combinations thereof.Such as, " inorganic phosphorous compound is selected from phosphorus pentoxide or phosphorus oxychloride " represents Phos
Compound can be the one among phosphorus pentoxide or phosphorus oxychloride, it is also possible to be its more than one combination.
The beneficial effects of the present invention is:
The invention provides a kind of new surfactant one fluorine-containing phosphate ester surfactant, the surface tension of this aqueous surfactant solution
Low, activity is high, and has preferable water and oil-resistant, wettability and emulsifying capacity and good environment friendly, can be as emulsifying agent, wetting agent
Etc. being applied in real life；Additionally, the method synthesizing this fluorine-containing phosphate ester surfactant that the present invention provides is simple, raw material is cheap and easily-available, and
Gained fluorine-containing surfactant excellent performance, reaction yield is high.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred embodiment.It should be pointed out that, for this
For the technical staff in field on the basis of these innovation and creation are conceived, the some deformation made and improvement, broadly fall into protection scope of the present invention.Real
Executing raw material used in example all can be by being either commercially available.
Embodiment 1
30mL acetonitrile, 6.22g (0.01mol) 4-perfluorinated nonene epoxide benzene sulfonyl chloride, 0.75g (0.01mol) is added in 100mL four-hole boiling flask
2-methyl aminoethanol, 1.06g (0.01mol) natrium carbonicum calcinatum, stirring, it is warming up to 0 DEG C, keeps temperature stirring 2h, reactant liquor decompression is distilled, extremely
Till solvent-free abjection, it is cooled to room temperature, washes gained sticky oil thing, with recrystallized from acetonitrile, obtain white crystal N-ethoxy-N-methyl-4-complete
Fluorine alkenyloxy group benzsulfamide, yield 85%, by gained N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide equipped with agitator, condensing tube,
In the four-hole boiling flask of the 250mL of thermometer, starting agitator temperature and be increased to 30 DEG C, be dividedly in some parts 3.55g phosphorus pentoxide, temperature gradually rises
Height, reaction starts, and reaction temperature maintains 30 DEG C, and response time 24h cools the temperature to room temperature, is then added to 30% sodium hydroxide solution 5
In g after stirring, reacting 5h, dehydration obtains target product, and yield 87.5%, through measuring the aqueous solution minimum surface that target product consumption is 0.1%
Tension force 19 dynes per centimeter.
Embodiment 2
30mL dichloromethane, 6.22g (0.01mol) 4-perfluorinated nonene epoxide benzene sulfonyl chloride, 3.75g (0.05 is added in 100mL four-hole boiling flask
Mol) 2-methyl aminoethanol, 4.04g (0.04mol) triethylamine, stirring, it is warming up to 80 DEG C, keeps temperature stirring 12h, reactant liquor decompression is distilled,
To solvent-free abjection, it is cooled to room temperature, washes gained sticky oil thing, with recrystallized from acetonitrile, obtain white crystal N-ethoxy-N-methyl-4-
Perfluoro alkene oxygen base benzsulfamide, yield 98.7%, by gained N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide equipped with agitator, condensation
Pipe, thermometer 250mL four-hole boiling flask in, start agitator temperature and be increased to 80 DEG C, be dividedly in some parts 3.55g phosphorus pentoxide, temperature by
Edge up height, and reaction starts, and reaction temperature maintains 90～110 DEG C, and response time 6h cools the temperature to 45 DEG C, is then added to 30% hydroxide
After potassium solution 5g stirs 3.5h, dehydration acquisition target product, yield 98.5% is minimum through measuring the aqueous solution that target product consumption is 0.1%
Surface tension 18.7 dynes per centimeter.
