CN104725268B - CO2/N2-light dual-stimulus-response type surfactant and synthesizing method - Google Patents
CO2/N2-light dual-stimulus-response type surfactant and synthesizing method Download PDFInfo
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Abstract
The invention relates to a CO2/N2-light dual-stimulus-response type surfactant, and belongs to the field of colloid and interfacial chemistry. The surfactant is an azobenzene bicarbonate surfactant prepared by using 4-alkylaniline and phenol as raw materials by means of diazotization, substitution reaction, ammoniation and introduction of carbon dioxide. The surfactant has excellent surfactant performance, has response to ultraviolet ray and visible light, as well as CO2 and N2, namely having double response.
Description
(1) technical field
The present invention relates to a kind of co2/n2- light double stimuli responsive type surfactant, belongs to Colloid and interface chemistry neck
Domain.
(2) background technology
The regulation and control of the structure of surfactant molecule and its aggregation, property and function are one of focuses of current research.
Traditional regulation and control method generally by change temperature or adds chemical agent such as acid, alkali, salt and cosurfactant etc., after
Person inevitably increases discharge and the pollution of chemical substance, and is difficult to reversible regulation and control and the simplicity of surfactant
Separate.Therefore develop new, efficient, easy, eco-friendly green hue prosecutor method to have great importance.Therefore, environment thorn
Sharp response type surfactant just arises at the historic moment.
The corresponding type surfactant of so-called environmental stimuluses is it is simply that by the method for certain chemistry or electrochemistry, induce water
The structure change of surfactant molecule in solution, so that the surface tension of solution is widely varied；Correspondingly, system
Some macro surface properties also change therewith.Environmental stimuluses corresponding type surfactant can be in excited state form and non-
Can experience inverible transform between excited state form, adjust the "on" and "off" of switch surfactant so that surfactant
Regeneration becomes easy, so that reducing application cost in environment remediation and commercial production for the surfactant to become possibility.
But the exact controllability that present high-technology field Surfactant is applied will be met, current research is also deposited
In certain limitation, document report is mainly substance stimuli responsive type surfactant, dual or multiple stimulation response type surface
The report of activating agent is less.The co of such as current most application prospect2/n2Surfactant is although it has co2/n2
Regulation and control method is gentle, cheap and environmentally friendly, and it is a series of excellent to make surfactant be easy to separation, recovery etc. from aqueous phase
Point, but this kind of surfactant can only be realized changing between hydrophilic group "ON" and "Off" two states, its hydrophobic base section
Lack regulation and control, therefore can not carry out finer regulation and control to its self-organizing structures, wettability of particle surface etc..And in co2/n2
Second sensitive group is introduced so that the hydrophobic base section of surfactant molecule also can be in surfactant
Obtain two grades of regulation and control to a certain extent, thus realize Surfactant more accurately regulating and controlling.This new regulation and control method
At aspects such as chemical reaction, materials synthesis, there are potential Research Prospects.Because the response group such as ph, temperature, oxidation-reduction is big
All it is directed to hydrophilic group, the photoresponse group being therefore directed to hydrophobic group becomes the first-selection of secondary response group.
(3) content of the invention
The purpose of the present invention is that design synthesis has to light and co2/n2The surfactant of dual responsiveness, investigates its light
And co2/n2Dual responsiveness, this surfactant has as follows a clearly molecular structure:
R in above formula1=h or c1～c12Alkyl；r2=c1～c16Alkyl；r3=c1～c4Alkyl.
Beneficial effects of the present invention: above formula surfactant occurs suitable under ultraviolet light (uv) and visible ray (vis) illumination
Anteiso- structure, surface tension, geometry arrangement parameter etc. change, and the macro surface property of system also changes therewith, that is, right
Photoresponse；Above formula surfactant is being passed through n2Or during heating, resolve into the oiliness compound of surfactant-free, be passed through co2Afterwards
Regenerate bicarbonate cationic surfactant, that is, to co2/n2Response.Therefore this surfactant has to light and co2/
n2Double-response performance.Surfactant can produce response to multiple stimulus signals, not only gives surfactant more
Function, also adapts to the wider application in the high-tech sectors such as chemical reaction, materials synthesis.
