CN114558528A - Preparation method of ionic liquid counterion-mixed surfactant thermal response and UV (ultraviolet) light and heat double response gel - Google Patents
Preparation method of ionic liquid counterion-mixed surfactant thermal response and UV (ultraviolet) light and heat double response gel Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a preparation method of ionic liquid counter ion-mixed surfactant thermal response and UV light and thermal double response gel, which comprises the steps of mixing SB3-12 and SDS to obtain spherical micelles, converting the spherical micelles into wormlike micelles under the induction of naphthyl modified imidazole ionic liquid [ NMMIm ] Br to form thermal response gel, replacing part of equimolar SDS with 4-butyl azobenzene-4' -phenoxyacetic acid sodium C4 Azonazalabyl azobenzene surfactant to prepare spherical micelles, and converting the spherical micelles into wormlike micelles under the induction of [ NMMIm ] Br to obtain UV light and thermal double response gel. The thermal response and UV light and thermal double response gel prepared by the invention can realize the reversible conversion function of gel and sol stimulated by external sources, and the sensitive thermal and UV light switch effect has important application value for the technical field related to the application of functional embedding-releasing or shear thinning.
Description
Technical Field
The invention belongs to the technical field of preparation of micromolecule self-assembly supramolecular hydrogel, and particularly relates to a preparation method of ionic liquid counterion-mixed surfactant thermal response and UV (ultraviolet) light and heat double response gel.
Background
Gels prepared from amphiphilic molecules have been extensively studied in the fields of drug encapsulation, wastewater treatment, solar cell electrolytes, catalysts, lubricants, and the like. The morphology of surfactant self-aggregates is largely related to the geometry of the surfactant molecules, and is generally evaluated using Packing parameters (Packing parameters) with specific calculation equations asP=V/(a·l) In the equationaRepresents the effective cross-sectional area of the polar head group of the surfactant,VAndlrespectively, the volume and extension length of the hydrophobic tail when the stacking parameter of the surfactant is 1/3<P <1/2, the molecular structure of the wormlike micelles is geometrically determined. For mixed surfactant systems, especially mixed ionic surfactants with opposite charges, it is possible to satisfy the stacking factor for wormlike micelles at a certain mixing ratio, due to the electrostatic attraction between the two head groups, which can significantly reduce the effective cross-sectional area of the head groups. However, many mixed anionic and cationic surfactant systems do not result in wormlike micelles. Firstly, due to poor water solubility of the counter-charged surfactant salts (cationic salts) which achieve or approach charge neutralization, crystalline or flocculent precipitates are easily formed; secondly, the effective area of the head base is too small, so that the stacking parameters are too large ( P>1/2 or evenPNot less than 1) to obtain aggregates related to the bilayer structure. Therefore, control of intermolecular interactions in aggregates, including electrostatic interactions, hydrophobic interactions, pi-pi stacking, hydrogen bonding, and the like, are important factors in regulating aggregate morphology. For the solution capable of forming the wormlike micelles, certain conditions such as concentration, mixing ratio, temperature and the like of the mixed surfactant are controlled, so that the growth of the wormlike micelles in one dimension can be promoted, flexible and disorderly oriented micelles are obtained and are mutually entangled to form a network structure, and the fluidity of the system is reduced to form gel. At present, no report is available about thermal response and UV light and heat dual response gel preparation methods of naphthyl modified ionic liquid counterion-zwitterion and anion mixed surfactant composition.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of ionic liquid counterion-mixed surfactant thermal response and UV light and thermal dual response gel, wherein the thermal response function of the gel is based on inducing the spherical mixed surfactant to form the thermal motion of the ionic liquid of the gel, and then adding the UV light response surfactant on the basis of the thermal response gel, so that the thermal response of the gel can be retained, and the gel and sol reversible conversion function of the UV light response can be endowed, thereby realizing the UV light and thermal dual response function of the gel.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the ionic liquid counterion-mixed surfactant thermal response and UV light and thermal dual response gel is characterized by comprising the following specific steps: mixing dodecyl sulfonic betaine zwitterionic surfactant SB3-12 and anionic surfactant SDS to prepare spherical micelle, and adding naphthyl modified imidazole ionic liquid [ NMMIm ]]Br induces the spherical micelles of the mixed ion surfactant to be transformed into wormlike micelles and forms a thermal response gel, the thermal response temperature of the thermal response gel is lower than 40 ℃, and the thermal response gel can be changed by [ NMMIm ]]Molar ratio of Br to SB3-12R LI/ZThe regulation and control of the thermal response temperature of the thermal response gel are realized;
the anionic surfactant in the thermal response gel is SDS, and in the process of preparing the spherical micelle, part of the SDS is prepared by using equimolar 4-butylazobenzene-4 '-phenoxyacetic acid (sodium (4-butyl-azobenzole-4' -phenoxy) -acetate, which is abbreviated as C4 Azona) carboxyl azobenzene surfactanttrans-C4 AzoaNa substitution, capable of preparing a UV light and thermal double-responsive gel, the thermal response temperature of which passesR LI/ZModulation, and UV light response sensitivity of UV light and thermal double response gel transMolar ratio of-C4 AzoaNa to SB3-12R Azo/ZAnd (5) regulating and controlling.