Embodiment 3
Addition 30mL DMF in 100mL four-hole boiling flask, 6.22g (0.01mol) 4-perfluorinated nonene epoxide benzene sulfonyl chloride,
1.5g (0.02mol) 2-methyl aminoethanol, 6.9g (0.05mol) Anhydrous potassium carbonate, stirring, it is warming up to 150 DEG C, keeps temperature stirring 6h, instead
Answer liquid decompression distillation, to solvent-free abjection, be cooled to room temperature, wash gained sticky oil thing, with recrystallized from acetonitrile, obtain white crystal N-
Ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide, yield 93%, by gained N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide at dress
Have in the four-hole boiling flask of 250mL of agitator, condensing tube, thermometer, start agitator temperature and be increased to 200 DEG C, be dividedly in some parts 3.55g five oxygen
Changing two phosphorus, temperature gradually rises, and reaction starts, and reaction temperature maintains 180～200 DEG C, and response time 10h cools the temperature to 45 DEG C, then
Joining after stirring 3h in ammonia spirit (35%) 5g, dehydration obtains target product, yield 92%, is 0.1% through measuring target product consumption
Aqueous solution lowest surface tension 18.5 dynes per centimeter.
Embodiment 4
30mL oxolane, 6.22g (0.01mol) 4-perfluorinated nonene epoxide benzene sulfonyl chloride, 1.5g (0.02mol) is added in 100mL four-hole boiling flask
2-methyl aminoethanol, 0.8 (0.02mol) sodium hydroxide, stirring, it is warming up to 90 DEG C, keeps temperature stirring 8h, reactant liquor decompression distillation, to without molten
Till agent abjection, it is cooled to room temperature, washes gained sticky oil thing, with recrystallized from acetonitrile, obtain white crystal N-ethoxy-N-methyl-4-perfluor alkene
Epoxide benzsulfamide, yield 95.6%, by gained N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide equipped with agitator, condensing tube, temperature
In the four-hole boiling flask of the 250mL of degree meter, starting agitator temperature and be increased to 90 DEG C, be dividedly in some parts 3.55g phosphorus pentoxide, temperature gradually rises,
Reaction starts, and reaction temperature maintains 120～130 DEG C, and response time 12h cools the temperature to 35 DEG C, is then added to ammonia spirit (35%) 5g
After middle stirring 2h, dehydration obtains target product, yield 94%, reaches through measuring the aqueous solution lowest surface tension 20 that target product consumption is 0.1%
Because of/centimetre.
Embodiment 5
30mL chloroform, 6.22g (0.01mol) 4-perfluorinated nonene epoxide benzene sulfonyl chloride, 2.25g (0.03mol) is added in 100mL four-hole boiling flask
2-methyl aminoethanol, 1.2 (0.03mol) sodium hydroxide, stirring, it is warming up to 70 DEG C, keeps temperature stirring 6h, reactant liquor decompression distillation, to nothing
Till solvent abjection, it is cooled to room temperature, washes gained sticky oil thing, with recrystallized from acetonitrile, obtain white crystal N-ethoxy-N-methyl-4-perfluor
Alkenyloxy group benzsulfamide, yield 96%, by gained N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide equipped with agitator, condensing tube, temperature
In the four-hole boiling flask of the 250mL of degree meter, starting agitator temperature and be increased to 80 DEG C, be dividedly in some parts 3.55g phosphorus pentoxide, temperature gradually rises,
Reaction starts, and reaction temperature maintains 110～120 DEG C, and response time 10h cools the temperature to 35 DEG C, is then added to ammonia spirit (35%) 5g
After middle stirring 0.5h, dehydration obtains target product, and yield 91%, through measuring the aqueous solution lowest surface tension 19 that target product consumption is 0.1%
Dynes per centimeter.
Embodiment 6
Obtained target product is carried out the test of surface tension performance, wettability, contact angle, Water-proof and oil-proof, concrete method of testing and result
As follows:
1) interfacial tension
Test on the impact of oil-water system interfacial tension: fluorine-containing polyoxyethylene ether nonionic surfactant obtained in embodiment 1-5 is joined
Make the aqueous solution that mass concentration is 0.1%, then contact mixing with organic solvent toluene, hexamethylene, ethyl acetate respectively, depend on by surface tension instrument
Testing its interfacial tension respectively according to adopting platinum plate method, test result is as follows:
The table 1 impact on oil-water system interfacial tension
| Oil phase | Toluene | Hexamethylene | Ethyl acetate |
| Pure water | 35.00 | 50.46 | 6.66 |
| Embodiment 1 | 5.56 | 5.05 | 6.19 |
| Embodiment 2 | 5.85 | 5.54 | 6.21 |
| Embodiment 3 | 6.25 | 5.38 | 6.34 |
| Embodiment 4 | 6.08 | 5.52 | 6.28 |
| Embodiment 5 | 6.21 | 5.16 | 6.38 |
Immiscible You Heshui biphase by the modes such as stirring makes oil phase and aqueous phase mixing, wherein one in microspheroidal droplet distribution in another phase,
Form a kind of thermodynamic unstable system.In order to make the emulsion long period of formation keep stable, need to add the composition reducing its interfacial tension
(i.e. emulsifying agent) makes the dispersion of instability become the most stable.Emulsifying ability is closely related with interfacial tension, and interfacial tension is the lowest, the easiest
Emulsifying, as can be known from the above table, fluorine-containing phosphate ester surfactant has relatively low interfacial tension can be widely used in the polymerization of fluoropolymer as emulsifying agent.
