CN105481744A - CO2/N2-H2O2 dual-stimulation response surfactant and preparation method thereof - Google Patents
CO2/N2-H2O2 dual-stimulation response surfactant and preparation method thereof Download PDFInfo
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- CN105481744A CN105481744A CN201510831798.9A CN201510831798A CN105481744A CN 105481744 A CN105481744 A CN 105481744A CN 201510831798 A CN201510831798 A CN 201510831798A CN 105481744 A CN105481744 A CN 105481744A
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- active agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
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Abstract
The invention discloses a CO2/N2-H2O2 dual-stimulation response surfactant and a preparation method thereof. CO2 is introduced to a surfactant to form a bicarbonate cationic surfactant, N2 is introduced to decompose the surfactant to lose surface activity, H2O is added to the surfactant to oxidize in order to form a selenium oxide, vitamin C is added to reduce the selenium oxide into the initial surfactant, so the surfactant has CO2/N2-H2O2 dual-stimulation responsiveness.
Description
(1) technical field
The present invention relates to a class CO
2/ N
2-light double stimuli responsive type tensio-active agent and preparation method thereof, belongs to Colloid and interface chemistry field.
(2) background technology
The regulation and control of the structure of surfactant molecule and aggregate thereof, character and function are one of focuses of current research.Traditional regulate and control method is generally by changing temperature or adding chemical agent as acid, alkali, salt and cosurfactant etc., the latter inevitably increases discharge and the pollution of chemical substance, and is difficult to realize reversible regulation and control and is separated with the easy of tensio-active agent.Therefore development of new, efficient, easy, eco-friendly green hue control method have great importance.Therefore, environmental stimulus response type tensio-active agent just arises at the historic moment.
The corresponding type tensio-active agent of so-called environmental stimulus is exactly by certain chemistry or electrochemical method, the structural changes of surfactant molecule in the induction aqueous solution, thus makes the surface tension of solution occur significantly to change; Correspondingly, some macro surface character of system also changes thereupon.The corresponding type tensio-active agent of environmental stimulus can experience reversible transformation between excited state form and nonexcitation state form, and its outside stimulus mainly passes through CO
2the means such as/air, electrochemical action, photochemical effect, temperature, soda acid realize.Due to this feature, the "on" and "off" of by-pass cock tensio-active agent, makes the regeneration of tensio-active agent become easy, thus makes the application cost of reduction tensio-active agent in environment remediation and industrial production become possibility.
But the exact controllability of present high-technology field Surfactant application will be met, also there is certain limitation in current research, such as the CO of current most application prospect
2/ N
2surfactant, although it has CO
2/ N
2regulate and control method is gentle, cheap and environmentally friendly, and makes tensio-active agent to be easy to from aqueous phase the series of advantages such as separation, recovery, but its application in drug delivery is restricted.And at CO
2/ N
2introducing the second sensitive group in surfactant can make the stuctures and properties of surfactant molecule also can obtain secondary regulation and control to a certain extent, thus realizes Surfactant and regulate and control more accurately.This novel regulate and control method has potential Research Prospects in drug conveying, self-assembly etc.Can at the H of lower concentration containing Se tensio-active agent
2o
2the change of recurring structure under condition, therefore it can produce response to multiple stimulus signal, not only gives tensio-active agent more function, also can adapt to the application widely in high-tech sector.
(3) summary of the invention
The present invention relates to a kind of CO
2/ N
2?H
2o
2double stimuli responsive type tensio-active agent, its structural formula is as follows:
Wherein, R
1to be carbon element be 1 ~ 6 any one alkyl; R
2any one alkyl of to be carbon element be 6-18; R
3to be carbon element be 1 ~ 3 any one alkyl.
As Fig. 1, this tensio-active agent is passing into CO
2time form supercarbonate cationic surfactant, pass into N
2time surfactant decomposes generate alkylamine, lose surfactivity; As Fig. 2, this tensio-active agent adds H
2o
2time be oxidized to selenolite compound, when adding vitamin C, this selenolite compound can be reduced to tensio-active agent original state, and namely this tensio-active agent has CO
2/ N
2-H
2o
2stimuli-responsive.
Above-mentioned CO
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent is preparation method comprise the following steps:
(1) substitution reaction: monosubstituted for N-alkyl alcoholamine is dissolved in ethanol, add alkali, 50 ~ 78 DEG C are warming up to when magnetic agitation, slow dropping brominated alkanes, reaction overnight, after reaction terminates, except desolventizing, after washing, underpressure distillation obtains substitution product, wherein the monosubstituted alkyl alcoholamine of N-is N-monomethyl-ethanolamine, the mono-ehtylethanolamine of N-, the mono-propyl group thanomin of N-, N-monobutyl ethylethanolamine, the mono-hexyl ethylethanolamine of N-, N-monomethyl Propanolamine, one or both mixtures in N-monomethyl butanolamine, alkali is sodium carbonate, salt of wormwood, sodium hydroxide, one or both mixtures in potassium hydroxide,
(2) chlorination: be dissolved into by substitution product in methylene dichloride, slowly drips sulfur oxychloride under the condition of stirring at room temperature, and reaction terminates rear underpressure distillation, obtains chloro-product;
(3) selenium reaction is joined: dissolved in deionized water by reductive agent, in nitrogen protection, slowly be added drop-wise in the aqueous solution of selenium powder under room temperature condition, obtain the sodium selenide solution of reddish-brown, add the N of chloro-product gradually, dinethylformamide solution, 20 ~ 100 DEG C of reactions 8 ~ 48 hours under protection of inert gas, after reaction terminates, reaction solution is poured in deionized water, use dichloromethane extraction product, target product is obtained after removing methylene dichloride, wherein reductive agent is sodium borohydride, POTASSIUM BOROHYDRIDE, zinc powder, one or both mixtures in magnesium, rare gas element is nitrogen, one or both mixed gass of argon gas.