Further defining, the molar ratio of SB3-12 to SDS during the preparation of the thermally responsive gelR A/Z=1，[NMMIm]Molar ratio of Br to SB3-12R LI/Z= 0.2-0.4; the UV light and heat double-response gelSB3-12 in the preparation procedure was paired with SDS andtransmolar ratio of the sum of-C4 AzoaNaR A/Z=1, andtransmolar ratio of-C4 AzoaNa to SB3-12R Azo/Z=0.1-0.3，[NMMIm]Molar ratio of Br to SB3-12R LI/Z=0.2-0.4。
The specific preparation process of the ionic liquid counterion-mixed surfactant thermal response and UV light and thermal dual response gel comprises the following steps:
the thermoresponsive gel was prepared by formulating SB3-12 and SDS at 160mM, [ NMMIm]A mixture with a Br concentration of 32-64mM, andR IL/Z=0.2-0.4、R A/Z=1, forming homogeneous viscous fluid at 50 ℃, cooling to 40 ℃, keeping the temperature for 15min, and then cooling to 8-40 ℃ to obtain thermal response gel;
preparation of UV light and Heat responsive gels with SB3-12 concentration of 160mM, SDS andtransthe sum of the concentrations of-C4 AzoaNa is 160mM, [ NMMIm]A Br concentration of 32-64mM, wherein the SDS concentration is 112-144mM,transThe concentration of-C4 AzoaNa is 16-48mM, i.e.R A/Z=1、R Azo/Z=0.1-0.3、R LI/ZAnd =0.2-0.4, forming homogeneous viscous fluid at 50 ℃, cooling to 40 ℃, keeping the temperature for 15min, and cooling to 8-40 ℃ to obtain the UV light and heat double-response gel.
The invention adds the ionic liquid NMMIm ]Br induces the spherical micelle with the surface being negative charge to be converted into wormlike micelle, thermal response gel is obtained in the concentration ratio and the concentration interval, and the light response azobenzene anionic surfactant replaces part of the SDS anionic surfactant with equal molar quantity, so that the gel has the double response functions of UV light and heat, and the gel is in C4The molar ratio of the Azonas to the SBS-12 is 0.01<R Azo/Z <0.2, the thermal response gel and the UV light and thermal dual response gel have basically unchanged thermal response temperature intervals, and simultaneously, the C is caused4The UV light-excited trans-cis configuration transformation property of the Azonas endows the gel-sol transformation function of the gel UV light response, and the thermal response temperature can pass throughR LI/ZModulation, sensitivity of UV light responseR Azo/ZAnd (5) regulating and controlling.