This photo absorption property is investigated with the ultra-violet absorption spectrum (as schemed) of this surfactant and surface tension, with 4- fourth
As a example base -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide bicarbonate, such as Fig. 3～6, surfactant is in ultraviolet light
(uv) there is large change, critical micelle concentration (cmc) 2.29*10 of surfactant in illumination front and rear surfaces tension force-4Mol/l becomes
For 2.33*10-3mol/l；As Fig. 9～11, the absorbance generation at λ=350nm of ultraviolet light (uv) illumination front and rear surfaces activating agent
Reversible change.
co2/n2Performance is investigated with the electrical conductivity of this surfactant, with 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide
Amine) as a example diphenyl diimide bicarbonate, such as Fig. 8, when surfactant decomposes, electrical conductivity declines, and is passed through co2Generate surface activity afterwards
Agent, electrical conductivity raises.
The synthetic method of described surfactant, synthesis step is:
(1) diazo coupling reaction: 4- alkyl benzene amine is in -10～10 DEG C of hydrochloric acid adding mol ratios 1～4, nano2, mix
After compound reacts 0.5～3 hour, the phenol of mol ratio 1～2 is dissolved in mol ratio 1～3, mass content 10～90%na2co3Molten
In liquid, with constant pressure funnel, mixed liquor is added drop-wise in said mixture, reacts 1～5 hour, by product vacuum sucking filtration, vacuum is done
Dry, obtain 4- alkyl -4 ' hydroxyazobenzene；
(2) substitution reaction: by two bromoalkanes of 4- alkyl -4 ' hydroxyazobenzene and mol ratio 1～3 and mol ratio 1～3
K2co3In, 30～100 DEG C of reaction temperature, react 8～24 hours；, after reaction terminates, filter, filtrate obtains after removing solvent
Substitution product；
(3) aminating reaction: substitution product is added in the dialkylamine solution of mol ratio 1～10, add mol ratio 1～
5 k2co3In, react 24h at 10～60 DEG C, reaction is filtered after terminating, and filtrate obtains aminate after being evaporated；
(4) aminate is passed through carbon dioxide, generates bicarbonate surfactant, target product through recrystallization or
Pure compound is obtained after the purification of person's column chromatography.
, synthetic reaction formula is as follows taking 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide bicarbonate as a example:
Surfactant-intermediate 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) azo of the present invention of the present invention
The synthetic method of benzene is simple, and the product purity of synthesis is very high, and the surfactant that it forms has good surface property, and
To co2/n2There is stimuli-responsive energy with light.
(5) brief description
Accompanying drawing 1 is the LC-MS figure of 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide
Wherein m/z 354.2 is [m+h] of target product+Peak, m/z 100.1 is 4- butyl -4 '-(4-n, n- dimethyl
Butoxy amine) diphenyl diimide fragment peak.
Accompanying drawing 2 is the nucleus magnetic hydrogen spectrum figure of 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide
Wherein1H nmr (400mhz, dmso) δ 7.86 (d, j=8.9hz, 2h), 7.76 (d, j=8.3hz, 2h), 7.38
(d, j=8.3hz, 2h), 7.11 (d, j=9.0hz, 2h), 4.08 (s, 2h), 2.66 (s, 2h), 2.25 (s, 2h), 2.11 (d, j
=12.4hz, 6h), 1.76 (s, 2h), 1.57 (s, 4h), 1.32 (s, 2h), 0.91 (s, 3h).
Accompanying drawing 3 is the liquid phase figure of 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide, wherein second peak face
Long-pending percentage ratio 97.96%, represents the active matter content of 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide.
Accompanying drawing 4 is the surface tension curve before surfactant illumination, and its cmc is 2.29*10-4Mol/l, γcmc=
32.03.