Beneficial effect of the present invention:
Tensio-active agent of the present invention has CO
2/ N
2and H
2o
2stimuli-responsive energy, and there is good surface property, synthetic method is simple, and product purity is higher.
(4) accompanying drawing explanation
Accompanying drawing 1 is CO
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent is passing into CO
2and N
2the change that rear structure occurs;
Accompanying drawing 2 is CO
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent is adding H
2o
2with the change that structure after vitamin C occurs;
Accompanying drawing 3 is the mass spectrum of two dodecyl methyl tertiary amine selenide, and wherein m/z533 is [M+H] of target product
+peak, m/z228 is the fragment peak of target product, and m/z244 is N-monomethyl-ethanolamine peak;
Accompanying drawing 4 is the nucleus magnetic hydrogen spectrum figure of two dodecyl methyl tertiary amine selenide, wherein
1hNMR (400MHz, DMSO) δ 3.453 (br, 4H), 2.664 (br, 6H), 2.356 (t, 4H), 2.268 (d, 2H), 1.270 (s, 40H), 0.892 (t, 6H);
Accompanying drawing 5 is that the water/ethanolic soln specific conductivity of two dodecyl methyl tertiary amine selenide is with CO
2/ N
2change.
(5) embodiment
Embodiment 1: the synthesis of the two dodecyl methyl tertiary amine selenide of surfactant-intermediate
(1) synthesis of dodecyl methyl thanomin:
Get the there-necked flask that 35.591g (0.5mol) 4-N-monomethyl-ethanolamine and 11.66g (0.11mol) join 250ml, add 100ml ethanol, be warming up to 50 DEG C, 24.9g (0.1mol) bromododecane is dripped in there-necked flask, reaction overnight by constant pressure funnel.Revolve and steam removing etoh solvent, washing removing inorganic salt and excessive N-monomethyl-ethanolamine, anhydrous magnesium sulfate desalination, fractionation obtains pure dodecyl methyl thanomin transparent liquid;
(2) synthesis of Chloroethyl dodecyl methyl tertiary amine:
The dodecyl methyl thanomin taking 24.3g joins in 250ml there-necked flask, add 100ml methylene dichloride, take 11.897g sulfur oxychloride constant pressure funnel to be slowly added drop-wise in there-necked flask, by mixture magnetic agitation, under room temperature condition, reaction 12h, carrys out following response process with silica gel chromatography.After reaction terminates, revolve and steam removing methylene dichloride and excessive sulfur oxychloride, anhydrous diethyl ether washing solid three times. use methylene dichloride lysate, aqueous sodium hydroxide solution washing methylene dichloride three times, deionized water wash three times, anhydrous magnesium sulfate desalination, revolves and steams removing methylene dichloride, obtain Chloroethyl dodecyl methyl tertiary amine;
(3) synthesis of two dodecyl methyl tertiary amine selenide
0.2771g sodium borohydride is dissolved in 10ml deionized water, in nitrogen protection, is slowly added drop-wise in the aqueous solution of 0.2718g selenium powder under room temperature condition, be warming up to the complete solvent of selenium powder after reaction for some time, obtain the sodium selenide solution of reddish-brown.1.8g Chloroethyl dodecyl methyl tertiary amine is dissolved in 20DMF, joins in sodium selenide and react 48h under the condition of 50 DEG C of nitrogen protections; After reaction terminates, reaction solution is poured in deionized water, use dichloromethane extraction product, anhydrous magnesium sulfate is except the water in methylene dichloride, the filtrate of suction filtration, revolve and steam removing methylene dichloride, silica gel chromatography is separated the brown oil obtaining two dodecyl methyl tertiary amine selenides.
Embodiment 2:CO
2/ N
2switch
Conductivity test proves CO at present
2/ N
2one of surfactant switch and the reversible reliable method of switch, pass into CO by water/ethanol (1:1) solution of surfactant-intermediate
2, survey the specific conductivity of its solution at set intervals, when specific conductivity does not change, pass into N
2survey the specific conductivity of solution equally at set intervals.Tensio-active agent passes into CO
2and N
2conductivity variations see accompanying drawing 5.