2) mensuration of wetting power:
The aqueous solution becoming concentration to be 0.1% fluorine-containing phosphate ester surfactant formulatory obtained in embodiment 1-5, according to canvas sedimentation (GB
5557 1985 fish hook methods) it is measured, concrete outcome is as follows:
The impact of table 2 embodiment 1-5 aqueous solution wetting power
| Test group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| T/s | 13.4 | 13.7 | 14.3 | 13.9 | 14.7 |
As can be known from the above table, synthesized fluorine-containing polyoxyethylene ether nonionic surfactant has good wettability, can be extensive as wetting agent
It is applied to the field such as coating, ink.
3) mensuration of water contact angle:
The aqueous solution becoming concentration to be 0.1% fluorine-containing phosphate ester surfactant formulatory obtained in embodiment 1-5, with water contact angle measurement instrument respectively
Test solution and synthetic leather, cotton and the contact angle of glass surface, test result is as follows:
Table 3 surface water contact angle
| Test group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Synthetic leather | 102.1° | 99.6° | 101.2° | 97.8° | 102.8° |
| Cotton | 110.2° | 108.2° | 110.0° | 102.5° | 112.0° |
| Glass | 114.0° | 110.3° | 112.0° | 109.3° | 114.6° |
From above-mentioned test result, this fluorine-containing phosphate ester surfactant is relatively big with the surface contact angle of solid, the Young equation according to famous:
γ S=γ SL+ γ Lcos θ understands, and this fluorine-containing polyoxyethylene ether nonionic surfactant has preferable water repellency.
4) waterproof and oilproof test
Waterproof test: carry out open flow trickle test according to AATCC-22.Represent anti-shower resistance with classification of waterproof.Be attached to the suffix after data "+" table
Show that performance is slightly better than the grade performance of numerical representation method.Evaluation criteria is shown in Table 4:
5 test fluid are gently dropped on fabric by grease proofing test: test by AATCC-118 standard by micropipette pipe, an amount
For 0.05mL, if left standing for still remaining with 4 or 5 on fabric after 30s, then test fluid is by test.Grease proofness by by test test fluid
Big score value represents.Grease proofness is cited as 8 grades, and they are 1,2,3,4,5,6,7 and 8 by the order of poor rank to excellent rank.Comment
Calibration standard is shown in Table 4:
The standard of the waterproof and grease proofing test of table 4
Waterproof and oilproof is tested: the aqueous solution becoming concentration to be 0.1% fluorine-containing phosphate ester surfactant formulatory obtained in embodiment 1-5, presses respectively
Testing according to above-mentioned testing standard, concrete outcome is as follows:
Table 5 fabric water repellent, oil repellent test result
| Test group | Water repellent rank | Refuse oil rank |
| Embodiment 1 | 5 | 5 |
| Embodiment 2 | 4+ | 4 |
| Embodiment 3 | 5 | 6 |
| Embodiment 4 | 4 | 3 |
| Embodiment 5 | 4+ | 4 |
Knowable to result above, fluorine-containing phosphate ester surfactant has preferable water and oil-resistant.