Compared with the prior art, the invention has the following advantages and beneficial effects: the invention adopts the mixture of dodecyl sulfonic acid betaine (SB 3-12), Sodium Dodecyl Sulfate (SDS) and 1-naphthylmethyl-3-methylimidazolium bromide ([ NMMIm ] Br) to prepare the ionic liquid counterion-mixed surfactant thermal gel; a small amount of photoresponse 4-butyl azobenzene-4 '-phenoxyacetic acid (sodium (4-butyl-azobenzene-4' -phenoxy) -acetate, which is abbreviated as C4 Azona) carboxyl azobenzene surfactant is added to replace SDS with the same amount, so that a gel with double responses of UV light and heat can be obtained, the gel and the sol can be reversibly transformed for infinite times, the two gels are both exogenous triggered reversible transformation functional gels, have sensitive heat and UV light switch effects, and have important application value in the technical fields closely related to the functional embedding-releasing or shear thinning application.
Drawings
FIG. 1 (a) UV-responsive gel-sol transition; (b) a change in configuration of the Azo group UV response; (c) ionic liquid counterion-mixed surfactant thermoresponsive gel (20 ℃) sol (40 ℃); (d) ionic liquid counterion-mixed surfactant photoresponsive gels (trans-Azo) -sol (cis-Azo）；
FIG. 2 is a schematic representation of the formation of wormlike micelles of ionic liquid counterion-mixed surfactant;
FIG. 3 [ NMMIm ] Br/SB3-12/SDS three-component system (a) isothermal phase diagram at 5 deg.C, 20 deg.C and typical digital pictures in each phase region. Pictures belong to phase regions (c) laminar Fluid, (d) Gel, (e) Crystal Gel, (f) L-S and (g) Fluid, respectively;
FIG. 4 Ionic liquid counterion-mixed surfactant photoresponsive gel before UV illumination ((II))trans-C4AzoOA−Dash curve), after UV illumination (cis-C4AzoOA−Solid curve) and after recovery under natural light (trans-C4AzoOA−Dot-dash curve). The gel composition is SB3-12 SDS: C4AzoNa :[NMMIm]Br =1:0.8:0.2:0.3, concentration of SB3-12 was 160 mM, and the gel sample was diluted 800 times when measuring the spectrum;
FIG. 5 the conductivity as a function of the concentration of SB3-12 at a fixed concentration of [ NMMIm ] Br of 16.5 mM;
fig. 6 temperature response behavior of ionic liquid counter ion-mixed surfactant gels, symbols (Ä) and (), respectively, represent storage modulus and loss modulus. Both the SB3-12 and SDS concentrations were 160 mM, R IL/Z=0.3, fixed strain is 1%, oscillation frequency is 1 Hz, and heating rate is 1 ℃/min;
FIG. 7 temperature response behavior of Ionic liquid counterion-mixed surfactant UV photoresponsive gel, with symbols (Ä) and () representing storage modulus, respectivelyG' and loss modulusG’'. The concentration of the SB3-12 is 160 mM,R A/Z=0.8、R Azo/Z=0.2 andR IL/Zstrain of 0.3, 1%, oscillation frequency of 1 Hz, and heating rate of 1 deg.C/min;
FIG. 8 Steady State shear viscosity curvestrans-C4Azona andcis-C4change in AzoNa concentration. The concentration of SB3-12 in the mixed system was fixed at 160 mM,R IL/Z=0.3, R A/Z+ R Azo/Zand = 1. The data in the figure representing a mixed systemR Azo/ZValues, before UV illumination, of 0, 0.01, 0.03, 0.07, 0.10, 0.13, 0.17, 0.20, respectively; after illumination, 0.17 and 0.20. The measurement temperature was 20 ℃;
FIG. 9 is a graph of the change in storage modulus (¢ before UV radiation, Ä after radiation) versus loss modulus (£ before UV radiation, after radiation) for an ionic liquid counter-ionic-mixed surfactant system before and after UV radiation. SB3-12, SDS, [ NMMIm ] Br and C4Azona were used at concentrations of 160 mM, 128 mM, 48mM and 32 mM, respectively, and the temperature was measured at 20 ℃ with a strain of 1% fixed.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
The thermal response mechanism of the common surfactant (pure or mixed) wormlike micelle gel is heat transportThe one-dimensional size of the micelle is gradually shortened by moving, and the response temperature range is wide; the gel provided by the invention depends on the electrostatic action of the counter ions of the ionic liquid and the pi-pi interaction between naphthalene rings, the thermal response mechanism is thermal motion stripping of the counter ions, the one-dimensional micelle is spontaneously converted into the spherical micelle, the response temperature interval is narrow, and the thermal response switching effect is realized. The pi-pi attraction between the counter ions of the ionic liquid enables the counter ions to form self-assembled linker-like supramolecules, and is the key for forming the thermal response gel. The mechanism of photoresponse is derived from azobenzene (Azo) group of carboxyl azobenzene amphiphilic molecule in neutral aqueous solution at normal temperaturetransAzo is in a stable configuration, excited by UV light,trans-Azo tocisAzo, as shown in FIG. 1. The photoresponse function is characterized in that the physical state change of gel (gel) to sol (sol) occurs under the irradiation of UV light, and the sol is converted into gel after the irradiation of the UV light or visible light is stopped. This exogenous, remote stimulus-responsive function is completely reversible in terms of morphological transition, with the rate of reverse transition from sol to gel being accelerated by visible light irradiation and/or heating.
