CN103965071A - N-perfluorohexyl acetamide compounds as well as preparation method and application thereof - Google Patents
N-perfluorohexyl acetamide compounds as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides N-perfluorohexyl acetamide compounds as well as a preparation method and application thereof. The N-perfluorohexyl acetamide compounds are novel amide fluorocarbon surfactants which are produced by performing acylating chlorination on perfluorohexyl acetic acid by using sulfoxide chloride firstly and then reacting the acylating chlorination product with six amine in the presence of a catalyst, respectively; the surfactants are simple in preparation method, and have excellent surface activity; the number of fluorine-containing carbon atoms of the surfactants is 6 and lower than 8, and therefore, the surfactants meet the requirement of environmental protection and have quite wide application prospect.
Description
(1) technical field
The present invention relates to a kind of amides fluorocarbon surfactant and preparation method thereof.
(2) background technology
Perfluorocaprylic Acid (PFOA) molecular formula is C
7f
15cOOH, there is very strong hydrophobicity and oleophobic property, its chemical structure is stable far beyond other tensio-active agents, and there is high temperature resistant and powerful oxidation corrosion resistance, be widely used in hundreds of industry and the daily perfluorination chemical products such as electron trade, science and technology of aviation, paint, textiles and leathers product surface stain control agent.The ammonium salt of Perfluorocaprylic Acid, the ionic emulsifying agent of metallic salt, certainly research and develop tetrafluoroethylene dispersion polymerization, is the perfluor emulsifying agent always using; In the emulsion polymerization of fluorine-containing rubber, be also widely used simultaneously.
Relevant research shows, PFOA is difficult to degrade in physical environment, has the essential characteristic of persistence environmental organic pollutant.Although PFOA is also indefinite on the impact of human body, the PFOA of high dosage has demonstrated and has caused that the effect of canceration occurs at animal bodies multiple positions in experimentation on animals, and the PFOA that therefore whether stops using is all circles' bone of contention always.The harm that at present some developed countries and non governmental organization may cause PFOA to environment and HUMAN HEALTH is paid close attention to as focus.Wherein: " PFOA " that (1) Environmental Protection Agency and Duo Jiafu products production enterprise (as 3M, DuPont) sign reduces discharging in agreement and specify, before 2015, in all products, forbids.In December, (2) 2006, European Parliament and council of ministers combine issue " instruction of selling and using about restriction perfluoro octane sulfonate compound ", and putting goods on the market and using of perfluoro octane sulfonate (PFOS) and related substances thereof made to strict restriction.(3) " 12 plan " of country explicitly pointed out the research of focus development PFOA/PFOS substitute technology.
At present, in order to overcome the above problems, the developing thought that substitutes PFOA mainly contains following two kinds: (1) explores the fluorochemical surfactant of low-carbon (LC), to reduce the C of PFOA
8biological residual and biohazardous thereof.(2) explore containing heteroatoms, as contained the heteroatomic fluorochemical surfactants such as O, N.Because heteroatomic introducing contributes to fluorochemical surfactant biological degradation, can eliminate well residual in organism.Chinese Patent Application No. 201110007554.0 discloses the perfluoro hexyl acetic acid of being prepared under oxygenant by perfluoro hexyl ethanol, obtain corresponding anionic fluorochemical surfactant with alkali neutralization again, its CMC and surface tension are all less than corresponding perfluorooctanoic acid salt, can effectively reduce the surface tension of water.But aforesaid method comes with some shortcomings, in synthetic perfluoro hexyl acetic acid process, find that perfluoro hexyl acetic acid is impure, its purification is improved, it is carried out to rectifying, reached high purity, and ionogenic surfactant affected by pH and inorganic salt larger, range of application is subject to certain restrictions.
For above thinking, C just provided by the invention
6and contain the heteroatomic fluorocarbon surfactant of N.This class tensio-active agent belongs to nonionic surface active agent, all has good solubility property in water and organic solvent, and has excellent surface property.
