CN111298711A - Mesoporous Janus nanosheet emulsifier with pH responsiveness and preparation method and application thereof - Google Patents

Mesoporous Janus nanosheet emulsifier with pH responsiveness and preparation method and application thereof Download PDF

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CN111298711A
CN111298711A CN202010168581.5A CN202010168581A CN111298711A CN 111298711 A CN111298711 A CN 111298711A CN 202010168581 A CN202010168581 A CN 202010168581A CN 111298711 A CN111298711 A CN 111298711A
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mesoporous
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CN111298711B (en
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刘益江
杨江燕
王佳琳
黎华明
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Xiangtan University
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Abstract

The invention discloses a mesoporous Janus nanosheet emulsifier with pH responsiveness, which is used for obtaining core-shell structured nanoparticles (ZIF @ mSiO) by combining the sol-gel action of methyl orthosilicate (TMOS) under the action of a surfactant2). Then, the outer layer (mSiO) of the mesoporous silica is modified by 4- (chloromethyl) phenyltrimethoxysilane2) And grafting a polymer with pH responsiveness on the outer side of the mesoporous silica through ATRP polymerization reaction. And finally, carrying out hydrophobic modification on the inner side of the mesoporous silica to obtain a mesoporous Janus nanosheet emulsifier with pH responsiveness. The emulsifier has amphiphilic property and large specific surface area, and the sheet material can greatly improve the stability of the emulsion. Meanwhile, the controllable emulsification-demulsification process is realized by adjusting the pH value, and the recovery and the reutilization of the mesoporous Janus nanosheet emulsifier are facilitated.

Description

Mesoporous Janus nanosheet emulsifier with pH responsiveness and preparation method and application thereof
Technical Field
The invention relates to a mesoporous Janus nanosheet emulsifier, in particular to a preparation method and application of a mesoporous Janus nanosheet emulsifier with pH responsiveness, and belongs to the field of nano composite materials.
Background
Janus is a two-sided spirit in ancient Roman mythical, and since the first use of Janus in its Nobel prize congratulation by the French scientist Pierre-Gilles DeGennes in 1991 to describe particles with dual properties (P.G.DeGennes.Rev.Mod.Phys.1992,64, 645-. Janus material has shape asymmetry or composition/property asymmetry, including particles, rods, sheets, hollow spheres and the like, and has wide application prospects in various fields of drug delivery, emulsion catalysis, optical probes and the like. The flaky Janus nano material has more unique performance due to the fact that the flaky Janus nano material has chemical composition asymmetry and geometric structure asymmetry. When Janus nanosheets are used as emulsifiers, anchoring at the oil/water interface in a "mosaic" manner enables a more stable oil/water emulsion to be formed. Researches show that the mesoporous structure is beneficial to material transmission and increases the contact area of reactants. Meanwhile, the polymer with environmental responsiveness can respond to environmental changes correspondingly, and has important application in the fields of drug carriers, drug delivery, controllable catalysts and the like. Therefore, the combination of the Janus nanosheets, the mesoporous structure and the polymer with environmental responsiveness and the research of the application of the combination as an emulsifier in the controllable emulsification-demulsification process have important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the inventor combines a Janus nanosheet, a mesoporous structure and a polymer with environmental responsiveness by an interface protection method to prepare a mesoporous Janus nanosheet emulsifier with pH responsiveness. The emulsifier has good emulsifying property, can realize the controllable emulsification-demulsification process of an emulsion system by utilizing the pH responsiveness of the emulsifier, and is beneficial to the recovery and the reutilization of the emulsifier.
The invention aims to controllably prepare a mesoporous Janus nanosheet emulsifier with pH responsiveness, which is mainly characterized in that core-shell nanoparticles (ZIF @ mSiO) are obtained by performing sol-gel action on methyl orthosilicate (TMOS) on a ZIF template2) Then, 4- (chloromethyl) phenyl trimethoxy silane is modified on core-shell structure nano particles (ZIF @ mSiO)2) mSiO of2On the outer side of the layer to obtain ZIF @ mSiO with ATRP reaction activity2-Cl, extracting to remove the surfactant and etching the ZIF template with an acid solution to obtain HO-mSiO2-Cl mesoporous nanosheets, finally at HO-mSiO2-Cl mesoporous nanosheet mSiO2Grafting a polymer with pH responsiveness on the-Cl side and carrying out hydrophobic modification on the inner side (-OH side) of the polymer to obtain the mesoporous Janus nanosheet emulsifier with pH responsiveness.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to a first embodiment of the present invention, there is provided a mesoporous Janus nanosheet emulsifier having pH responsiveness, which is prepared by the following method: firstly, under the action of a surfactant, the sol-gel action of methyl orthosilicate (TMOS) is combined, and the surface of a zeolite imidazole ester framework material (ZIF) is coated with mesoporous SiO2Layer (mSiO)2) Obtaining the core-shell structure nano-particles (ZIF @ mSiO)2). Modifying the core-shell structure nanoparticles (ZIF @ mSiO) with 4- (chloromethyl) phenyltrimethoxysilane2) mSiO of2On the outer side of the layer to obtain ZIF @ mSiO with ATRP reaction activity2-Cl; removing the surfactant by extraction, and etching the ZIF template by using an acid solution to obtain HO-mSiO2-Cl mesoporous nanosheets. Then through ATRP polymerization grafting of pH-responsive polymers to HO-mSiO2mSiO of-Cl mesoporous nano-sheet2-Cl side to obtain HO-mSiO2-polymeric mesoporous nanoplatelets. Finally, the HO-mSiO is coupled by a hydrophobic silane coupling agent2Carrying out hydrophobic modification on the inner side (-OH side) of the polymer mesoporous nanosheet to obtain a mesoporous Janus nanosheet emulsifier with pH responsiveness.
