CN102921347A - Preparation method and application of quaternary ammonium salt surfactant containing branch-type fluorocarbon chain - Google Patents
Preparation method and application of quaternary ammonium salt surfactant containing branch-type fluorocarbon chain Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a quaternary ammonium salt surfactant containing a branch-type fluorocarbon chain, synthesis and application of [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-buteneoxy)benzenesulfonamido]ethyltrimethylammonium iodide, and a preparation method of the surfactant. The research on the surface tension, interfacial tension, contact angles, water and oil repellency, oil displacement and other surface performance of the surfactant prove that the quaternary ammonium salt surfactant has low surface tension and interfacial tension and excellent water and oil repellency and has certain oil displacement after being compounded.
Description
(1)
Technical field
The present invention relates to the synthetic and uses thereof of a kind of quaternary ammonium salt cationic surfactant [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] oxypropyl trimethyl ammonium iodide that contains branch type fluorocarbon chain.
(2)
Background technology
Fluorine-containing surfactant is owing to having a characteristic of " three height, two are hated ", and along with demand international, the domestic market increases day by day, the fluorine-containing surfactant excellent performance, with high content of technology, added value is large, causes domestic and international researcher's very big interest.Its fluorine-containing alkyl has water and oil repellant [new chemical materials, 2004,32 (8): 46], is widely used in industry and the agriculture fields [household chemicals, 2011,41 (4): 40-43] such as oil, coal, mining and metallurgy, machinery, weaving, medicine.
Fluorine-containing surfactant is divided into: cation, anion, nonionic, both sexes etc., wherein cation is one of important kind, mainly be divided into amine salt type and quaternary two classes [fluorocarbon surfactant [M]. Beijing, Chemical Industry Press, 2001,6]; Its hydrophilic radical both can be quaternary ammonium salt cationic [fine chemistry industry, 2012,6:554-559], also can be amido [dyestuff and dyeing, 2006,43, (1): 31-33]; The hydrophobic group group generally also has common hydrocarbon chain except fluorine-containing carbon-chain structure; Containing the fluorocarbon chain major part is the straight chain of 6-10 carbon atom.
The novel molecular structure continues to bring out, the simultaneously application of fluorine-containing surfactant has also broken through traditional field gradually, has 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 [the Tomokazu Yoshimura that in succession is in the news, Langmuir, 2006,22,4643-4648; R. Kapla ' nek, Journal of Fluorine Chemistry, 2009,130:308-316; Y.X. Wang, Journal of Fluorine Chemistry, 2011,132:489-494].
The developed countries such as the U.S., West Europe, Japan develop this series products in succession, as: Dupont, Britain ICI, French Atochem, German Hoechst and Bayer, Switzerland Ciba-Geigy and the companies such as Japan AGC, Da Jin and Neos have the international market more than 80%.With abroad compare, China's fluorine-containing surfactant, all relatively weaker no matter on production capacity, or in study on the synthesis, application study.
Take the Fluorine containing olefine that obtains by the oligomerisation method as raw material, overcome the shortcomings such as electrofluorination method, telomerization method energy consumption are large, expensive, can for the preparation of branch type fluorine-containing surfactant, have synthetic simple, cost is low, the cost performance high.At present, there is no such branch type fluorine-containing cationic surfactant of bibliographical information.
(3) summary of the invention
The object of the present invention is to provide a kind of quaternary ammonium salt cationic surfactant [N-methyl-N-(4-perfluor-(1 that contains branch type fluorocarbon chain, the 3-dimethyl-2-isopropyl)-and the 1-butenyloxy) benzene sulfonamido] preparation method and the application thereof of oxypropyl trimethyl ammonium iodide, the present invention has excellent surface-active.
Structural formula of the present invention is as follows:
The above-mentioned preparation method who contains the quaternary ammonium salt cationic surfactant of branch type fluorocarbon chain comprises the steps:
In the fluorine-containing phenyl ether solution of branch type, add sulfonylation agent, remove excessive sulfonylation agent after the reaction after, obtain containing the sulfonic acid chloride of branch type fluorocarbon chain; Further with N, N, N '-trimethyl propane diamine base obtains containing the sulfonamide of branch type fluorocarbon chain; Obtain containing at last the quaternary ammonium salt cationic surfactant of branch type fluorocarbon chain with the methylating reagent reaction.
