CN103657513A - Gemini-type ampholytic surfactant based on perfluoroolefine and preparation method thereof - Google Patents
Gemini-type ampholytic surfactant based on perfluoroolefine and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Gemini-type ampholytic surfactant based on perfluorononene and perfluorohexene, and a preparation method thereof. The preparation method comprises the following steps: taking perfluorononene and perfluorohexene as the raw materials, carrying out phenol condensation reactions and chlorosulfonation reactions so as to obtain perfluoroolefineoxyl benzene sulfonyl chloride, then subjecting the perfluoroolefineoxyl benzene sulfonyl chloride to carry out condensation reactions with 2-dimethylamino ethylamine or 3-dimethylamino propylanmine so as to obtain perfluoroolefineoxyl benzene sulfonamide whose amine part comprises a tertiary amine group, then subjecting the perfluoroolefineoxyl benzene sulfonamide to carry out condensation reactions with 1,2-dihaloethane, 1,3-dihalopropane, 1,4-dihalobutane, 1,5-dihalopentane, 3-oxa-1,5-dihalopentane, or 1,3-dihaloacetone, wherein the halogen element is chlorine or bromine, and finally subjecting the reaction product to carry out condensation reactions with vinyl sulfonate, chloroethyl sulfonate, bromoethyl sulfonate or 1,3-propanesultone so as to obtain the Gemini-type ampholytic fluorine surfactant with excellent surface activity and low critical micelle concentration. The Gemini-type ampholytic fluorine surfactant has the prominent characteristics of simple synthetic operation, low cost, high surface activity, and low using concentration, and has a vast market prospect.
Description
Technical field
The present invention relates to a class fluorine surfactant, the particularly Gemini ampholytic surfactant of a class based on perfluoroolefine, and preparation method thereof.
Background technology
Surfactant is important fine chemical product, has the several functions such as moistening, emulsification, foaming, froth breaking, dispersion, have the title of industrial monosodium glutamate.Surfactant is generally divided into anionic, cationic, amphoteric and nonionic.
Normally used surfactant, its hydrophobic group is hydrocarbon alkyl, in molecule, probably containing other elements such as aerobic, sulphur, nitrogen, chlorine, bromines, the conventional surfactant of this class is called as conventional surfactants.The surfactant that contains the elements such as fluorine, phosphorus, silicon, boron in surfactant molecule is called as special surfactant.
Fluorine surfactant is the special surfactant of a class, and it has high thermal stability, high chemical stability, high surface, not only hates the characteristic of oil but also hydrophobic, so have been widely used at aspect tools such as fire-fighting, oil recoveries.Fluorine surfactant mainly contains three kinds of electrolysis, fluoroolefins telomerization method and fluoroolefins oligomerisation methods in industrial synthetic method.
The fluorine surfactant of extensive use is perfluoro caprylic acid (PFOA) and perfluoro octyl sulfonic acid (PFOS) and derivative thereof all the time, but this compounds has been subject to people on the impact of environmental and human health impacts, pays close attention to widely.Various experiments show, under various physico chemical factors, there is hardly any degraded that can observe in PFOA and PFOS, for current one of organic pollution of difficult degradation in the world, there are the many organ toxicities of very high bioconcentration and human body, various countries have limited or have banned use of.
Hexafluoropropene oligomers particularly hexafluoropropylene dimmer and hexafluoropropylene trimer cheap, avoided the with serious pollution shortcoming of electrolysis, by its derivative fluorine surfactant, be the potential PFOA of a class and PFOS substitute.Yet hexafluoropropene oligomers has branched structure, its surface-active does not reach the level of PFOA and PFOS and derivative thereof, and the application of such substitute has been produced to very large restriction.
Summary of the invention
In order to overcome the defect of existing hexafluoropropene oligomers derivative class surfactant surface-active deficiency, the present invention has prepared a kind of Gemini ampholytic surfactant based on perfluorinated nonene (hexafluoropropylene trimer) and perfluor hexene (hexafluoropropylene dimmer), and general formula is
R wherein
ffor perfluorinated nonene base or perfluor hexenyl; M is 2 or 3; N is 2 or 3; R is (CH
2)
2or (CH
2)
3or (CH
2)
4or (CH
2)
5or (CH
2)
2o (CH
2)
2or CH
2cOCH
2.