The thermal response gel of the invention is prepared from SB3-12, SDS and [ NMMIm ]]Preparation of Br with small amounttransUV light and heat double-responsive gels were obtained by replacing equimolar amounts of SDS with C4 AzooNa. SB3-12 is a zwitterionic surfactant, forms a spherical micelle after the concentration is higher than cmc, the polar shell of the micelle is composed of double layers with opposite positive and negative charges, the outer layer is electronegative, and the inner layer is electropositive. Adding anionic surfactant SDS, the sulfate head group of negative charge and the positive charge part of SB3-12 head group produce electrostatic interaction to form ion pair. While neutralizing the positive charge of SB3-12, the charge density of the terminal sulfonic acid group increased. Therefore, the volume of the hydrophobic chain of the ion pair is increased as compared with SB3-12, but the electrostatic repulsion between the sulfonic acid head groups is increased, the cross-sectional area of the head groups is also increased to some extent, and the stacking parameters of the mixed surfactant are increasedPStill in the interval of values where spherical micelles are formed. Adding ionic liquid [ NMMIm ]]Br, ionized cation as counter ion and sulfonic acid group at periphery of mixed micelle are subjected to electrostatic interaction, so that electrostatic repulsion of micelle surface charge is reduced, and apparent stacking parameter is increasedAnd (4) number, which favors the transition to wormlike micelles. [ NMMIm]+Another important property of (a) is the pi-pi interaction of the aromatic naphthalene rings, which can draw the distance between the surfactant head groups and suppress thermal motion, facilitating one-dimensional growth of the micelle, as shown in fig. 2.
Formation of UV light and thermal bifunctional gels with zwitterionic surfactant (SB 3-12) concentration, molar ratio of anionic surfactant (SDS) to zwitterionic surfactant component (S) ()R A/Z = n SDS/n SB3-12) And the molar ratio of ionic liquid cation to zwitterionic surfactant component (b: (R IL/Z = n [NMMIm]Br/n SB3-12) And (6) correlating. In the concentration interval studied, the higher the surfactant concentration, the stronger the elasticity of the gel; high-elasticity gel can be obtained at the molar ratio of SDS to SB 3-12; [ NMMIm]There is an optimum concentration region for the molar ratio of Br. FIG. 3 is a schematic view ofR A/ZWhen the concentration of SB3-12 is changed, the sum ofR IL/ZIsothermal phase diagram of (a). The equilibrium time of the sample was 10 days, and the division of the boundary between Gel and Fluid phases was obtained by repeatedly inverting the sample bottle in order to visually observe the fluidity and light transmittance of the sample, rather than plotting by quantitative measurement of physical properties, and therefore the phase boundaries used were represented by broken lines. The transition between Crystal Gel phase and L-S is time dependent and can be considered as a thermodynamically unstable intermediate phase. As can be seen from FIG. 3, the temperature increased from 5 ℃ to 20 ℃ and the Crystal Gel and L-S phases disappeared, the ionic liquid mole fraction of whichR IL/ZThe larger part is incorporated into the Gel phase region, and R IL/ZThe smaller part is converted into the Fluid phase, and the part of the bluil Fluid phase region is converted into the Gel phase region. The experimental results show that Gel is destroyed when the temperature rises to 50 deg.CR IL/Z<The 0.4 region is the Fluid phase,R IL/Z>the region 0.4 is the Bluish Fluid phase. The digital image of the corresponding phase zone state is also given in fig. 3.