Accompanying drawing 5 reaches the surface tension curve after photoisomerization balance for surfactant ultraviolet lighting, and its cmc is
2.33*10-3Mol/l, γcmc=38.48.
Accompanying drawing 6 is the surface tension curve contrast of illumination front and rear surfaces activating agent.
Accompanying drawing 7 is passed through co for deionized water2And n2The conductivity variations of solution afterwards.
Accompanying drawing 8 is that surfactant-intermediate 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) azo benzene aquatic solution leads to
Enter co2And n2The conductivity variations of solution afterwards.
Accompanying drawing 9 is 9.17 × 10 for concentration-5The change of the surfactant of mol/l its ultra-violet absorption spectrum under uv irradiation
Change, before wherein a is illumination；B is illumination 30s；C is illumination 90s and 150s (two curve co-insides).
Accompanying drawing 10 is 3.05 × 10-5UV absorption figure under uv and vis visible ray for the mol/l surfactant.
For 6 × 10-5mol/l surfactant under uv and vis radiation of visible light, it inhales at λ=350nm accompanying drawing 11
Luminosity reversible change.
(6) specific embodiment
Embodiment 1: the synthesis of surfactant-intermediate 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide
(1) synthesis of 4- butyl -4 '-hydroxyazobenzene
10g 4- butylaniline (aniline) is taken to be added to the there-necked flask of 250ml, with constant pressure funnel Deca 20ml mol ratio 1
～4 hydrochloric acid to there-necked flask, hydrochloric acid to be dripped and temperature drops to -10～10 DEG C, then the nano of Deca mol ratio 1～42,
React 1～5 hour after Deca.Then a certain amount of phenol is dissolved in mol ratio 1～3 mass content 10～90%na2co3Solution
In, with constant pressure funnel, mixed liquor is added drop-wise in said mixture, reacts 1～5 hour.By product vacuum sucking filtration, it is vacuum dried,
Obtain 4- butyl -4 '-hydroxyazobenzene；
(2) synthesis of 4- butyl -4 '-(4- bromine butoxy) diphenyl diimide
By excessive 1.5 times of k2co3It is added in there-necked flask (with reflux) with excessive 2 times of Isosorbide-5-Nitrae-dibromobutane,
Weigh 5g 4- butyl -4 '-hydroxyazobenzene to be dissolved in acetone soln, be slowly dropped in reactor with constant pressure funnel, will mix
Compound magnetic agitation, is warming up to 65 DEG C of backflows, reacts 12 hours.After reaction terminates, filter, then remove solvent, vacuum drying
After obtain 4- butyl -4 '-(4- bromine butoxy) diphenyl diimide；
(3) synthesis of 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide
Excessive 1～10 times of dimethylamine solution and excessive 1～5 times of k is added in there-necked flask2co3, weigh 3g 4- fourth
Base -4 '-(4- bromine butoxy) diphenyl diimide is dissolved in acetone soln, is added drop-wise to there-necked flask with constant pressure funnel, reacts 24h, instead
Filtered with funnel after should terminating and remove inorganic salt, remove solvent, obtain 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) idol
Pyridine.Structural characterization as shown in Figure 1, Figure 2 and Figure 3.
Embodiment 2: surface tension performance
The aqueous solution of surfactant-intermediate 4- butyl -4 '-(4-n, n- dimethyl butyrate epoxide amine) diphenyl diimide is passed through
co2, form surfactant, using the surface tension dripping profile method survey surfactant, survey surfactant solution respectively and exist
Surface tension curve before and after ultraviolet light.As shown in Figure 4, Figure 5.
Embodiment 3:co2/n2Switch
Conductivity test is to prove co at present2/n2Surfactant switch property and the reversible reliable method of switch
One of, the aqueous solution of surfactant-intermediate is passed through co2, survey the electrical conductivity of its solution at set intervals, treat electrical conductivity
When not changing, it is passed through n2Equally survey the electrical conductivity of solution at set intervals.Surfactant is passed through co2And n2Electrical conductivity become
Change and see accompanying drawing 7.