(3) summary of the invention
It is simple that the object of the invention is to provide a kind of preparation method, has excellent surfactivity and meet the fluorocarbon surfactant of environmental requirement.
The technical solution used in the present invention is:
The invention provides the acetamides of N-perfluoro hexyl shown in a kind of formula I:
In formula I m1 and m2 be simultaneously 0 or 1, n be 2,3 or 4, this compound molecular weight is 420～462.
The present invention also provides a kind of method of preparing described N-perfluoro hexyl acetamides, described method is: (1) is by perfluoro hexyl acetic acid, organic solvent a and catalyst mix, then slowly drip sulfur oxychloride, 10～120 DEG C react completely after, reaction solution is evaporated to absence of liquid to flow out, get concentrated solution, obtain perfluoro hexyl Acetyl Chloride 98Min., perfluoro hexyl Acetyl Chloride 98Min. is dissolved and makes perfluoro hexyl chloride solution with organic solvent b; Described organic solvent a is the one in toluene, benzene, trichloromethane, methylene dichloride or sherwood oil; Described organic solvent b is with organic solvent a; Described catalyzer is pyridine or dimethyl formamide; (2) the perfluoro hexyl chloride solution of being prepared by step (1) is slowly added dropwise in acid binding agent and organic amine, at 40～100 DEG C, reacts completely, and after reaction finishes, by reaction solution separation and purification, obtains N-perfluoro hexyl acetamides; Described acid binding agent is triethylamine, pyridine, sodium carbonate or salt of wormwood; Described organic amine is quadrol, propylene diamine, butanediamine, N, N-dimethyl-1,2-quadrol, N, N-dimethyl-1,3-propylene diamine or N, N-dimethyl-1,4-butanediamine, described organic amine adds with the form of the organic solvent c of 0.05～0.2g/ml organic amine, and described organic solvent c is with organic solvent a, in same reaction, organic solvent a, organic solvent b are identical with organic solvent c.
Further, the described reaction of step (1) is at 40～100 DEG C of reaction 10～22h.
Further, the described perfluoro hexyl acetic acid of step (1) is 1:1～5 with the ratio of the amount of substance of sulfur oxychloride, preferably 1:2～3, the volumetric usage of described organic solvent a is counted 1～30ml/g (preferably 2～4ml/g) with perfluoro hexyl quality of acetic acid, the volumetric usage of described catalyzer is counted 0.001～0.1ml/g with perfluoro hexyl quality of acetic acid, preferably 0.004ml/g.The volumetric usage of described organic solvent b, can dissolve perfluoro hexyl Acetyl Chloride 98Min., is counted 4～6ml/g with perfluoro hexyl Acetyl Chloride 98Min. quality conventionally.
Further, the described temperature of reaction of step (2) is 40～60 DEG C.
Further, in the described acid binding agent of step (2) and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1～3:1, and in described organic amine and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1.2～4:1.
Further, the method of the described reaction solution separation and purification of step (2) is: after reaction finishes, in reaction solution, add aqueous hydrochloric acid (preferred mass concentration 5～10%) washing, take off layer, with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography, ethyl acetate using volume ratio as 1:3～10 and sherwood oil mixed solution are as elutriant, collect containing target components effluent liquid, dry, obtain N-perfluoro hexyl acetamides.