When a small amount of photoresponsive azobenzene surfactant is usedtrans-When the SDS was replaced with C4 AzoaNa in equal amounts, the phase diagram did not change significantly, but the SDS was subjected to UVIn gels after irradiation with lighttrans-Stimulated conversion of C4 AzoaNacis-C4AzoOANa, the phase behavior changed significantly.trans-andcis-the reversible transformation of the C4 AzoaNa configuration can be characterized by UV-vis spectroscopy, shown in FIG. 4 as 160 mM SB3-12,R A/Z=0.8、R Azo/Z=0.2 andR IL/Zwith a composition of =0.3, the sample was diluted to a UV-vis absorption spectrum of about 0.04 mM C4AzoOANa before and after UV light irradiation. The maximum absorption wavelength before illumination is 351 nmtrans-absorption spectrum typical of C4 AzoOANa; shows two absorption peaks at 311 nm and 437 nm after illumination respectively, and iscis-Typical absorption spectra of the C4AzoOANa structure can be calculated to have a cis-conformational content of about 90%. This indicates that in the gel system, the C4 AzoaNa has a sensitive photoresponse function, although the thermal movement of the molecule is limited. The Gel-sol phase transition behavior shown in fig. 1 (d) is thus derived from the trans-cis photoresponse of C4AzoOANa (fig. 1 (b)), and when the initial state of the selection system is in the Gel phase region, the Gel can be converted to a homogeneous sol phase by heating to 50 ℃ or by irradiation with UV light.
The action of the ionic liquid cation and the sulfonic acid group on the surface of the micelle is a key factor for inducing the mixed surfactant micelle to be transformed from a spherical shape to a worm-shaped shape, and the existence of the interaction can be proved by a method of measuring conductivity. Using SB3-12 at a concentration of 50 mM, [ NMMIm]Titration of a Mixed solution having a Br concentration of 16.5 mM with the same concentration [ NMMIm]Br in water, and the conductivity was measured as a function of the concentration of SB3-12, as shown in FIG. 5. The conductivity is unchanged in the range that the concentration of SB3-12 is less than or equal to 2.72 mM. Since the amphoteric SB3-12 molecule contributes negligible to the conductance of high conductivity systems, the constant conductivity results indicate free [ NMMIm ] in the system]+And Br−The concentration was unchanged. When the concentration of SB3-12 is high>At 2.72 mM, the conductivity decreased with increasing concentration of SB3-12, and it was not difficult to analyze the components in solution because [ NMMIm]+As a result of the electrostatic interaction with the sulfonic acid groups on the micelle surface, the concentration corresponding to the inflection point is the critical aggregation concentration cac at which worm-like micelles are formed, as shown in the model of fig. 2.
The content of the invention specifically comprises two items: firstly, aromatic ring modified imidazole ionic liquid is used as a molecular switch to induce the spherical micelle of the sulfobetaine-anionic surfactant to be converted into a wormlike micelle, and ionic liquid counterion-mixed surfactant thermal response gel is prepared; secondly, on the basis of the prepared thermal response gel, a small amount of carboxylic acid radical azobenzene surfactant is used for replacing equimolar anionic surfactant in the thermal response gel to prepare the ionic liquid counterion-mixed surfactant UV light and thermal response gel.