Claims (6)
1. a CO
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent, this tensio-active agent is passing into CO
2time form supercarbonate cationic surfactant, pass into N
2time surfactant decomposes, lose surfactivity, tensio-active agent adds H
2o
2time be oxidized to selenolite compound, when adding vitamin C, this selenolite compound can be reduced to tensio-active agent original state, and namely this tensio-active agent has CO
2/ N
2-H
2o
2stimuli-responsive, the structure of this tensio-active agent is:
Wherein, R
1to be carbon element be 1 ~ 6 any one alkyl; R
2any one alkyl of to be carbon element be 6-18; R
3to be carbon element be 1 ~ 3 any one alkyl.
2. CO according to claim 1
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent preparation method, comprises the following steps:
(1) substitution reaction: monosubstituted for N-alkyl alcoholamine is dissolved in ethanol, adds alkali, be warming up to 50 ~ 78 DEG C when magnetic agitation, slow dropping brominated alkanes, reaction overnight, after reaction terminates, except desolventizing, after washing, underpressure distillation obtains substitution product;
(2) chlorination: be dissolved into by substitution product in methylene dichloride, slowly drips sulfur oxychloride under the condition of stirring at room temperature, and reaction terminates rear underpressure distillation, obtains chloro-product;
(3) selenium reaction is joined: dissolved in deionized water by reductive agent; in nitrogen protection; slowly be added drop-wise in the aqueous solution of selenium powder under room temperature condition, obtain the sodium selenide solution of reddish-brown, add the N of chloro-product gradually; dinethylformamide solution; 20 ~ 100 DEG C of reactions 8 ~ 48 hours under protection of inert gas, after reaction terminates, reaction solution is poured in deionized water; use dichloromethane extraction product, after removing methylene dichloride, obtain target product.
3. CO according to claim 2
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent preparation method, it is characterized in that: the monosubstituted alkyl alcoholamine of described N-is N-monomethyl-ethanolamine, the mono-ehtylethanolamine of N-, the mono-propyl group thanomin of N-, N-monobutyl ethylethanolamine, the mono-hexyl ethylethanolamine of N-, N-monomethyl Propanolamine, one or both mixtures in N-monomethyl butanolamine.
4. CO according to claim 2
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent preparation method, is characterized in that: described alkali is sodium carbonate, salt of wormwood, sodium hydroxide, one or both mixtures in potassium hydroxide.
5. CO according to claim 2
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent preparation method, is characterized in that: described reductive agent is sodium borohydride, POTASSIUM BOROHYDRIDE, zinc powder, one or both mixtures in magnesium.
6. CO according to claim 2
2/ N
2-H
2o
2double stimuli responsive type tensio-active agent preparation method, is characterized in that: described rare gas element is nitrogen, one or both mixed gass in argon gas.
Priority Applications (1)
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|---|---|---|---|
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| CN201510831798.9A CN105481744B (en) | 2015-11-25 | 2015-11-25 | CO2/N2‑H2O2Double stimuli responsive type surfactant and preparation method thereof |
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| CN105481744B CN105481744B (en) | 2017-03-29 |
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Cited By (6)
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|---|---|---|---|---|
| CN106589001A (en) * | 2016-12-06 | 2017-04-26 | 江南大学 | Ferrocenyl double stimulation responsive surfactant |
| CN107435532A (en) * | 2016-05-27 | 2017-12-05 | 中国石油化工股份有限公司 | One kind utilizes CO2Response surface activating agent controls CO2The method that purging is altered |
| CN108940116A (en) * | 2018-07-04 | 2018-12-07 | 江南大学 | A kind of Gemini surface active agent and preparation method thereof of the interval base containing selenium atom |
| CN110302717A (en) * | 2018-12-19 | 2019-10-08 | 江南大学 | A method of utilizing the Krafft temperature for adjusting pH method regulation surfactant |
| CN110302718A (en) * | 2018-12-20 | 2019-10-08 | 江南大学 | A method of utilizing the Krafft temperature of oxidation-reduction method regulation surfactant |
| CN114181716A (en) * | 2021-10-19 | 2022-03-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107435532A (en) * | 2016-05-27 | 2017-12-05 | 中国石油化工股份有限公司 | One kind utilizes CO2Response surface activating agent controls CO2The method that purging is altered |
| CN106589001A (en) * | 2016-12-06 | 2017-04-26 | 江南大学 | Ferrocenyl double stimulation responsive surfactant |
| CN106589001B (en) * | 2016-12-06 | 2019-11-08 | 江南大学 | A kind of ferrocenyl double stimuli responsive type surfactant |
| CN108940116A (en) * | 2018-07-04 | 2018-12-07 | 江南大学 | A kind of Gemini surface active agent and preparation method thereof of the interval base containing selenium atom |
| CN110302717A (en) * | 2018-12-19 | 2019-10-08 | 江南大学 | A method of utilizing the Krafft temperature for adjusting pH method regulation surfactant |
| CN110302718A (en) * | 2018-12-20 | 2019-10-08 | 江南大学 | A method of utilizing the Krafft temperature of oxidation-reduction method regulation surfactant |
| CN114181716A (en) * | 2021-10-19 | 2022-03-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction |
| CN114181716B (en) * | 2021-10-19 | 2023-08-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application thereof in Suzuki reaction |
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