Claims (11)
1. a fluorine-containing phosphate ester surfactant, it is characterised in that the general structure such as Formulas I of described fluorine-containing phosphate ester surfactant:
Wherein n=2 or 3, M are Na, K, Mg, Ca or NH4。
2. the preparation method of a fluorine-containing phosphate ester surfactant as claimed in claim 1, it is characterised in that include following reactions steps:
1) with 4-perfluoro alkene oxygen base benzene sulfonyl chloride and 2-methylaminoethanol as raw material, in the presence of acid binding agent, in organic solvent after reaction, through after
Process obtains product N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide；
2) by after above-mentioned N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide and inorganic phosphorous compound hybrid reaction, add alkali liquor and continue reaction,
Gained reactant liquor is separated, after dehydrate fluorine-containing phosphate ester surfactant.
Preparation method the most according to claim 2, it is characterised in that step 1) in reaction temperature be 0～150 DEG C, the response time is 2～12
h；Step 2) in reaction temperature be 30～200 DEG C, the response time is 2～24h.
Preparation method the most according to claim 2, it is characterised in that described 4-perfluoro alkene oxygen base benzene sulfonyl chloride (Formulas I), 2-methylamino second
The structural formula of alcohol (Formula II) and N-ethoxy-N-methyl-4-perfluoro alkene oxygen base benzsulfamide (formula III) is as follows: wherein n=2 or 3；
The preparation method of fluorine-containing phosphate ester surfactant the most according to claim 2, it is characterised in that step 1) in 4-perfluoro alkene oxygen base
The ratio of the amount of the material of benzene sulfonyl chloride, 2-methylaminoethanol and acid binding agent is 1:1～5:1～5.
The preparation method of fluorine-containing phosphate ester surfactant the most according to claim 2, it is characterised in that step 2) in N-ethoxy-N-
Methyl-4-perfluoro alkene oxygen base benzsulfamide is 1～3:1 with the ratio of the amount of the material of inorganic phosphorous compound.
The preparation method of fluorine-containing phosphate ester surfactant the most according to claim 2, it is characterised in that step 1) in organic solvent choosing
From acetonitrile, ethyl acetate, dichloroethanes, trichloroethane, dichloromethane, chloroform, chlorobenzene, Nitrobenzol, oxolane, N, N-dimethyl formyl
Amine or dimethyl sulfoxide.
8. according to the preparation method of fluorine-containing phosphate ester surfactant described in claim 2 or 7, it is characterised in that described organic solvent and 4-
The mass ratio of perfluoro alkene oxygen base benzene sulfonyl chloride is 1～3:1.
The preparation method of fluorine-containing phosphate ester surfactant the most according to claim 2, it is characterised in that described alkali liquor selected from KOH solution,
NaOH solution or ammonia.
The preparation method of fluorine-containing phosphate ester surfactant the most according to claim 2, it is characterised in that described inorganic phosphorous compound is selected from
Phosphorus pentoxide or phosphorus oxychloride.
The preparation method of 11. fluorine-containing phosphate ester surfactants according to claim 2, it is characterised in that described acid binding agent is selected from hydroxide
Sodium, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate or carbonic acid, triethylamine, diethylamine,
At least one in ethamine, aniline, phenethylamine or n-butylamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116496828A (en) * | 2023-04-25 | 2023-07-28 | 湖南鸿福实业有限公司 | Environment-friendly trace lubricating oil and preparation method thereof |
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| US3948819A (en) * | 1970-05-20 | 1976-04-06 | Minnesota Mining And Manufacturing Company | Cleaning composition |
| WO1989004350A1 (en) * | 1987-11-03 | 1989-05-18 | Eastman Kodak Company | Adhesion promoting composition and coated film |
| CN101406816A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for producing sulfuric acid fluorinated surfactants |
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2016
- 2016-01-28 CN CN201610058415.3A patent/CN105833790B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948819A (en) * | 1970-05-20 | 1976-04-06 | Minnesota Mining And Manufacturing Company | Cleaning composition |
| WO1989004350A1 (en) * | 1987-11-03 | 1989-05-18 | Eastman Kodak Company | Adhesion promoting composition and coated film |
| CN101406816A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for producing sulfuric acid fluorinated surfactants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116496828A (en) * | 2023-04-25 | 2023-07-28 | 湖南鸿福实业有限公司 | Environment-friendly trace lubricating oil and preparation method thereof |
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