Examples
1. Thermal response of the gel: the concentrations of the zwitterionic surfactant SB3-12 and the anionic surfactant SDS were prepared to be 160 mM (respectively: (M) (M))R A/Z= 1) and [ NMMIm]Mixed solution of Br concentration of 48 mM (R IL/Z= 0.3), forming a homogeneous viscous fluid at 50 ℃, then slowly cooling to 40 ℃, keeping the temperature for 15 min, and then cooling to any temperature between 8 ℃ and 40 ℃. FIG. 6 is a graph showing the behavior of the gel with respect to the change in modulus with temperature, with a storage modulus higher than the loss modulus at a temperature lower than 41 ℃ with substantially constant values and a gradual increase in loss modulus, which is indicative of the rheological behavior of a typical sample in the gel state; at (41.1 ± 0.4) ° c, the storage modulus intersects the loss modulus, corresponding to the sample being at a temperature at which the gel and sol coexist (gel ↔ sol); the temperature is further raised and enters the sol phase region. The existence of the phase transition temperature indicates that the developed gel system has the temperature response function, and the phase diagram at two temperatures according to the figure 3 is in a certain rangeR IL/ZRegulation of mixed systems within the scope [ NMMIm]Br, and the response temperature can be regulated and controlled, so that the temperature control system can meet the requirements of different application fields in a certain temperature interval.
2. Characterization of thermal response of UV light responsive gel: SB3-12 was prepared at a concentration of 160 mM and SDS at a concentration of 128 mM ( R A/Z=0.8）、transA concentration of C4 AzoloNa of 32 mM (C4-AzoloNaR Azo/Z= 0.2) and [ NMMIm = 0.2)]Br concentration of 48 mM (R IL/Z= 0.3) and then the UV light-responsive gel having a temperature between 8 ℃ and 40 ℃ is obtained by the same procedure as the preparation of the above thermal-responsive gel. FIG. 7 is a graph of modulus versus temperature for a UV light responsive gelThe degree of change was the same as that of the thermally responsive gel not containing C4 AzoaNa, and the rheological property was (41.1. + -. 0.4). degree.C.to obtain a cross point where the gel coexisted with the sol, indicating that the amount of the compound was changed byR Azo/ZAfter the trans-carboxyazobenzene surfactant of =0.2 was substituted for SDS, the sample was still in the gel state and had approximately the same storage modulus and loss modulus. This is for illustrationR Azo/Z=0.2transThe gel after the-C4 azoOANa replaces SDS has basically the same temperature response function as the original system. The experimental results of other composition samples in the gel phase region also show that the temperature of the response can be changedR IL/ZAnd (5) regulating and controlling.
3. Effect of C4AzoOANa concentration on UV light response: the UV light response function of the ionic liquid counterion-mixed surfactant gel is derived from C4AzoOA−Is transformed.trans-C4AzoOA−The ions are excited by UV light and converted intocis-C4AzoOA−The ions will influence the ordered arrangement of the molecules in the aggregates of the mixed system and even the aggregation morphology. In the thermally responsive mixed surfactant gels studied, a small amount of C4AzoOA was used −Ion replacement of SDS anion (DS)−) The UV light and heat double-response function can be realized. FIG. 8 shows the results of the tests at fixed SB3-12 and [ NMMIm ]]The sum of Br concentration and SDS and C4 AzoaNa concentration was variedR Azo/ZEffect of value on shear viscosity. At a ratio ofR Azo/Z<In the range of 0.03, the plateau viscosity is higher than that withouttrans-C4AzoOANa, followed by a sequential decrease in plateau viscosity and a corresponding increase in critical shear rate. The structure of trans-azobenzene and an alkyl chain in a hydrophobic domain of the micelle is not matched, so that the apparent stacking parameter of the system is increased, and the C4AzoOA−Carboxylic acid anion and DS of−The sulfate anion of (a) is different from the SB3-12 head group in acting force, but can simultaneously induce one-dimensional growth of a worm-like micelle and generation of a branch structure. After the gel is irradiated by UV light, the gel is in micelletransStimulated in situ conversion of-C4 AzoaNacisThe hydrophobic part loses the original symmetry and the extension length, so that the molecular arrangement order of the micelle is changed, the one-dimensional length is shortened, and the shear viscosity is reduced by about three timesOf order of magnitude and withR Azo/ZThe increase is decreased. This result indicates that the quaternary mixture IL-SB3-12-SDS-Azo system has a sensitive UV/Vis response function in addition to the thermal response function shown in FIG. 7. Exposed to uv light, is a low viscosity fluid, exposed to visible light, and even shielded from light, is an elastic gel. In principle, gels and sols can be reversibly transformed an unlimited number of times without the occurrence of chemical reactions.