It is oleophilic moiety that above-claimed cpd be take perfluorinated nonene oxygen base phenyl or perfluor hexene oxygen base phenyl, take quaternary ammonium root and sulfonate radical as hydrophilic segment, between two surfactants with methene chain (CH
2)
n(n=2,3,4,5) or 3-oxa-pentylidene chain (CH
2)
2o (CH
2)
2or 2-oxo propylidene is for connecting bridge; Oleophilic moiety is connected by sulfonamide key with hydrophilic segment.Owing to having possessed said structure feature, make described compound there is very high surface-active, surface tension, between 15.2mN/m and 20.2mN/m, approaches the level of PFOA and PFOS; Critical micelle concentration is lower, between 6.0x10
-5mol/L and 2.3x10
-4between mol/L.
The present invention is applied to the theory and design method of Gemini surface active agent in the fluorine surfactant based on perfluoroolefine, has prepared the Gemini ampholytic fluorine surfactant based on perfluoroolefine.
The preparation of surfactant of the present invention is with perfluorinated nonene or perfluor hexene and phenol condensation, chlorosulfonation, or with phenol condensation, sulfonation, chlorination, or with the perfluoro alkene oxygen base benzene sulfonyl chloride that p-hydroxy benzenyl sulfonate sodium condensation, chlorination obtain be raw material.Perfluoro alkene oxygen base benzene sulfonyl chloride and 2-dimethylaminoethylam,ne or the condensation of 3-DIMAPA obtain amine moiety with the perfluoro alkene oxygen base benzsulfamide intermediate (A) of tertiary amine, then with 1,2-dihalo-ethane, 1,3-bis-halopropanes, 1,4-dihalo-butane, 1,5-dihalo-pentane, 3-oxa--1,5-dihalo-pentane, 1,3-dihalo-condensation of acetone makes double quaternary ammonium salt type intermediate (B) (halogen is chlorine or bromine), and the last reaction of N sulfoalkylation under alkalescence again obtains a series of Gemini ampholytic fluorine surfactants (C).
In the present invention preparation method used, the reaction of being prepared perfluoro alkene oxygen base benzene sulfonyl chloride by perfluorinated nonene and perfluor hexene is open in the literature, as US Patent No. 4788321.This condensation reaction relates generally to the selection of solvent and acid binding agent.The strong polar aprotic solvent of the general use of solvent, as DMF, acetonitrile, oxolane etc.Acid binding agent is generally used triethylamine, tri-n-butylamine, pyridine etc.Perfluoro alkene oxygen base benzene sulfonyl chloride also can first be prepared perfluoro alkene oxygen base benzene sulfonic acid through sulfonation by perfluoro alkene oxygen base benzene, through chlorinating agent, as phosphorus pentachloride, chlorination makes again, also can be by perfluorinated nonene or perfluor hexene and p-hydroxy benzenyl sulfonate sodium condensation, then make through chlorinating agent chlorination, these methods are also open in the literature, as (fine chemistry industries 2012 such as European patent EP 0420235, Cao Yougui, 29(2), and 174-177, Shen Haimin etc. (agricultural chemicals 2007,46(8), 520-522,534).
In the present invention preparation method used, the aminating reaction of being prepared perfluoro alkene oxygen base benzsulfamide intermediate (A) by perfluoro alkene oxygen base benzene sulfonyl chloride and 2-dimethylaminoethylam,ne or the condensation of 3-DIMAPA is open in the literature, as (Zhejiang Polytechnical University's journals 2009 such as Chinese patent CN1743062 and Shi Hongxin, 37(6), 619-622) etc.It is characterized in that hydrogen chloride that reaction produces can be by adding tertiary amine acid binding agent to absorb as triethylamine, pyridine etc., also can utilize amine moiety self with tertiary amine absorb, reaction finish after again with inorganic base as NaOH, sodium carbonate etc. neutralizes, to discharge tertiary amine, carry out next step reaction.
In the present invention preparation method used, the quaterisation of being prepared double quaternary ammonium salt type intermediate (B) by perfluoro alkene oxygen base benzsulfamide intermediate (A) and saturated dihalide condensation had report in Gemini surface active agent is synthetic, but not yet had report for take double type fluorine surfactant that perfluorinated nonene or perfluor hexene be lipophilic group synthetic.Saturated dihalide can be bromo or chlorohydrocarbon, and bromo-hydrocarbons reactivity is higher, but chlorohydrocarbon price is lower.
In the present invention preparation method used, hydrogen on double quaternary ammonium salt type midbody sulfamide nitrogen has higher acidity, be easy to generate nitrogen anion with alkali effect, then obtain amphoteric Gemini surface active agent with sulfoalkylation reagent reacting, concrete reaction condition can be adjusted according to reaction raw materials.Sulfoalkylation reagent is generally vinyl sulfonic acid sodium, chloroethyl sodium sulfonate, bromoethyl sodium sulfonate or 1,3-propane sultone etc.