The reaction equation of described reaction is:
Substantive distinguishing features of the present invention can be achieved from following examples of implementation, but these examples of implementation only as an illustration, rather than limits the invention.
(4) description of drawings
Fig. 1 is aqueous solution surface tension and the concentration logarithmic curve of embodiment
(5) specific implementation method:
The preparation of example 1:4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzene sulfonyl chloride
Add 50 mL acetonitriles in the four-hole boiling flask of 100mL, the fluorine-containing phenyl ether of branch type (0.97 g, 0.05 mol) is heated with stirring to backflow, slowly drips chlorosulfonic acid (0.97 g, 0.05 mol), and approximately 30 min continue reaction 5 h.Reaction is left standstill and is cooled to room temperature after finishing, and pours in the 250 mL frozen water, tells organic phase, with 3*50 mL ethyl acetate extraction water, spends the night with anhydrous sodium sulfate drying, merges, and removal of solvent under reduced pressure obtains viscous liquid; Ethyl acetate-benzinum recrystallization obtains white crystal, yield 70 %, fusing point: 53.0-54.1 ℃.IR(cm
1)：υ(C=C)1594; υ(C-O)1241, υ(C-F)1184,1132,1042,1010；
1H-NMR (CDCl
3)δ: 7.28(t,2H,ArH),7.20(t, 1H, ArH),6.92(d,2H,ArH)；ESI-MS: 622.68。
Example 2:N-methyl-N-[2-(dimethylamino) propyl group]-preparation of 4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy benzsulfamide
In the four-hole boiling flask of 100mL, add the product (3.11 g, 0.005mol) that example 1 obtains, Anhydrous potassium carbonate (0.69 g, 0.005mol) be dissolved in 40 mL acetonitriles, stirring is warming up to backflow, slowly drips N, N, N '-trimethyl propane diamine (0.57 g, 0.005mol) acetonitrile (20mL) solution, about 30 min continue reaction 6 h.Reaction is left standstill and is cooled to room temperature after finishing, and the solids removed by filtration residue obtains yellow solution, use activated carbon decolorizing, removal of solvent under reduced pressure obtains white thick material, crosses post with ethyl acetate-benzinum, obtain white solid, yield 78 %, fusing point: 62.0-62.9 ℃.IR(cm
1): υ(N-H) 3426,υ(C=C) 1590,1300, υ(C-O)1242,υ(S=O)1014,υ(C-F) 979,734；
1H-NMR (DMSO-
d 6 )δ:7.94 (d,2H,ArH),7.36(d,2H,ArH),2.88(t,2H,CH
2),2.19 (t,2H, CH
2),2.01(s,9H, CH
3),1.85(m,2H,CH
2)；ESI-MS: 702.08。
Example 3:[N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] preparation of oxypropyl trimethyl ammonium iodide
In the four-hole boiling flask of 100mL, add the product (3.44 g, 0.005 mol) that example 2 obtains, be dissolved in 50 mL DMF, stir and be warming up to 70 ℃, slowly drip iodomethane (1.42 g, 0.01 DMF(10mL mol)) solution, approximately 30 min continue reaction 5 h.Reaction is left standstill and is cooled to room temperature after finishing, and removal of solvent under reduced pressure obtains yellow thick liquid; After the methyl alcohol dissolving, activated carbon decolorizing, after the desolventizing, use ethyl acetate: benzinum (7:3) is crossed post, obtains white solid, productive rate 75 %, fusing point: 213.0-214.2 ℃; IR (cm
1): υ (N-H) 3446, υ (C=C) 1626,1590,1491, υ (C-O) 1242, υ (S=O) 1014, υ (C-F) 1240,979,742;
1H-NMR (CDCl
3) δ: 8.00 (d, 2H, ArH), 7.28 (d, 2H, ArH), 3.82 (m, 2H, CH
2), 3.25 (m, 2H, CH
2), 2.52 (s, 12H, CH
3), 1.97 (m, 2H, CH
2); ESI-MS:844.01.