4. Rheological profile of UV light responsive gel: the UV light responsive gel ↔ sol transition function of ionic liquid counterion-mixed surfactant gels can be characterized by storage and loss moduli. The results in FIG. 9 show that before UV light irradiation, i.e., when C is present4When the azo na is mainly a trans-isomer, both the storage modulus indicating elasticity and the loss modulus indicating viscosity are larger than those of the case where the cis-isomer is mainly present after UV light irradiation, and a significant UV light response function is exhibited. Gel relaxation time before light irradiationτAt 0.45 s, no intersection of the two moduli occurred in the measured frequency interval after illumination.
5. When observed by using a polarized light microscope, no birefringence image exists in the gel phase region, which indicates that the liquid crystal structure is not anisotropic, and the gel phase is determined to be a worm-like micelle aggregate by considering the lower surfactant concentration and the rheological curve shown in FIG. 9.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (4)
1. The preparation method of the ionic liquid counterion-mixed surfactant thermal response and UV light and thermal dual response gel is characterized by comprising the following specific steps: mixing dodecyl sulfonic betaine zwitterionic surfactant SB3-12 and anionic surfactant SDS to obtain spherical micelle, and adding naphthyl modified amphoteric surfactantImidazole ionic liquid [ NMMIm]Br induces the spherical micelles of the mixed ion surfactant to be transformed into wormlike micelles and forms a thermal response gel, the thermal response temperature of the thermal response gel is lower than 40 ℃, and the thermal response gel can be changed by [ NMMIm ]]Molar ratio of Br to SB3-12R LI/ZThe regulation and control of the thermal response temperature of the thermal response gel are realized;
the anion surfactant in the thermal response gel is SDS, and in the process of preparing the spherical micelle, part of the SDS is prepared by using equimolar 4-butylazobenzene-4' -phenoxyacetic acid sodium carboxyl azobenzene surfactanttrans-C4 AzoaNa substitution, capable of preparing a UV light and thermal double-responsive gel, the thermal response temperature of which passesR LI/ZModulation, and UV light response sensitivity of UV light and thermal double response geltransMolar ratio of-C4 AzoaNa to SB3-12R Azo/ZAnd (5) regulating and controlling.
2. The method for preparing ionic liquid counterion-mixed surfactant thermoresponsive and UV light and thermal dual-responsive gel according to claim 1, characterized in that: molar ratio of SB3-12 to SDS during preparation of the thermally responsive gel R A/Z=1，[NMMIm]Molar ratio of Br to SB3-12R LI/Z0.2-0.4; SB3-12 vs SDS and in the preparation of the UV light and heat dual response geltransMolar ratio of the sum of-C4 AzoaNaR A/Z=1, andtransmolar ratio of-C4 AzoaNa to SB3-12R Azo/Z=0.1-0.3，[NMMIm]Molar ratio of Br to SB3-12R LI/Z=0.2-0.4。
3. The method for preparing ionic liquid counterion-mixed surfactant thermal response and UV light and thermal dual response gel according to claim 1, which is characterized by comprising the following steps:
the thermoresponsive gel was prepared by formulating SB3-12 and SDS at 160mM, [ NMMIm]A mixture with a Br concentration of 32-64mM, andR IL/Z=0.2-0.4、R A/Z=1, forming homogeneous viscous fluid at 50 ℃, cooling to 40 ℃, keeping the temperature for 15min, and then cooling to 8-40 ℃ to obtain thermal response gel;
preparation of UV light and Heat responsive gels with SB3-12 concentration of 160mM, SDS andtransthe sum of the concentrations of-C4 AzoaNa is 160mM, [ NMMIm]A Br concentration of 32-64mM, wherein the SDS concentration is 112-144mM,transThe concentration of-C4 AzoaNa is 16-48mM,R A/Z=1、R Azo/Z=0.1-0.3、R LI/ZAnd =0.2-0.4, forming homogeneous viscous fluid at 50 ℃, cooling to 40 ℃, keeping the temperature for 15min, and cooling to 8-40 ℃ to obtain the UV light and heat double-response gel.
