CN103611469A - Preparation and application of fluorine-containing polyethyleneglycol monomethyl ether benzoate - Google Patents
Preparation and application of fluorine-containing polyethyleneglycol monomethyl ether benzoate Download PDFInfo
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- CN103611469A CN103611469A CN201310669609.3A CN201310669609A CN103611469A CN 103611469 A CN103611469 A CN 103611469A CN 201310669609 A CN201310669609 A CN 201310669609A CN 103611469 A CN103611469 A CN 103611469A
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- monomethyl ether
- glycol monomethyl
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Abstract
The invention discloses synthesis and application of a fluorine-containing polyethyleneglycol monomethyl ether benzoate [4-perfluoro-(1,3-dimethyl-2-isopropyl-1-butenyloxy)] benzoate. The research of application of surface tension, interfacial tension, water solution foamability, wettability and emulsibility detects that the polyethyleneglycol monomethyl ether benzoate has lower surface tension and lower interfacial tension, which indicates that the polyethyleneglycol monomethyl ether benzoate has excellent surface activity.
Description
(1)
technical field
The present invention relates to a kind of poly glycol monomethyl ether benzoic ether surfactant of fluorine-containing nonionic, preparation and the application thereof of poly glycol monomethyl ether [4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy)] benzoic ether.
(2)
background technology
The synthetic during World War II that starts from of fluorine-containing surfactant, Minnesota Mining and Manufacturing Company adopts Electrofluorination technology to successfully synthesize first fluorine-containing surfactant in nineteen fifty-one, development through more than 50 years, synthetic and the application of fluorine-containing surfactant has all obtained significant progress, after relay solution fluoride process is produced fluorine surfactant, in succession occurred fluoroolefins telomerization method, fluoroolefins oligomerisation method is produced the technique of fluorine-containing surfactant.U.S. West Europe Japan and other countries and area are in succession developed the companies such as this type of product Dupont, Britain ICI, French Atochem, German Hoechst and Bayer, Switzerland Ciba-Geigy and Japan AGC, great Jin and Neos and are had more than 80% market subsequently.3M company is wherein maximum manufacturer.
Synthesizing of China's fluorine-containing surfactant, start from the beginning of the seventies at the end of the sixties in last century, development through nearly 40 years, research unit is mainly organic chemistry research institute of the Chinese Academy of Sciences and Shanghai fluorine organic material research institute, manufacturer mainly contains Changjiang Chemical Plant, Wuhan City etc., and what be engaged in fluorine-containing surfactant fundamental research is mainly Chemical and Molecular Engineering College of Beijing Univ.'s colloid chemistry research department.With abroad comparing, China's fluorine-containing surfactant, no matter in production capacity, or at study on the synthesis, all weaker in application study.
Along with demand international, domestic market increases day by day, fluorine-containing surfactant excellent performance, with high content of technology, added value is large, the very big interest that causes domestic and international researcher, novel molecular structure continues to bring out, and the application of fluorine-containing surfactant simultaneously has also broken through traditional field gradually.Having the novel fluorine surfactants such as two carbon fluorine chains, the hydrocarbon heteroduplex of carbon fluorine, two hydrophilic chain, many hydrophilic chains and fluorine-containing surfactant synthetic intermediate is in the news in succession, therefore, green substitute as hc-surfactant, the research order of functional fluorine-bearing surfactant has larger development space, be going deep into of science and technology, can bring huge economic and social benefit again.
(3) summary of the invention
The object of the present invention is to provide a kind of synthetic and application of poly glycol monomethyl ether benzoic ether surfactant of fluorine-containing nonionic, the present invention has excellent surface-active.
Structural formula of the present invention is as follows:
Wherein:
The integer of n=6～50
Comprise: MPEG-400, MPEG-500, MPEG-600, MPEG-750, MPEG-850, MPEG-1000, MPEG-1100, MPEG-1200, MPEG-1300, MPEG 1900, MPEG-2000, MPEG-3000, MPEG-5000.
The preparation method of above-mentioned fluorine-containing poly glycol monomethyl ether [4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy)] benzoic ether, comprises the steps:
With 4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy) chlorobenzoyl chloride, be that raw material reacts with poly glycol monomethyl ether, obtain corresponding fluorine-containing poly glycol monomethyl ether benzoic ether non-ionic surface active agent.
Reaction equation is:
The compounds of this invention (1) be by 4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy) benzoic acid and acylating reagent applicable temperature, solvent, base catalyst and certain amount of substance than under react and prepare.
Substantive distinguishing features of the present invention can be achieved from following examples of implementation, but the only conduct explanation of these examples of implementation, rather than limit the invention.