Further, the preparation method of described N-perfluoro hexyl acetamides carries out as follows: (1) is by perfluoro hexyl acetic acid, organic solvent a and catalyst mix, then slowly drip sulfur oxychloride with the speed of 1～2 drop/sec, 40～100 DEG C react completely after, reaction solution being evaporated under 60～80 DEG C, 10pa condition to absence of liquid flows out, get concentrated solution, obtain perfluoro hexyl Acetyl Chloride 98Min., perfluoro hexyl Acetyl Chloride 98Min. is dissolved and makes perfluoro hexyl chloride solution with organic solvent b; Described organic solvent a is the one in toluene, benzene, trichloromethane, methylene dichloride or sherwood oil; Described organic solvent b is with organic solvent a; Described catalyzer is pyridine or dimethyl formamide; Described perfluoro hexyl acetic acid is 1:2～3 with the ratio of the amount of substance of sulfur oxychloride, the volumetric usage of described organic solvent a is counted 2～4ml/g with perfluoro hexyl quality of acetic acid, and the volumetric usage of described catalyzer is counted 0.002～0.005ml/g with perfluoro hexyl quality of acetic acid; (2) the perfluoro hexyl chloride solution of being prepared by step (1) is added dropwise in acid binding agent and organic amine, reaction at 40～100 DEG C, HPLC follows the tracks of detection, after reaction finishes, in reaction solution, add mass concentration 5～15% aqueous hydrochloric acid washings, taking off layer saturated sodium-chloride water solution washs, after removing washings, carry out silica gel column chromatography, ethyl acetate using volume ratio as 1:5～8 and sherwood oil mixed solution are as elutriant, collect the effluent liquid containing target components, dry, obtain N-perfluoro hexyl acetamides; Described acid binding agent is triethylamine, pyridine, sodium carbonate or salt of wormwood; Described organic amine is quadrol, propylene diamine, butanediamine, N, N-dimethyl-1，2-diaminoethane, N, N-dimethyl-1,3-propylene diamine or N, N-dimethyl-Putriscine; In described acid binding agent and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1.2～3:1, in described organic amine and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1.5～3:1, described organic amine adds with the form of the organic solvent c of 0.1～0.2g/ml organic amine, and described organic solvent c is with organic solvent a.
The invention still further relates to the application of a kind of described N-perfluoro hexyl acetamides as tensio-active agent.
The reaction equation of preparation N-perfluoro hexyl acetamides:
Organic solvent a of the present invention, organic solvent and organic solvent c are organic solvent, name for ease of distinguishing different step organic solvent amount difference used, and letter itself does not have implication.
The invention has the beneficial effects as follows: the invention provides a kind of N-perfluoro hexyl acetamides, the fluorine-containing carbonatoms of this compound is 6, be less than 8, meet environmental requirement, for nonionogenic tenside, show excellent surfactivity (than ammonium perfluorocaprylate excellent performance), can attempt being applied in emulsion polymerization systems.
(4) brief description of the drawings
Fig. 1 is the purify rectifier unit of Perfluoroamidated compound of the present invention.
Fig. 2 is that the surface tension of the prepared Perfluoroamidated compound of the present invention and ammonium perfluorocaprylate is with volumetric molar concentration change curve.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
Get 5.0g (13.2mmol) perfluoro hexyl acetic acid, add 10ml toluene, drip 2 (0.02ml) DMF, then slowly drip 2eq (3.14g with the speed of 1～2 drop/sec, 26.4mmol) sulfur oxychloride, perfluoro hexyl acetic acid dissolves gradually, transfers in 100 DEG C of oil baths, reaction 10h, obtains yellow solution; Then till being evaporated to concentrated solution quality constant weight and producing without white cigarette under 60～80 DEG C, 10pa condition, except desolventizing and sulfur oxychloride, obtain 4.2g (10.6mmol) perfluoro hexyl Acetyl Chloride 98Min., add 20ml toluene to be made into perfluoro hexyl chloride solution, stand-by.
Get 3eq (1.91g, 31.8mmol) quadrol is dissolved in the there-necked flask that 10ml toluene is housed, add 2eq (2.14g, acid binding agent triethylamine 21.2mmol), under ice bath, (0～5 DEG C) slowly drips above-mentioned perfluoro hexyl chloride solution, after dropwising, be transferred in 100 DEG C of oil baths, continue reaction, and HPLC follow the tracks of detect to acyl chlorides peak disappear, react completely.After reaction finishes, obtain red tan solution, add the aqueous hydrochloric acid washing of mass concentration 10%; take off layer; with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography separation, the ethyl acetate using volume ratio as 1:10 and sherwood oil mixed solution are as elutriant; collect the effluent liquid containing target components; 65 DEG C dry, obtains N-perfluoro hexyl acetylethylenediamine, m1=0 in formula I; m2=0, n is 2.