4. The method for preparing ionic liquid counterion-mixed surfactant thermoresponsive and UV light and thermal dual-responsive gel according to claim 1, characterized in that: by adding ionic liquids [ NMMIm ] ]Br induces the spherical micelle with the surface being negative charge to be converted into wormlike micelle, thermal response gel is obtained in the concentration ratio and the concentration interval, and the light response azobenzene anionic surfactant replaces part of the SDS anionic surfactant with equal molar quantity, so that the gel has the double response functions of UV light and heat, and the gel is in C4The molar ratio of the Azonas to the SBS-12 is 0.01<R Azo/Z <0.2, the thermal response gel and the UV light and thermal dual response gel have basically unchanged thermal response temperature intervals, and simultaneously, the C is caused4The UV light-excited trans-cis configuration transformation property of the Azonas endows the gel-sol transformation function of the gel UV light response, and the thermal response temperature can pass throughR LI/ZModulation, sensitivity of UV light responseR Azo/ZAnd (5) regulating and controlling.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009062477A (en) * | 2007-09-07 | 2009-03-26 | Yokohama National Univ | Photoresponsive ionic liquid |
| CN103920432A (en) * | 2014-04-21 | 2014-07-16 | 河北工业大学 | Light and flexible super-hydrophobic porous gas gel material and preparation method thereof |
| CN104292475A (en) * | 2014-09-30 | 2015-01-21 | 华东师范大学 | Temperature-sensitive and photosensitive dual-response polypeptide based host-guest composite intelligent hydrogel as well as preparation method and application thereof |
| CN106582433A (en) * | 2016-12-28 | 2017-04-26 | 中国石油大学(华东) | Method for preparing triple-stimulation intelligent-response worm micelle system |
| CN109897133A (en) * | 2019-03-28 | 2019-06-18 | 南京林业大学 | A kind of ionic gel and its preparation method and application with temperature and optical Response |
| KR20210048475A (en) * | 2019-08-23 | 2021-05-03 | 성균관대학교산학협력단 | Freestanding ion gel and method of fabricating thereof |
| CN113292979A (en) * | 2021-05-20 | 2021-08-24 | 武汉大学 | Shear thickening type wormlike micelle and preparation method and application thereof |
-
2022
- 2022-02-06 CN CN202210115218.6A patent/CN114558528B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009062477A (en) * | 2007-09-07 | 2009-03-26 | Yokohama National Univ | Photoresponsive ionic liquid |
| CN103920432A (en) * | 2014-04-21 | 2014-07-16 | 河北工业大学 | Light and flexible super-hydrophobic porous gas gel material and preparation method thereof |
| CN104292475A (en) * | 2014-09-30 | 2015-01-21 | 华东师范大学 | Temperature-sensitive and photosensitive dual-response polypeptide based host-guest composite intelligent hydrogel as well as preparation method and application thereof |
| CN106582433A (en) * | 2016-12-28 | 2017-04-26 | 中国石油大学(华东) | Method for preparing triple-stimulation intelligent-response worm micelle system |
| CN109897133A (en) * | 2019-03-28 | 2019-06-18 | 南京林业大学 | A kind of ionic gel and its preparation method and application with temperature and optical Response |
| KR20210048475A (en) * | 2019-08-23 | 2021-05-03 | 성균관대학교산학협력단 | Freestanding ion gel and method of fabricating thereof |
| CN113292979A (en) * | 2021-05-20 | 2021-08-24 | 武汉大学 | Shear thickening type wormlike micelle and preparation method and application thereof |
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