(4) accompanying drawing explanation
Aqueous solution surface tension and the concentration logarithmic curve of accompanying drawing 1. embodiment 1
Foam volume and the concentration curve of accompanying drawing 2 embodiment 1,2,3
The lather collapse half-life of accompanying drawing 3 embodiment 1,2,3 aqueous solution is with the change curve of concentration logarithm
(5) specific implementation method
Embodiment 1: in the four-hole boiling flask of 100mL, add 50 mL acetonitriles, Anhydrous potassium carbonate 0.97g(0.05mol), 4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy) chlorobenzoyl chloride 29.3 g(0.05mol), be heated with stirring to backflow, slowly drip 30.0 g(0.05mol) poly glycol monomethyl ether (MPEG-600), approximately 30 min, continue reaction 5 h.After reaction finishes, remove by filter after residue, removal of solvent under reduced pressure, obtains faint yellow viscous liquid, the surface tension (γ of its 0.01% aqueous solution
cMC) be 20. 8 mN/m(pure water surface tension 71.0 mN/m).
Embodiment 2: in the four-hole boiling flask of 100mL, add 50 mL oxolanes, triethylamine 0.97g(0.05mol), 4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy) chlorobenzoyl chloride 29.3 g(0.05mol), be heated with stirring to backflow, slowly drip 37.5 g(0.05mol) poly glycol monomethyl ether (MPEG-750), approximately 30 min, continue reaction 5h.After reaction finishes, removal of solvent under reduced pressure, obtains faint yellow viscous liquid, the surface tension (γ of its 0.01% aqueous solution
cMC) be 21.0 mN/m(pure water surface tension 71.0 mN/m).
Embodiment 3: in the four-hole boiling flask of 100mL, add 50 mL oxolanes, triethylamine 0.97g(0.05mol), 4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy) chlorobenzoyl chloride 29.3 g(0.05mol), be heated with stirring to backflow, slowly drip 75.0 g(0.05mol) poly glycol monomethyl ether (MPEG-1000), approximately 30 min, continue reaction 5h.After reaction finishes, removal of solvent under reduced pressure, obtains faint yellow viscous liquid, the surface tension (γ of its 0.01% aqueous solution
cMC) be 22.8 mN/m(pure water surface tension 71.0 mN/m).
Embodiment 4: surface tension performance
With hanging sheet method, measure (Wilhelmy hangs sheet method), the perpendicular dull and stereotyped test liquid that inserts of employing cover glass, mica sheet, filter paper or platinum foil, makes its base contact with liquid level, measures and hangs the required maximum pull F contending with surface tension of sheet disengaging liquid.Hang sheet method and have, intuitive and reliable, do not need correction factor, this and other spin off method is different, can also measure liquid-liquid interface tension force.By accompanying drawing 1, the compound in test implementation example 1, can show that its critical micelle concentration is 3.8 * 10
-4mol/L, the now surface tension (γ of its aqueous solution
cMC) be 21. 2 mN/m, see accompanying drawing 1.
Interfacial tension refers to along interface between immiscible two-phase (liquid-solid, liquid-liquid, liquid-gas) and vertically acts on the surperficial convergent force on unit length liquid surface.Its unit is mN/m.Liquid contacts with another kind of not miscible liquid, and the power of its generation of interfaces is the interfacial tension between liquid phase and liquid phase.
The impact of table 1 on oil-water system interfacial tension
| Oil phase | Toluene | Cyclohexane | Ethyl acetate |
| Pure water | 35.00 | 50.46 | 6.66 |
| |
6.22 | 5.20 | 6.23 |
| |
6.90 | 5.80 | 6.10 |
| |
7.12 | 6.23 | 6.45 |
The foaming properties of surfactant is mainly to weigh by the foaming power of foam and two indexs of foam stability.Foaming power refer to the complexity of formation of foam and foam generated amount how many.The stability of foam refers to the persistence of the foam of generation, the complexity of froth breaking, the i.e. length of foam average life.
Foam foaming power is to take foam volume M as ordinate, and mass concentration is abscissa, draws embodiment 1,2, and the foam volume of 3 aqueous solution is with the change curve of concentration, wherein: curve 1,2, the compound (accompanying drawing 2) in the corresponding embodiment 1,2,3 of 3 difference.
Foam stability is with lather collapse half-life T
1/2for ordinate, mass concentration is abscissa, obtains embodiment 1,2, and the lather collapse half-life of 3 aqueous solution is with the change curve (accompanying drawing 3) of concentration logarithm.
Wet processes refers to that lip-deep a kind of fluid is by the another kind immiscible process that fluid replaced with it.Wetting action is a kind of Surface and interface process, so surfactant must have remarkable effect in this process.Adopt canvas sedimentation to survey sinking time, measure the wetting power of solution, in Table 2.
The impact of table 2 embodiment 1,2,3 aqueous solution wetting powers
| Fluorine-containing poly glycol monomethyl ether | Embodiment | 1 | |
Embodiment 3 |
| T/s | 13.0 | 13.7 | 14.8 |
Immiscible oil and water two-phase mix oil phase and water by modes such as stirrings, wherein one be mutually microspheroidal drop be scattered in another mutually in, form a kind of thermodynamic unstable system.For the emulsion long period that makes to form keeps stable, need to add the composition (being emulsifying agent) that reduces its interfacial tension to make unsettled dispersion become relatively stable.