Respectively by ammonium perfluorocaprylate, N-perfluoro hexyl acetylethylenediamine is soluble in water, be made into a series of concentration (0.004, 0.008, 0.012, 0.014, 0.016, 0.018, 0.021, 0.022, 0.025, 0.03, 0.045, solution 0.074mol/L), hang sheet method (being adopting platinum plate method) and measure surface tension to volumetric molar concentration graphic representation, in Fig. 2, provide the surface tension of N-perfluoro hexyl acetylethylenediamine with volumetric molar concentration change curve, experimental result shows that N-perfluoro hexyl acetylethylenediamine has excellent surfactivity, the micelle-forming concentration (CMC) of this water phase surfactant mixture is 21.0mmol/L, surface tension is now 19.3mN/m, show that performance is better than ammonium perfluorocaprylate.
Embodiment 2
Get 5.0g (13.2mmol) perfluoro hexyl acetic acid, add 20ml benzene, drip 2 (0.02ml) DMF, then slowly drip 2eq (3.14g with the speed of 1～2d/s, 26.4mmol) sulfur oxychloride, perfluoro hexyl acetic acid dissolves gradually, transfers in 60 DEG C of oil baths, reaction 20h, obtains yellow solution; Then till being evaporated to concentrated solution quality constant weight and producing without white cigarette under 60～80 DEG C, 10pa condition, revolve and steam except desolventizing and sulfur oxychloride, obtain 4.0g (10.1mmol) perfluoro hexyl Acetyl Chloride 98Min., add 20ml benzene to be made into perfluoro hexyl chloride solution, stand-by.
Get 2.5eq (1.86g, 25.25mmol) propylene diamine is dissolved in the there-necked flask that 10ml benzene is housed, add 3eq (2.39g, acid binding agent pyridine 30.3mmol), under ice bath, (0～5 DEG C) slowly drips above-mentioned solution of acid chloride, after dropwising, is transferred in 80 DEG C of oil baths, continue reaction, and detect to perfluoro hexyl Acetyl Chloride 98Min. peak and disappear and react completely with HPLC.After reaction finishes, obtain red tan solution, add mass concentration 10% aqueous hydrochloric acid washing; take off layer; with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography separation, the ethyl acetate using volume ratio as 1:10 and sherwood oil mixed solution are as elutriant; collect the elutriant containing target components; 65 DEG C dry, obtains N-perfluoro hexyl ethanoyl propylene diamine, m1=0 in formula I; m2=0, n is 3.
Respectively that ammonium perfluorocaprylate, N-perfluoro hexyl ethanoyl propylene diamine is soluble in water; be made into the solution of a series of concentration (0.004,0.008,0.012,0.014,0.016,0.018,0.021,0.022,0.025,0.03,0.045,0.074mol/L), hang sheet method (being adopting platinum plate method) and measure surface tension to volumetric molar concentration graphic representation.In Fig. 2, provide the surface tension of N-perfluoro hexyl ethanoyl propylene diamine with volumetric molar concentration change curve; experimental result shows that N-perfluoro hexyl ethanoyl propylene diamine has excellent surfactivity; the micelle-forming concentration (CMC) of this water phase surfactant mixture is 18.1mmol/L; surface tension is now 19.0mN/m, shows that performance is better than ammonium perfluorocaprylate.
Embodiment 3
Get 5.0g perfluoro hexyl acetic acid, add 20ml trichloromethane, drip 1～2 pyridine (0.02ml), then slowly drip 3eq (4.71g, 39.6mmol) sulfur oxychloride, perfluoro hexyl acetic acid dissolves gradually, transfer in 40 DEG C of oil baths, reaction 18h, obtains yellow solution; Then till being evaporated to concentrated solution quality constant weight and producing without white cigarette under 60～80 DEG C, 10pa condition, revolve and steam except desolventizing and sulfur oxychloride, obtain 3.5g (8.8mmol) perfluoro hexyl Acetyl Chloride 98Min..Add 20ml trichloromethane wiring solution-forming, stand-by.