Preferably, the surfactant is a surfactant having a pore-forming effect. Preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 (PEO)20-PPO70-PEO20) Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer F127 (PEO)106-PPO70-PEO106) One or more of Sodium Dodecyl Sulfate (SDS), polyvinylpyrrolidone (PVP) and 1-alkyl-3-methylimidazole (CnMIM).
Preferably, the Zeolitic Imidazolate Framework (ZIF) is in solid particulate form. Preferably one or more of ZIF-5, ZIF-7, ZIF-8, ZIF-12, ZIF-67 and ZIF-L.
Preferably, the particle size of the ZIF solid template particle is 200-800nm, preferably 300-600nm, and more preferably 400-500 nm.
Preferably, the acid in the acid solution etching is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Preferably, the concentration of the acid solution is 0.05 to 6mol/L, preferably 0.1 to 4mol/L, and more preferably 0.15 to 3 mol/L.
Preferably, the polymer with pH responsiveness is selected from one or more of poly (dimethylamino ethyl methacrylate) (PDMAEMA), poly (2-vinylpyridine) (P2VP), poly (2-morpholinoethyl methacrylate) (PMEMA) and poly (vinyl imidazole) (PVI).
Preferably, the hydrophobic silane coupling agent is selected from one or more of Octadecyltrimethoxysilane (ODTMS), octyltrimethoxysilane, Phenyltriethoxysilane (PETS), 4-fluorophenyltrimethoxysilane.
According to a second embodiment of the present invention, there is provided a method for preparing the pH-responsive mesoporous Janus nanosheet emulsifier of the first embodiment, the method comprising the steps of:
1) coating mesoporous SiO on the surface of a zeolite imidazole ester framework material (ZIF) under the pore-forming action of a surfactant and the sol-gel action of methyl orthosilicate (TMOS)2Layer (mSiO)2) Obtaining the core-shell structure nano-particles (ZIF @ mSiO)2)。
2) Modifying the core-shell structure nanoparticles (ZIF @ mSiO) obtained in the step 1) with 4- (chloromethyl) phenyltrimethoxysilane by utilizing the protection effect of a ZIF template2) mSiO of2On the outer side of the layer to obtain ZIF @ mSiO with ATRP reaction activity2-Cl; after the surfactant is removed by extraction, the ZIF template is etched by acid solution to obtain HO-mSiO2-Cl mesoporous nanosheets.
3) Grafting a polymer having pH responsiveness to the HO-mSiO obtained in step 2) by ATRP polymerization in the presence of a catalyst and a ligand2mSiO of-Cl mesoporous nano-sheet2-Cl side to obtain HO-mSiO2-polymeric mesoporous nanoplatelets.
4) The HO-mSiO obtained in the step 3) is treated by a hydrophobic silane coupling agent2Carrying out hydrophobic modification on the inner side (-OH side) of the polymer mesoporous nanosheet to obtain a mesoporous Janus nanosheet emulsifier with pH responsiveness.
Preferably, in the step 1), the zeolite imidazolate framework material (ZIF), the surfactant and The Methyl Orthosilicate (TMOS) are added in a mass ratio of 1:0.5-3: 0.1-2; preferably 1:0.8-2.5: 0.3-1.5; more preferably 1:1 to 2:0.5 to 1.
Preferably, in step 2), the core-shell structured nanoparticles (ZIF @ mSiO)2) And 4- (chloromethyl) phenyltrimethoxysilane are added in a mass ratio of 1:0.3-2, preferably 1:0.5-1.5, more preferably 1: 0.8-1.2.
