CN103623743A

CN103623743A - Fluorine-containing non-ionic surfactant, and preparation method and application thereof

Info

Publication number: CN103623743A
Application number: CN201310669611.0A
Authority: CN
Inventors: 武宏科; 史鸿鑫; 沈海民
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2013-12-11
Filing date: 2013-12-11
Publication date: 2014-03-12

Abstract

The invention discloses a fluorine-containing non-ionic surfactant polyethylene glycol bi-[4-perfluor-(1,3-dimethyl-1-butenyloxy)] besilate, and a preparation method and application of the fluorine-containing non-ionic surfactant, makes researches on the surface tension and interfacial tension of the fluorine-containing non-ionic surfactant and the foaminess, wettability and emulsibility of an aqueous solution of the fluorine-containing non-ionic surfactant, and finds out that the fluorine-containing non-ionic surfactant has lower surface tension and interfacial tension and excellent surface activity.

Description

A kind of preparation method of fluorine-containing non-ionic surface active agent and application thereof

(1) technical field

The present invention relates to preparation method and the application thereof of a kind of fluorine-containing non-ionic surface active agent polyethylene glycol two [4-perfluor-(1,3-dimethyl-1-butenyloxy)] benzene sulfonate.

(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 preparation method and the application thereof of a kind of fluorine-containing non-ionic surface active agent polyethylene glycol two [4-perfluor-(1,3-dimethyl-1-butenyloxy)] benzene sulfonate, the present invention has excellent surface-active and application prospect.

Structural formula of the present invention is as follows:

Wherein:

The integer of n=6～50

Comprise: PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1200, PEG-1400, PEG-1600, PEG-1800, PEG-2000 etc.

The preparation method of above-mentioned fluorine-containing non-ionic surface active agent, comprises the steps:

With 4-perfluor-(1,3-dimethyl-1-butenyloxy) benzene sulfonyl chloride, be that raw material reacts with polyethylene glycol, obtain corresponding fluorine-containing non-ionic surface active agent.

Reaction equation is:

The compounds of this invention (1) be by 4-perfluor-(1,3-dimethyl-1-butenyloxy) phenyl ether and sulfonylation agent 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-1-butenyloxy) benzene sulfonyl chloride 47.2 g(0.10 mol), be heated with stirring to backflow, slowly drip 30.0 g(0.05mol) polyethylene glycol (PEG-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 18.9 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-1-butenyloxy) benzene sulfonyl chloride 47.2 g(0.10 mol), be heated with stirring to backflow, slowly drip 40.0 g(0.05mol) polyethylene glycol (MPEG-800), 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 19.0 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-1-butenyloxy) benzene sulfonyl chloride 47.2 g(0.10 mol), be heated with stirring to backflow, slowly drip 50.0 g(0.05mol) polyethylene glycol (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 21.2 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 3.1 * 10 ^-4mol/L, the now surface tension (γ of its aqueous solution _cMC) be 19.8 mN/m, see accompanying drawing 1.

Embodiment 5 interfacial tension performances

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.

Embodiment

1,2, and the interfacial tension of 3 the aqueous solution and benzene, cyclohexane, ethyl acetate is as shown in table 1-.

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
Embodiment 1	5.14	5.01	6.10
				Embodiment 2	6.02	5.18	6.48
Embodiment 3	6.46	5.56	6.89

Embodiment 6 foaminess application

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.

Embodiment 7 wetability application

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 non-ionic surface active agent	Embodiment	1	Embodiment 2	Embodiment 3
					T/s	11.5	12.4	13.5

Embodiment 8 emulsibility application

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 abilities, 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.

Table 3

embodiment

1,2,3 emulsifying abilities

Fluorine-containing non-ionic surface active agent	Embodiment	1	Embodiment 2	Embodiment 3
					T / min	8.5	11.8	12.8

Table 4

embodiment

1,2, the interfacial tension of 3 aqueous solution-benzene

Fluorine-containing non-ionic surface active agent	Embodiment	1	Embodiment 2	Embodiment 3
					Interfacial tension mN/m	5.34	5.65	5.73

Claims

1. one kind suc as formula a kind of fluorine-containing non-ionic surface active agent shown in I:

Figure 2013106696110100001DEST_PATH_IMAGE002

I

。

2. the preparation method suc as formula the polyethylene glycol two shown in I [4-perfluor-(1,3-dimethyl-1-butenyloxy)] benzene sulfonate as claimed in claim 1, is characterized in that described method is:

Figure 2013106696110100001DEST_PATH_IMAGE004

Ⅱ

With iI4-perfluor-(1,3-dimethyl-1-butenyloxy) benzene sulfonyl chloride and polyethylene glycol 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 polyethylene glycol two [4-perfluor-(1,3-dimethyl-1-butenyloxy)] benzene sulfonate;

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-1-butenyloxy) benzene sulfonyl chloride: polyethylene glycol: the amount of substance ratio of base catalyst is: 1:0.5 ~ 0.8:0.8-1.2.

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, is characterized in that polyethylene glycol two [4-perfluor-(1,3-dimethyl-1-butenyloxy)] benzene sulfonate is as a kind of synthetic and application of fluorine-containing non-ionic surface active agent.