Get 1.5eq (1.17g, 13.2mmol) butanediamine is dissolved in the there-necked flask that 10ml trichloromethane is housed, add 2eq (1.39g, acid binding agent pyridine 17.6mmol), under ice bath, (0～5 DEG C) slowly drips above-mentioned solution of acid chloride, after dropwising, is transferred in 60 DEG C of oil baths, continue reaction, and detect to perfluoro hexyl Acetyl Chloride 98Min. peak and disappear and react completely with HPLC.After reaction finishes, obtain red tan solution, add mass concentration 10% aqueous hydrochloric acid washing; take off layer; with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography separation, the ethyl acetate using volume ratio as 1:8 and sherwood oil mixed solution are as elutriant; collect the elutriant containing target components; 65 DEG C dry, obtains N-perfluoro hexyl ethanoyl butanediamine, m1=0 in formula I; m2=0, n is 4.
Respectively that ammonium perfluorocaprylate, N-perfluoro hexyl ethanoyl butanediamine is soluble in water; be made into the solution of a series of concentration (0.004,0.008,0.012,0.014,0.016,0.018,0.021,0.022,0.025,0.03,0.045,0.074mol/L), hang sheet method (being adopting platinum plate method) and measure surface tension to volumetric molar concentration graphic representation.In Fig. 2, provide the surface tension of N-perfluoro hexyl ethanoyl butanediamine with volumetric molar concentration change curve; experimental result shows that N-perfluoro hexyl ethanoyl butanediamine has excellent surfactivity; the micelle-forming concentration (CMC) of this water phase surfactant mixture is 17.8mmol/L; surface tension is now 18.2mN/m, shows that performance is better than ammonium perfluorocaprylate.
Embodiment 4
Get 5.0g perfluoro hexyl acetic acid, add 20ml toluene, drip 2 (0.02ml) DMF, then slowly drip 4eq (6.28g with the speed of 1～2d/s, 26.4mmol) sulfur oxychloride, perfluoro hexyl acetic acid dissolves gradually, transfers in 80 DEG C of oil baths, reaction 15h, obtains yellow solution; Then till being evaporated to concentrated solution quality constant weight and producing without white cigarette under 60～80 DEG C, 10pa condition, revolve and steam except desolventizing and sulfur oxychloride, obtain 4.1g (10.3mmol) perfluoro hexyl Acetyl Chloride 98Min..Add 20ml toluene to be made into solution of acid chloride, stand-by.
Get 2.0eq (1.82g, 20.6mmol) N, N-dimethyl-1，2-diaminoethane is dissolved in the there-necked flask that 10ml toluene is housed, and adds 3eq (3.13g, acid binding agent triethylamine 31.0mmol), under ice bath, (0～5 DEG C) slowly drips above-mentioned solution of acid chloride, after dropwising, is transferred in 100 DEG C of oil baths, continue reaction, and detect to perfluoro hexyl Acetyl Chloride 98Min. peak and disappear and react completely with HPLC.After reaction finishes, obtain red tan solution, add mass concentration 10% aqueous hydrochloric acid washing; take off layer, with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography separation; ethyl acetate using volume ratio as 1:8 and sherwood oil mixed solution are as elutriant; collect the elutriant containing target components, 65 DEG C dry, obtains N; N-dimethyl-N '-perfluoro hexyl acetylethylenediamine; m1=1 in formula I, m2=1, n is 2.
Respectively by ammonium perfluorocaprylate N; N-dimethyl-N '-perfluoro hexyl acetylethylenediamine is soluble in water; be made into the solution of a series of concentration (0.004,0.008,0.012,0.014,0.016,0.018,0.021,0.022,0.025,0.03,0.045,0.074mol/L), hang sheet method (being adopting platinum plate method) and measure surface tension to volumetric molar concentration graphic representation.In Fig. 2, provide N; the surface tension of N-dimethyl-N '-perfluoro hexyl acetylethylenediamine is with volumetric molar concentration change curve; experimental result shows N; N-dimethyl-N '-perfluoro hexyl acetylethylenediamine has excellent surfactivity; the micelle-forming concentration (CMC) of this water phase surfactant mixture is 16.5mmol/L; surface tension is now 15.2mN/m, shows that performance is better than ammonium perfluorocaprylate.