Embodiment 4: ultra-violet absorption spectrum
The surfactant of present invention synthesis contains azobenzene group, and it can occur under the irradiation of ultraviolet light and visible ray
Photoisomerization behavior, under the irradiation of uv light it may occur that transconfiguration to cis-structure transformation, and under the irradiation of visible ray
Transconfiguration can be changed into from cis-structure again, simultaneously reversible during this conversion, can be characterized by ultra-violet absorption spectrum
This change.Under ultraviolet light, it is changed into the corresponding uv absorption of cis photoisomerization from trans to surfactant
Spectrum is shown in accompanying drawing, and photoisomerization ultra-violet absorption spectrum under ultraviolet light and visible ray for the surfactant is shown in accompanying drawing 9 and Figure 10, its
The reversibility of photoisomerization is shown in Figure 11.
Claims (4)
1. a kind of co2/n2The surfactant of-light dual responsiveness, is characterized in that both thering is response to ultraviolet light, visible ray；Also right
co2、n2There is response, that is, there is dual responsiveness, its molecular structure is:
Wherein r1=h or c1～c12Straight or branched alkyl；r2=c1～c16Straight or branched alkyl；r3=c1～c4Alkyl.
2. co described in claim 12/n2The synthetic method of-light dual responsiveness surfactant is it is characterised in that step is as follows:
(1) diazonium coupled reaction: to the hydrochloric acid of Deca mol ratio 1～4 in aniline or 4- alkyl benzene amine at -10～10 DEG C
Solution and the nano of mol ratio 1～42Solution, reaction 0.5～3 hour after, by mol ratio 1～2 phenol be dissolved in mol ratio 1～3,
Mass content 10～90%na2co3In solution, mixed liquor is added drop-wise in said mixture, reacts 1～5 hour, product is taken out
Filter, vacuum drying, obtain 4- hydroxyazobenzene or 4- alkyl -4 '-hydroxyazobenzene；
(2) substitution reaction: 4- hydroxyazobenzene or 4- alkyl -4 '-hydroxyazobenzene are added to the dibromo alkane of mol ratio 1～3
Hydrocarbon and the k of mol ratio 1～32co3In, 30～100 DEG C of reaction temperature, react 8～24 hours, after reaction terminates, filter, filtrate is gone
Except obtaining substitution product after solvent；
(3) aminating reaction: substitution product is added in the dialkylamine solution of mol ratio 1～10, adds mol ratio 1～5
k2co3In, react 24h at 10～60 DEG C, reaction is filtered after terminating, and filtrate obtains aminate after being evaporated；
(4) aminate is passed through carbon dioxide, generates bicarbonate surfactant, target product is through recrystallization or post
Pure compound is obtained after Chromatographic purification.
3. according to claim 2 surfactant synthetic method it is characterised in that: used by substitution reaction, two bromoalkanes are
1,2 Bromofumes, 1,2 dibromopropanes, 1,2 dibromobutanes, 1,3 dibromopropanes, 1,3 dibromobutanes, 1,4 dibromo fourths
Alkane, 1,5 dibromo pentanes, 1,6 dibromo-hexanes, 1,7 dibromo-heptanes, 1,8 2 bromooctanes, 1,9 2 bromononanes, 1,10 dibromos
Decane, 1,11 2 bromo-n-11s, 1,12 dibromo-dodecanes, 1,14 2 bromo-tetradecanes, 1,16 dibromo hexadecanes.
4. according to claim 2 surfactant synthetic method it is characterised in that: used by aminating reaction, dialkylamine is
Dimethylamine, diethylamine, di-n-propylamine, dibutyl amine.
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| CN105481744B (en) * | 2015-11-25 | 2017-03-29 | 江南大学 | CO2/N2‑H2O2Double stimuli responsive type surfactant and preparation method thereof |
| CN105536641B (en) * | 2015-12-17 | 2017-07-18 | 江南大学 | A kind of compound emulsifying agent with stimuli-responsive energy |
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