The compound with formula (C) of gained of the present invention, characterizes through the detection means such as infrared spectrum, mass spectrum, elementary analysis, the raw materials used and reaction condition of association reaction etc., with shown in structure conform to.The surface property of product also shows that they have the feature of Shuangzi structure.
The prepared amphoteric Shuangzi fluorine surfactant of the present invention has high surface, add on a small quantity and can significantly reduce surface tension, have excellent dispersiveness, can rewetting lubricant nature etc., can be used for textile finishing, washing industry, tertiary oil production in oil field, fire-fighting, the inhibition of chromium mist, Treatment of Metal Surface etc.
The specific embodiment
For the present invention is further illustrated, below in conjunction with specific embodiment, be illustrated.
embodiment 1 N-(3-dimethylamino-propyl) preparation of perfluorinated nonene oxygen base benzsulfamide (A)
Perfluorinated nonene oxygen base benzene sulfonyl chloride 62.3g (0.1mol), 3-DIMAPA 10.2g (0.1mol) and oxolane 100mL are added in four-hole bottle, at 20 ℃, drip triethylamine 20.2g (0.2mol), about 40min drips off, 60 ℃ of reaction 5h, are poured into water reactant liquor, separate organic phase, oxolane extraction three times, merge organic phase, precipitation obtains light yellow solid, yield 94.6%.
the preparation of the double quaternary ammonium salt type intermediate (B) of embodiment 2 based on perfluorinated nonene oxygen base
Getting embodiment 1 products therefrom 34.4g (0.05mol) and toluene 80mL is heated to reflux, stir the lower 3.2g of dropping (0.025mol) 1,3-dichloroacetone and 20mL toluene solution, back flow reaction 10 h, be chilled to room temperature, filter toluene wash, vacuum drying obtains white solid, yield 92.2%.
the preparation of the amphoteric Gemini surface active agent (C) of embodiment 3 based on perfluorinated nonene
Embodiment 2 products therefrom 75.2g (0.05mol) and N, dinethylformamide 120mL is heated to 80 ℃, stir the solution of the lower 25.3g (0.12mol) of dropping bromoethyl sodium sulfonate, 4.8g (0.12mol) NaOH and 50mL water, insulation reaction 14h, is chilled to room temperature, is diluted with water, filter, successively, with water and methanol wash, vacuum drying obtains off-white color solid, yield 94.9%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1600(phenyl ring C=C), 1495(phenyl ring C=C), 1245(S=O), 1232(aryl-O), 1184(C-F), 1135(C-F), 1130(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
47h
44f
34n
4o
13s
4theoretical value C 34.26%, and H 2.67%, and F 39.25%; Measured value C 34.18%, H 2.55%, and F 39.04%.Mass spectrum: molecular weight 1646.
embodiment 4 N-(2-dimethylamino ethyls) preparation of perfluor hexene oxygen base benzsulfamide (A)
Perfluor hexene oxygen base benzene sulfonyl chloride 47.3g (0.1mol), 2-dimethylaminoethylam,ne 8.8g (0.1mol) and acetonitrile 100mL are added in four-hole bottle, at 20 ℃, drip triethylamine 20.2g (0.2mol), about 40min drips off, 60 ℃ of reaction 5h, are poured into water reactant liquor, separate organic phase, acetonitrile extracting twice, merge organic phase, precipitation obtains light yellow solid, yield 96.3%.
the preparation of the double quaternary ammonium salt type intermediate (B) of embodiment 5 based on perfluor hexene oxygen base
Getting embodiment 4 products therefrom 26.2g (0.05mol) and acetonitrile 80mL is heated to reflux, stir the lower 5.1g of dropping (0.025mol) 1,3-dibromopropane and 10mL acetonitrile solution, back flow reaction 16h, be chilled to room temperature, filter, successively with acetonitrile and cyclohexane washing, vacuum drying obtains off-white color solid, yield 93.8%.
the preparation of the amphoteric Gemini surface active agent (C) of embodiment 6 based on perfluor hexene
Embodiment 5 products therefrom 62.5g (0.05mol) and 1-METHYLPYRROLIDONE 130mL are heated to 80 ℃, stir the solution of the lower 26.6g (0.16mol) of dropping chloroethyl sodium sulfonate, 16.6g (0.12mol) potash and 45mL water, insulation reaction 13h, be chilled to room temperature, be diluted with water, filter, successively with water and ethanol washing, vacuum drying obtains white solid, yield 90.4%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1599(phenyl ring C=C), 1494(phenyl ring C=C), 1243(S=O), 1234(aryl-O), 1187(C-F), 1134(C-F), 1129(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
39h
42f
22n
4o
12s
4theoretical value C 35.89%, and H 3.22%, and F 32.06%; Measured value C 35.77%, H 3.11%, and F 31.94%.Mass spectrum: molecular weight 1304.