Embodiment 5
Get 5.0g perfluoro hexyl acetic acid, add 20ml methylene dichloride, drip 2 (0.02ml) DMF, then slowly drip 2eq (3.14g with the speed of 1～2d/s, 26.4mmol) sulfur oxychloride, perfluoro hexyl acetic acid dissolves gradually, transfers in 50 DEG C of oil baths, reaction 17h, obtains yellow solution; Then till being evaporated to concentrated solution quality constant weight and producing without white cigarette under 60～80 DEG C, 10pa condition, revolve and steam except desolventizing and sulfur oxychloride, obtain 4.3g (10.8mmol) perfluoro hexyl Acetyl Chloride 98Min..Add 20ml methylene dichloride to be made into solution of acid chloride, stand-by.
Get 1.5eq (1.66g, 16.3mmol) N, N-dimethyl-1,2-propylene diamine is dissolved in the there-necked flask that 10ml methylene dichloride is housed, and adds 2eq (2.19g, acid binding agent triethylamine 21.7mmol), under ice bath, (0～5 DEG C) slowly drips above-mentioned solution, after dropwising, is transferred in 40 DEG C of oil baths, continue reaction, and detect to perfluoro hexyl Acetyl Chloride 98Min. peak and disappear and react completely with HPLC.After reaction finishes, obtain red tan solution, add mass concentration 10% aqueous hydrochloric acid washing; take off layer, with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography separation; ethyl acetate using volume ratio as 1:5 and sherwood oil mixed solution are as elutriant; collect the elutriant containing target components, 65 DEG C dry, obtains N; N-dimethyl-N '-perfluoro hexyl ethanoyl propylene diamine; m1=1 in formula I, m2=1, n is 3.
Respectively by ammonium perfluorocaprylate N; N-dimethyl-N '-perfluoro hexyl ethanoyl propylene diamine is soluble in water; be made into the solution of a series of concentration (0.004,0.008,0.012,0.014,0.016,0.018,0.021,0.022,0.025,0.03,0.045,0.074mol/L), hang sheet method (being adopting platinum plate method) and measure surface tension to volumetric molar concentration graphic representation.In Fig. 2, provide N; the surface tension of N-dimethyl-N '-perfluoro hexyl ethanoyl propylene diamine is with volumetric molar concentration change curve; experimental result shows N; N-dimethyl-N '-perfluoro hexyl ethanoyl propylene diamine has excellent surfactivity; the micelle-forming concentration (CMC) of this water phase surfactant mixture is 15.4mmol/L; surface tension is now 14.3mN/m, shows that performance is better than ammonium perfluorocaprylate.
Embodiment 6
Get 5.0g (13.2mmol) perfluoro hexyl acetic acid, add 20ml methylene dichloride, drip 2 (0.02ml) pyridines, then slowly drip 3eq (4.71g with the speed of 1～2d/s, 39.6mmol) sulfur oxychloride, perfluoro hexyl acetic acid dissolves gradually, transfers in 40 DEG C of oil baths, reaction 22h, obtains yellow solution; Then till being evaporated to concentrated solution quality constant weight and producing without white cigarette under 60～80 DEG C, 10pa condition, revolve and steam except desolventizing and sulfur oxychloride, obtain 3.8g (9.6mmol) perfluoro hexyl Acetyl Chloride 98Min..Add 20ml methylene dichloride to be made into solution of acid chloride, stand-by.