The application of emulsifiability adopts a minute water Time Method to study.Emulsifying ability and interfacial tension are closely related, and interfacial tension is lower, easier emulsification; Time is longer shows that emulsifiability is better.Embodiment 1,2, and 3 emulsifying ability, in Table 3.With the aqueous solution of the embodiment 1,2,3 of 1.0 g/L, test the interfacial tension of itself and oil phase-benzene, in Table 4.
The emulsifying ability of table 3 embodiment 1,2,3
| Fluorine-containing poly glycol monomethyl ether | Embodiment | 1 | |
Embodiment 3 |
| T / min | 9.0 | 11.8 | 12.7 |
Table 4 embodiment 1,2, the interfacial tension of 3 aqueous solution-benzene
| Fluorine-containing poly glycol monomethyl ether | Embodiment | 1 | |
|
| Interfacial tension mN/m | 5.15 | 5.23 | 5.42 |
Claims (5)
1. the poly glycol monomethyl ether benzoic ether surfactant suc as formula a kind of fluorine-containing nonionic shown in I:
I。
2. the preparation method suc as formula the poly glycol monomethyl ether shown in I [4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy)] benzoic ether as claimed in claim 1, is characterized in that described method is:
Ⅱ
With
iI4-perfluor-(1,3-dimethyl-1-butenyloxy) chlorobenzoyl chloride and poly glycol monomethyl ether are raw material, at organic solvent
1in, under base catalyst exists, in-10 ~ 100 ℃ of reaction 1 ~ 5 h, after reaction finishes, remove solid residue, after removal of solvent under reduced pressure, obtain poly glycol monomethyl ether [4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy)] benzoic ether;
Described solvent
1for one of following: carrene, chloroform, carbon tetrachloride, acetonitrile, dichloroethanes, acetonitrile, DMF, benzene,toluene,xylene, carrene, chloroform, carbon tetrachloride, ethyl acetate, benzinum, dimethyl sulfoxide (DMSO), pyridine, triethylamine, piperidines, cyclohexanone, acetone, butanone, methyl alcohol, ethanol;
Described base catalyst is one of following: natrium carbonicum calcinatum, Anhydrous potassium carbonate, anhydrous sodium bicarbonate, NaOH, potassium hydroxide, triethylamine, diethylamine, pyridine, piperidines, N-methyl piperidine.
3. method as claimed in claim 2, is characterized in that described 4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy) chlorobenzoyl chloride: poly glycol monomethyl ether: the amount of substance ratio of base catalyst is: 1:1.0 ~ 2.0:0.8-1.2.
4. method as claimed in claim 2, is characterized in that described reaction temperature-10 ~ 100 ℃, reaction time 1 ~ 5 h.
5. application as claimed in claim 1, it is characterized in that poly glycol monomethyl ether [4-perfluor-(1,3-dimethyl-2-isopropyl-1-butenyloxy)] benzoic ether is as a kind of synthetic and application of poly glycol monomethyl ether benzoic ether surfactant of fluorine-containing nonionic.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079084A (en) * | 1972-03-15 | 1978-03-14 | Imperial Chemical Industries Limited | Fluorocarbon surfactants |
| US5126379A (en) * | 1989-12-19 | 1992-06-30 | Basf Aktiengesellschaft | Esters containing bonded fluorocarbon and oxypropylenealkylether groups, emulsions containing these esters and their use for the preparation of cellular plastics by polyisocyanate polyaddition |
| CN102974266A (en) * | 2012-12-04 | 2013-03-20 | 浙江工业大学 | Preparation method and application of flursulamid-containing sulfate anionic surfactant |
| CN102993058A (en) * | 2012-12-04 | 2013-03-27 | 浙江工业大学 | Preparation method and application of fluorine-containing benzamido sulfate anionic surfactant |
-
2013
- 2013-12-11 CN CN201310669609.3A patent/CN103611469A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079084A (en) * | 1972-03-15 | 1978-03-14 | Imperial Chemical Industries Limited | Fluorocarbon surfactants |
| US5126379A (en) * | 1989-12-19 | 1992-06-30 | Basf Aktiengesellschaft | Esters containing bonded fluorocarbon and oxypropylenealkylether groups, emulsions containing these esters and their use for the preparation of cellular plastics by polyisocyanate polyaddition |
| CN102974266A (en) * | 2012-12-04 | 2013-03-20 | 浙江工业大学 | Preparation method and application of flursulamid-containing sulfate anionic surfactant |
| CN102993058A (en) * | 2012-12-04 | 2013-03-27 | 浙江工业大学 | Preparation method and application of fluorine-containing benzamido sulfate anionic surfactant |
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Application publication date: 20140305 |