embodiment 7 N-(2-dimethylamino ethyls) preparation of perfluorinated nonene oxygen base benzsulfamide (A)
Perfluorinated nonene oxygen base benzene sulfonyl chloride 62.3g (0.1mol), 2-dimethylaminoethylam,ne 8.8g (0.1mol) and oxolane 100mL are added in four-hole bottle, at 20 ℃, drip triethylamine 20.2g (0.2mol), about 40min drips off, 60 ℃ of reaction 5h, are poured into water reactant liquor, separate organic phase, oxolane extraction three times, merge organic phase, precipitation obtains light yellow solid, yield 91.5%.
the preparation of the double quaternary ammonium salt type intermediate (B) of embodiment 8 based on perfluorinated nonene oxygen base
Getting embodiment 7 products therefrom 33.7g (0.05mol) and toluene 80mL is heated to reflux, stir the lower 3.2g of dropping (0.025mol) 1,4-dichloroetane and 20mL toluene solution, back flow reaction 10 h, be chilled to room temperature, filter toluene wash, vacuum drying obtains white solid, yield 90.8%.
the preparation of the amphoteric Gemini surface active agent (C) of embodiment 9 based on perfluorinated nonene
Embodiment 8 products therefrom 73.8g (0.05mol) and N, N-dimethylacetylamide 120mL is heated to 80 ℃, stir the solution of the lower 15.6g (0.12mol) of dropping vinyl sulfonic acid sodium, 4.8g (0.12mol) NaOH and 50mL water, insulation reaction 15h, is chilled to room temperature, is diluted with water, filter, successively, with water and methanol wash, vacuum drying obtains off-white color solid, yield 92.4%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1601(phenyl ring C=C), 1495(phenyl ring C=C), 1243(S=O), 1235(aryl-O), 1185(C-F), 1134(C-F), 1128(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
46h
44f
34n
4o
12s
4theoretical value C 34.12%, and H 2.72%, and F 39.93%; Measured value C 34.00%, H 2.58%, and F 39.74%.Mass spectrum: molecular weight 1618.
embodiment 10 N-(3-dimethylamino-propyls) preparation of perfluor hexene oxygen base benzsulfamide (A)
Perfluor hexene oxygen base benzene sulfonyl chloride 47.3g (0.1mol), 3-DIMAPA 10.2g (0.1mol) and acetonitrile 100mL are added in four-hole bottle, at 20 ℃, drip triethylamine 20.2g (0.2mol), about 40min drips off, 60 ℃ of reaction 5h, are poured into water reactant liquor, separate organic phase, acetonitrile extracting twice, merge organic phase, precipitation obtains light yellow solid, yield 94.8%.
the preparation of the double quaternary ammonium salt type intermediate (B) of embodiment 11 based on perfluor hexene oxygen base
Getting embodiment 10 products therefrom 26.9g (0.05mol) and acetonitrile 80mL is heated to reflux, stir the lower 3.6g (0.025mol) of dropping two (2-chloroethyl) ether and 10mL acetonitrile solutions, back flow reaction 14h, be chilled to room temperature, filter, successively, with acetonitrile and cyclohexane washing, vacuum drying obtains off-white color solid, yield 91.2%.
the preparation of the amphoteric Gemini surface active agent (C) of embodiment 12 based on perfluor hexene
Embodiment 11 products therefrom 61.0g (0.05mol) and dimethyl sulfoxide (DMSO) 140mL are heated to 90 ℃, stir the lower 12.2g of dropping (0.10mol) 1, the solution of 3-propane sultone, 16.6g (0.12mol) potash and 40mL water, insulation reaction 12h, is chilled to room temperature, is diluted with water, filter, successively, with water and ethanol washing, vacuum drying obtains white solid, yield 91.1%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1599(phenyl ring C=C), 1494(phenyl ring C=C), 1242(S=O), 1235(aryl-O), 1187(C-F), 1135(C-F), 1130(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
44h
52f
22n
4o
13s
4theoretical value C 37.99%, and H 3.74%, and F 30.07%; Measured value C 37.81%, H 3.63%, and F 29.90%.Mass spectrum: molecular weight 1390.