Example 4 surface tension tests (hanging the sheet method)
Measure with hanging the sheet method, claim again Wilhelmy to hang the 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 that contends with surface tension of sheet disengaging liquid.Hang the 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 table 1, can draw its critical micelle concentration is 4.5 * 10
-4Mol/L, the at this moment surface tension (γ of its aqueous solution
CMC) be 20. 8 mN/m(pure water surface tension, 71.0 mN/m), see Fig. 1.
Example 5 interfacial tensions tests (adopting platinum plate method)
Interfacial tension refers to vertically act on along interface between immiscible two-phase (liquid-solid, liquid-liquid, liquid-gas) the surperficial convergent force on the 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.Different from surface tension, be in the molecule of boundary layer, be subject on the one hand body mutually in the effect of same substance molecule, another that is subject on the other hand different in kind mutually in effect of material molecule, its active force may not necessarily be cancelled out each other.Therefore interfacial tension wants specific surface tension much smaller usually.The branch type is the fluorine surfactant 1 % aqueous solution also, and its pH is 7.9, can be fully water-soluble.0.1% solution interface tension force is: 0.35 mN/m.
The test of example 6 contact angles
When a drop of liquid dropped on the fabric face, possible complete wetting fabric formed water membrane on the surface, might form drops, and drop edge and the surface of solids form an angle theta, and this angle just is called contact angle.When 0 °＜θ＜90 °, liquid part wet fabric, and within the extremely short time, drop to around diffusion and infiltrating in the fabric, in the time of 90 °＜θ＜180 °, liquid can not the wet fabric surface and form the liquid pearl, drop tumbles during inclination.Reach the purpose of refusing water, contact angle θ will be the bigger the better.According to famous Young equation: γ S=γ SL+γ Lcos θ, the contact angle that liquid forms at the surface of solids and the relation between the interfacial tension are as can be known, because surface tension of liquid is constant, reach the purpose of refusing water, just must reduces solid surface tension or make the solid-liquid surface tension become large.See Table 1.
Table 1 arrangement rear surface water contact angle
| Sample | Water contact angle (°) |
| Synthetic leather | 99.5 |
| Cotton | 94.3 |
| Glass | 111.0 |
Example 7 water and oil repellant property testings
Refuse oily principle and to refuse the water principle very similar, all be to change fabric, fiber surface performance, its critical surface tension is reduced, and the contact angle that water and oil are larger with its generation reaches the purpose of water and oil repellant, and don't affects the gas permeability of fabric.
In the detection, the water rank of refusing of fabric is tested, generally use the trickle performance test methods.Carry out according to the sampling, operation sequence, the evaluation that require among the GB/T4745-1997 " textile fabric surface moisture resistance is measured to get wet and pressed test ", the warp-wise of fabric is parallel with water (flow) direction, test respectively wash front, wash rear sample refuse the water rank; Refuse the test of wet goods level and adopt method in GB/T19977-2005 " the anti-hydrocarbon test of the textile oil repellent " standard.At first be the experimental liquid with lowest number, carefully drip on fabric with 0.05 mL liquid, if in 30 s without infiltration and wetting phenomena generation, then and then drip on fabric with the experimental liquid of higher number.Experiment is carried out continuously, until experimental liquid is in 30 s till the fountain solution side of dripping and on every side the fabric.The wet goods level of refusing of fabric represents with the experimental liquid of high numbering that can not wet fabric in 30 s.The results are shown in Table 2.
Table 2 fabric is refused water, oil repellent test
| Sample | Solvent | Refuse the water rank | Refuse oily rank | The clear situation of spot | |
| | Acetone | 5 | 2 | Easy cleaning | |
| Synthetic | Isopropyl alcohol | 5 | 1.5 | Easy | |
| Cotton | Acetone | ||||
| 6 | 1.5 | Easy cleaning | |||
| | Isopropyl alcohol | 5 | 1.5 | Easy cleaning |
Example 8 displacement of reservoir oil property testings
There is for a long time a kind of traditional concept, thinks that namely cationic surfactant and anion surfactant can not mix in the aqueous solution, otherwise will lose surface-active or generate precipitation.But studies show that afterwards, anion surfactant and cationic surfactant can compositely use under the felicity condition, can not produce precipitation or lose surface-active.Owing to not only there not being the repulsion between the identical charges of ion head in the single surfactant situation when anion surfactant and cationic surfactant form mixed micelle in solution, and the gravitation between the negative ions has promoted two kinds of interionic associations, therefore make mixed micelle tightr, interfacial activity improves.In alkylbenzenesulfonate, add a certain amount of [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] oxypropyl trimethyl ammonium iodide, interfacial tension is studied discovery, such as table 3.