Preferably, in step 3), the HO-mSiO2The mass ratio of the added amounts of the-Cl mesoporous nanosheets, the catalyst, the ligand and the monomer is 1:0.05-0.5:0.1-0.5:1-5, preferably 1:0.08-0.4:0.15-0.4:1.5-4, and more preferably 1:0.1-0.3:0.2-0.3: 1.8-3.
Preferably, in step 4), the HO-mSiO2The mass ratio of the added amounts of the polymer mesoporous nanosheet and the hydrophobic silane coupling agent is 1:0.5-3, preferably 1:0.8-2.5, and more preferably 1: 1-2.
Preferably, step 1) is specifically: weighing zeolite imidazolate framework material (ZIF) and surfactant according to a proportion, and ultrasonically dispersing in a solution (such as an ethanol solution). Then the system is adjusted to be alkaline (for example, the pH value is adjusted to be 9-13, preferably 10-12 by using an alkaline solution), and the mixture is mixed evenly by ultrasonic. Then adding TMOS ethanol solution in multiple times (such as 1-8 times, preferably 2-5 times; each time interval is 10-60min, preferably 20-40min), and stirring well (such as magnetic stirring at room temperature for 8-24h, preferably 12-18 h). After the reaction is finished, centrifugal separation is carried out, and an alcohol-water mixed solution (preferably n) is adopted in sequenceEthanol:nWater (W)Is a mixed solution of 1: 1), ultrasonically washing with ethanol for 1-5 times (preferably 2-4 times), drying (such as drying in a vacuum drying oven at 40-80 deg.C for 8-24h, preferably at 50-70 deg.C for 10-18h) to obtain core-shell structured nanoparticles (ZIF @ mSiO)2)。
Preferably, step 2) is specifically: weighing the core-shell structure nanoparticles (ZIF @ mSiO) obtained in the step 1) in proportion2) Adding into organic solvent (such as toluene solution), adding 4- (chloromethyl) phenyl trimethoxy silane, ultrasonically dispersing uniformly, and heating for reflux reaction (the reaction temperature is 60-120 deg.C, preferably 80-110 deg.C, more preferably 90-100 deg.C); the reaction time is 3 to 24 hours, preferably 5 to 18 hours, more preferably 8 to 12 hours). After the reaction is completed, cooling (e.g., natural cooling to room temperature), centrifuging, washing (e.g., 1-5 times, preferably 2-4 times, washing with a toluene solution), and drying (e.g., drying in a vacuum oven at 50-120 deg.C for 6-24h, preferably at 60-100 deg.C for 8-18h) to obtain ZIF @ mSiO having ATRP reactivity2-Cl; after removing the surfactant by acetone extraction for 2-5 times (preferably 3 times, each time preferably 24 hours), etching the ZIF template by using an acid solution (such as 0.05-6mol/L, preferably 0.1-4mol/L, more preferably 0.15-3mol/L hydrochloric acid solution) to obtain HO-mSiO2-Cl mesoporous nanosheets.
Preferably, step 3) is specifically: weighing the HO-mSiO obtained in the step 2) according to the proportion2-Cl mesoporous nanoplates, a catalyst (preferably CuBr), a ligand (preferably PMDETA), a monomer, a solvent (preferably methanol solution) are added to the polymerization tube. Then introducing protective gas (such as nitrogen or helium or argon, preferably nitrogen) for 10-60min (preferably 20-50min, more preferably 30-40min), freezing with liquid nitrogen, vacuumizing, thawing, repeating freezing-thawing operation for 1-5 times (preferably 2-4 times), and sealing under vacuum. Then heating to carry out reaction (the reaction temperature is 30-80 ℃, preferably 40-70 ℃, more preferably 50-60 ℃, and the reaction time is 5-18h, preferably 8-15h, more preferably 10-12 h). After the reaction is completed, the sealed tube is opened, centrifuged, washed (for example, 1-5 times, preferably 2-3 times, by using a methanol solution), dried (for example, dried in a vacuum drying oven at 40-80 ℃ for 8-24h, preferably at 50-70 ℃ for 10-15h) to obtain HO-mSiO2-polymeric mesoporous nanoplatelets.
Preferably, the step 4) is specifically: weighing the HO-mSiO obtained in the step 3) according to the proportion2The polymer mesoporous nano-sheet and the hydrophobic silane coupling agent are ultrasonically dispersed in an organic solvent (preferably a toluene solution). Then heating to carry out reflux reaction (the reaction temperature is 60-120 ℃, preferably 80-110 ℃, more preferably 90-100 ℃, and the reaction time is 3-18h, preferably 5-15h, more preferably 8-12 h). After the reaction is finished, cooling (for example, naturally cooling to room temperature), centrifuging, and washing (for example, washing with a toluene solution for 1-5 times, preferably for 2-4 times) to obtain the mesoporous Janus nanosheet emulsifier with pH responsiveness.