the preparation of the double quaternary ammonium salt type intermediate (B) of embodiment 13 based on perfluorinated nonene oxygen base
Getting embodiment 1 products therefrom 34.4g (0.05mol) and toluene 80mL is heated to reflux, stir the lower 2.5g of dropping (0.025mol) 1,2-dichloroethanes and 20mL toluene solution, back flow reaction 10 h, be chilled to room temperature, filter toluene wash, vacuum drying obtains white solid, yield 90.4%.
the preparation of the amphoteric Gemini surface active agent (C) of embodiment 14 based on perfluorinated nonene
Embodiment 13 products therefrom 73.8g (0.05mol) and N, dinethylformamide 120mL is heated to 80 ℃, stir the solution of the lower 25.3g (0.12mol) of dropping bromoethyl sodium sulfonate, 4.8g (0.12mol) NaOH and 50mL water, insulation reaction 12h, is chilled to room temperature, is diluted with water, filter, successively, with water and methanol wash, vacuum drying obtains off-white color solid, yield 94.9%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1600(phenyl ring C=C), 1496(phenyl ring C=C), 1246(S=O), 1231(aryl-O), 1185(C-F), 1135(C-F), 1129(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
46h
44f
34n
4o
12s
4theoretical value C 34.12%, and H 2.72%, and F 39.93%; Measured value C 34.00%, H 2.58%, and F 39.74%.Mass spectrum: molecular weight 1618.
the preparation of the double quaternary ammonium salt type intermediate (B) of embodiment 15 based on perfluor hexene oxygen base
Getting embodiment 4 products therefrom 26.2g (0.05mol) and oxolane 80mL is heated to reflux, stir the lower 5.8g of dropping (0.025mol) 1, pentamethylene bromide and 10mL tetrahydrofuran solution, back flow reaction 28h, be chilled to room temperature, filter, successively with acetonitrile and cyclohexane washing, vacuum drying obtains off-white color solid, yield 89.6%.
the preparation of the amphoteric Gemini surface active agent (C) of embodiment 16 based on perfluor hexene
Embodiment 15 products therefrom 63.9g (0.05mol) and 1-METHYLPYRROLIDONE 130mL are heated to 80 ℃, stir the solution of the lower 26.6g (0.16mol) of dropping chloroethyl sodium sulfonate, 16.6g (0.12mol) potash and 45mL water, insulation reaction 13h, be chilled to room temperature, be diluted with water, filter, successively with water and ethanol washing, vacuum drying obtains white solid, yield 92.5%.
Diffuse reflectance infrared spectroscopy peak (cm
-1): 1599(phenyl ring C=C), 1494(phenyl ring C=C), 1244(S=O), 1234(aryl-O), 1188(C-F), 1134(C-F), 1129(S=O), 1040(S=O), there is no the N-H peak of 3330 left and right.Elementary analysis: C
39h
42f
22n
4o
12s
4theoretical value C 36.94%, and H 3.45%, and F 31.38%; Measured value C 36.77%, H 3.31%, and F 31.19%.Mass spectrum: molecular weight 1332.
Above example chemical raw material used, solvent etc. are technical grade product.Surface tension is measured by surface tension instrument, and critical micelle concentration is tried to achieve by measuring the relation curve of surface tension and concentration.Below for surface tension and the critical micelle concentration data of the made part surface activating agent of the present invention.
The lowest surface tension of all compounds prepared by the present invention all below 20.2mN/m, minimum only 15.2mN/m, close with the lowest surface tension (≤16.0mN/m) of PFOA and PFOS analog derivative.Comparatively speaking, similar structures but non-double type kind are as N-[3-(to perfluorinated nonene oxygen base benzene sulfonamido) propyl group] lowest surface tension of-DMG inner salt is 24.3mN/m, critical micelle concentration is 6.0 * 10
-5mol/L.Visible, by the Shuangzi of perfluor alkene type surfactant, can effectively improve surface-active.
The technical staff of the industry should understand, and the present invention is not restricted to the described embodiments, and what in above-described embodiment and description, describe is for principle of the present invention is described.Without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these all fall in the scope of protection of present invention.
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| CN111117787A (en) * | 2019-12-23 | 2020-05-08 | 万华化学集团股份有限公司 | Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent |
| CN115448999A (en) * | 2022-09-28 | 2022-12-09 | 国家电投集团氢能科技发展有限公司 | High-stability modified perfluorinated anion exchange resin and preparation method and application thereof |
| CN115572339A (en) * | 2022-09-28 | 2023-01-06 | 国家电投集团氢能科技发展有限公司 | Ion-modified perfluorinated anion resin and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103657513B (en) | 2015-06-17 |
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