Get 1.2eq (1.33g, 11.5mmol) N, N-dimethyl-1,2-butanediamine is dissolved in the there-necked flask that 10ml methylene dichloride is housed, and adds 2eq (2.65g, acid binding agent salt of wormwood 19.2mmol), under ice bath, (0～5 DEG C) slowly drips above-mentioned solution, after dropwising, is transferred in 40 DEG C of oil baths, continue reaction, and detect to perfluoro hexyl Acetyl Chloride 98Min. peak and disappear and react completely with HPLC.After reaction finishes, obtain red tan solution, add mass concentration 10% aqueous hydrochloric acid washing; take off layer, with saturated sodium-chloride water solution washing, after removal washings, carry out silica gel column chromatography separation; ethyl acetate using volume ratio as 15 and sherwood oil mixed solution are as elutriant; collect the elutriant containing target components, 65 DEG C dry, obtains N; N-dimethyl-N '-perfluoro hexyl ethanoyl butanediamine; m1=1 in formula I, m2=1, n is 4.
Respectively by ammonium perfluorocaprylate N; N-dimethyl-N '-perfluoro hexyl ethanoyl butanediamine is soluble in water; be made into the solution of a series of concentration (0.004,0.008,0.012,0.014,0.016,0.018,0.021,0.022,0.025,0.03,0.045,0.074mol/L), hang sheet method (being adopting platinum plate method) and measure surface tension to volumetric molar concentration graphic representation.In Fig. 2, provide N; the surface tension of N-dimethyl-N '-perfluoro hexyl ethanoyl butanediamine is with volumetric molar concentration change curve; experimental result shows N; N-dimethyl-N '-perfluoro hexyl ethanoyl butanediamine has excellent surfactivity; the micelle-forming concentration (CMC) of this water phase surfactant mixture is 13.6mmol/L; surface tension is now 13.4mN/m, shows that performance is better than ammonium perfluorocaprylate.
Claims (9)
1. N-perfluoro hexyl acetamides shown in a formula I:
In formula I m1 and m2 be simultaneously 0 or 1, n be 2,3 or 4.
2. prepare the method for N-perfluoro hexyl acetamides described in claim 1 for one kind, it is characterized in that described method is: (1) is by perfluoro hexyl acetic acid, organic solvent a and catalyst mix, then slowly drip sulfur oxychloride, 10～120 DEG C react completely after, reaction solution is evaporated to absence of liquid to flow out, get concentrated solution, obtain perfluoro hexyl Acetyl Chloride 98Min., perfluoro hexyl Acetyl Chloride 98Min. is dissolved and makes perfluoro hexyl chloride solution with organic solvent b; Described organic solvent a is the one in toluene, benzene, trichloromethane, methylene dichloride or sherwood oil; Described organic solvent b is with organic solvent a; Described catalyzer is pyridine or dimethyl formamide; (2) the perfluoro hexyl chloride solution of being prepared by step (1) is slowly added dropwise in acid binding agent and organic amine, at 40～100 DEG C, reacts completely, and after reaction finishes, by reaction solution separation and purification, obtains N-perfluoro hexyl acetamides; Described acid binding agent is triethylamine, pyridine, sodium carbonate or salt of wormwood; Described organic amine is quadrol, propylene diamine, butanediamine, N, N-dimethyl-1,2-quadrol, N, N-dimethyl-1,3-propylene diamine or N, N-dimethyl-Putriscine, described organic amine adds with the form of the organic solvent c of 0.05～0.2g/ml organic amine, and described organic solvent c is with organic solvent a.
3. prepare as claimed in claim 2 the method for N-perfluoro hexyl acetamides, it is characterized in that the described reaction of step (1) is at 40～100 DEG C of reaction 10～22h.
4. prepare as claimed in claim 2 the method for N-perfluoro hexyl acetamides, it is characterized in that the described perfluoro hexyl acetic acid of step (1) and the ratio of the amount of substance of sulfur oxychloride are 1:1～5, the volumetric usage of described organic solvent a is counted 1～30ml/g with perfluoro hexyl quality of acetic acid, and the volumetric usage of described catalyzer is counted 0.001～0.1ml/g with perfluoro hexyl quality of acetic acid.
5. prepare as claimed in claim 2 the method for N-perfluoro hexyl acetamides, it is characterized in that the described temperature of reaction of step (2) is 40～60 DEG C.