The adding of table 3 fluorine-containing cationic surfactant is on the impact of alkylbenzenesulfonate interfacial tension
Can find out, because the adding of fluorine-containing cationic surfactant improves the interfacial activity of alkylbenzenesulfonate.Because the gravitation when anion surfactant and cationic surfactant form mixed micelle in solution between the negative ions makes micella tightr, the Interfacial Adsorption amount increases, thereby interfacial activity improves.
Claims (6)
1. one kind suc as formula the quaternary ammonium salt cationic surfactant that contains the branch fluorocarbon chain shown in the I [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] oxypropyl trimethyl ammonium iodide:
I。
2. the preparation method suc as formula [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] the oxypropyl trimethyl ammonium iodide shown in the I as claimed in claim 1 is characterized in that described method is:
R
fFor
With
IIBe raw material to perfluorobuttene oxygen base phenyl ether, at organic solvent
1In, in-10 ~ 100 ℃ of reaction 1 ~ 5 h, after reaction finished, organic phase was told in washing, obtained crude product after the decompression and obtained perfluorobuttene oxygen base benzene sulfonyl chloride derivative with the double solvents recrystallization; At solvent
2In, add Fu's acid agent, N, N, N '-trimethyl propane diamine carries out aminolysis reaction in 0 ~ 100 ℃, goes out solid residue after the end, obtains N-methyl-N-(dimethylamino-propyl) after the removal of solvent under reduced pressure to perfluorobuttene oxygen base benzsulfamide; It is dissolved in solvent
3, carry out quaterisation in 0 ~ 100 ℃, obtain [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] oxypropyl trimethyl ammonium iodide;
Described solvent
1For one of following: carrene, chloroform, carbon tetrachloride, acetonitrile, dichloroethanes;
Described solvent
2For one of following: 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 solvent
3For one of following: acetonitrile, DMF, benzene,toluene,xylene, carrene, chloroform, carbon tetrachloride, ethyl acetate, benzinum, dimethyl sulfoxide (DMSO), cyclohexanone, acetone, butanone;
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, it is characterized in that described to perfluoro alkene oxygen base benzene sulfonyl chloride, N, N, the molar ratio of N '-trimethyl propane diamine, base catalyst, iodomethane is: 1:1.0 ~ 2.0:1.0 ~ 3.0:1 ~ 3.0.
4. method as claimed in claim 2 is characterized in that 0 ~ 100 ℃ of described amidation process temperature, reaction time 2 ~ 10 h.
5. the method for claim 1 is characterized in that 0 ~ 100 ℃ of described quaterisation temperature, reaction time 2 ~ 10 h.
6. application as claimed in claim 5, it is characterized in that [N-methyl-N-(4-perfluor-(1,3-dimethyl-2-isopropyl)-1-butenyloxy) benzene sulfonamido] oxypropyl trimethyl ammonium iodide is as surface property research and the application of the quaternary ammonium salt cationic surfactant that contains branch type fluorocarbon chain.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432959A (en) * | 2013-09-18 | 2013-12-11 | 华中师范大学 | Surface active agent containing hexafluoropropylene tripolymer group and preparation method thereof |
| CN103464049A (en) * | 2013-09-18 | 2013-12-25 | 华中师范大学 | Perfluorohexyl sulfonyloxy benzyl cation surfactant as well as preparation method and application thereof |
| CN103721626A (en) * | 2013-12-11 | 2014-04-16 | 浙江工业大学 | Synthesis and application of reticular non-ionic surfactant containing fluorine |
| CN110257039A (en) * | 2019-07-16 | 2019-09-20 | 上海建鸿实业有限公司 | A kind of terrestrial facies shale pressure break modifying agent and preparation method |
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| CN110257039A (en) * | 2019-07-16 | 2019-09-20 | 上海建鸿实业有限公司 | A kind of terrestrial facies shale pressure break modifying agent and preparation method |
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