6. prepare as claimed in claim 2 the method for N-perfluoro hexyl acetamides, the ratio that it is characterized in that the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. in the described acid binding agent of step (2) and perfluoro hexyl chloride solution is 1～3:1, and in described organic amine and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1.2～4:1.
7. prepare as claimed in claim 2 the method for N-perfluoro hexyl acetamides, the method that it is characterized in that the described reaction solution separation and purification of step (2) is: after reaction finishes, in reaction solution, add aqueous hydrochloric acid washing, take off layer, wash with saturated sodium-chloride water solution, after removing washings, carry out silica gel column chromatography, ethyl acetate using volume ratio as 1:3～10 and sherwood oil mixed solution are as elutriant, collect containing target components effluent liquid, dry, obtain N-perfluoro hexyl acetamides.
8. prepare as claimed in claim 2 the method for N-perfluoro hexyl acetamides, it is characterized in that described method carries out as follows: (1) is by perfluoro hexyl acetic acid, organic solvent a and catalyst mix, then slowly drip sulfur oxychloride with the speed of 1～2 drop/sec, 40～100 DEG C react completely after, reaction solution being evaporated under 60～80 DEG C, 10pa condition to absence of liquid flows out, get concentrated solution, obtain perfluoro hexyl Acetyl Chloride 98Min., perfluoro hexyl Acetyl Chloride 98Min. is dissolved and makes perfluoro hexyl chloride solution with organic solvent b; Described organic solvent a is the one in toluene, benzene, trichloromethane, methylene dichloride or sherwood oil; Described organic solvent b is with organic solvent a; Described catalyzer is pyridine or dimethyl formamide; Described perfluoro hexyl acetic acid is 1:2～3 with the ratio of the amount of substance of sulfur oxychloride, the volumetric usage of described organic solvent a is counted 2～4ml/g with perfluoro hexyl quality of acetic acid, and the volumetric usage of described catalyzer is counted 0.002～0.005ml/g with perfluoro hexyl quality of acetic acid; (2) the perfluoro hexyl chloride solution of being prepared by step (1) is added dropwise in acid binding agent and organic amine, reaction at 40～100 DEG C, HPLC follows the tracks of detection, after reaction finishes, in reaction solution, add mass concentration 5～15% aqueous hydrochloric acid washings, taking off layer saturated sodium-chloride water solution washs, after removing washings, carry out silica gel column chromatography, ethyl acetate using volume ratio as 1:5～8 and sherwood oil mixed solution are as elutriant, collect the effluent liquid containing target components, dry, obtain N-perfluoro hexyl acetamides; Described acid binding agent is triethylamine, pyridine, sodium carbonate or salt of wormwood; Described organic amine is quadrol, propylene diamine, butanediamine, N, N-dimethyl-1，2-diaminoethane, N, N-dimethyl-1,3-propylene diamine or N, N-dimethyl-Putriscine; In described acid binding agent and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1.2～3:1, in described organic amine and perfluoro hexyl chloride solution, the ratio of the amount of substance of perfluoro hexyl Acetyl Chloride 98Min. is 1.5～3:1, described organic amine adds with the form of the organic solvent c of 0.1～0.2g/ml organic amine, and described organic solvent c is with organic solvent a.
Described in a claim 1 N-perfluoro hexyl acetamides as the application of tensio-active agent.
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| CN116103021A (en) * | 2021-11-10 | 2023-05-12 | 中石化石油工程技术服务有限公司 | Foaming agent for oil-based drilling fluid and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535020A (en) * | 1978-09-01 | 1980-03-11 | Neos Co Ltd | Fluorine-containing compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535020A (en) * | 1978-09-01 | 1980-03-11 | Neos Co Ltd | Fluorine-containing compound |
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| CN116103021A (en) * | 2021-11-10 | 2023-05-12 | 中石化石油工程技术服务有限公司 | Foaming agent for oil-based drilling fluid and preparation method and application thereof |
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