According to a third embodiment of the present invention, there is provided a use of the mesoporous Janus nanosheet emulsifier with pH responsiveness of the first embodiment or the mesoporous Janus nanosheet emulsifier with pH responsiveness prepared by the method of the second embodiment, and a use of the mesoporous Janus nanosheet emulsifier with pH responsiveness for controlling a pH value to realize a controllable emulsification-demulsification process.
In the invention, the surfactant is a surfactant with a pore-forming effect, and under the action of the surfactant with the pore-forming effect, the silicon is treatedMethyl formate (TMOS) is subjected to sol-gel action on a solid template ZIF to obtain core-shell nano particles (ZIF @ mSiO)2) The solid template ZIF is etched by removing the surfactant through extraction and the acid solution, and then the nano mesoporous structure is rich, so that a larger specific surface area is obtained. When the emulsifier is used as an emulsifier, the contact area of reactants is greatly increased, the reaction efficiency is improved, the dosage is small, and the reaction speed is high.
In the invention, the alkaline solution for adjusting the system to be alkaline in the step 1) is one or more of an ammonia solution, a NaOH solution and a KOH solution. Preferably, the concentration of the alkali solution is 1 to 8mol/L, preferably 2 to 6mol/L, and more preferably 2 to 6 mol/L.
In the present invention, the solution used for ultrasonic dispersion in step 1) is a water-soluble organic solution, preferably an alcohol solution, such as an ethanol solution. In an amount such that the Zeolitic Imidazolate Framework (ZIF) and the surfactant are completely dispersed in the solution.
In the present invention, the organic solvent in step 2) is one or more of toluene, xylene, dimethyl sulfoxide (DMSO), and Dimethylacetamide (DMAC). In such an amount that core-shell structured nanoparticles (ZIF @ mSiO)2) And 4- (chloromethyl) phenyltrimethoxysilane were able to be dispersed completely in this solvent.
In the invention, the solvent in step 3) is an organic solvent, and the organic solvent is one or more of methanol, toluene, isopropanol and Dimethylformamide (DMF). In such an amount that HO-mSiO2the-Cl mesoporous nanosheets, the catalyst, the ligand (preferably PMDETA) and the pH-responsive polymer can be completely dispersed in the organic solvent.
Further, in the step 3), the catalyst is CuBr, CuCl or FeCl2、RuCl2、NiBr2One or more of (a). The ligand is Pentamethyldiethylenetriamine (PMDETA), Hexamethyltriethylenetetramine (HMTETA), 2' -bipyridine (bpy), and triphenylphosphine (PPh)3) Tris (2-dimethylaminoethyl) amine (Me)6TREN). The ligand has the function of forming a complex with the metal catalyst to strengthen goldThe solubility of the catalyst in organic monomers (or solvents).
In the present invention, step 3) is carried out by reacting HO-mSiO2After the-Cl mesoporous nanosheet, the catalyst, the ligand, the monomer and the solvent are added into the polymerization tube, protective gas is introduced for 10-60min under the state of half-open polymerization tube (the purpose is to eliminate oxygen in the polymerization tube by blowing the protective gas), then liquid nitrogen is used for freezing (the purpose is to further remove oxygen), and finally the polymerization tube is vacuumized and unfrozen. Repeated freezing-thawing is carried out for a plurality of times to strictly remove oxygen.
In the invention, the core-shell nano-particles (ZIF @ mSiO) are obtained by adopting methyl orthosilicate (TMOS) to perform sol-gel action on a solid template ZIF2) Modifying core-shell nanoparticles (ZIF @ mSiO) with 4- (chloromethyl) phenyltrimethoxysilane by utilizing the protection effect of a ZIF template2) mSiO of2On the outer side of the layer to obtain ZIF @ mSiO with ATRP reaction activity2-Cl; then acetone extraction is carried out to remove the surfactant and acid solution is used for etching the ZIF template to obtain HO-mSiO2-Cl mesoporous nanosheets. Finally at HO-mSiO2-Cl mesoporous nanosheet mSiO2Grafting a polymer with pH responsiveness on one side of-Cl and carrying out hydrophobic modification on the inner side (-OH side) of the polymer with hydrophobic silane coupling agent to obtain a mesoporous Janus nanosheet emulsifier with one side of the pH responsive polymer and the other side of the hydrophobic molecule. The mesoporous Janus nanosheet emulsifier with pH responsiveness obtained by the invention is of a sheet-shaped mesoporous structure, and the pH value can be regulated and controlled to control the hydrophilicity and hydrophobicity and the emulsifying property of the mesoporous Janus nanosheet emulsifier, so that the controllable emulsification-demulsification process is realized.
In the invention, the mesoporous Janus nanosheet emulsifier with pH responsiveness provided by the invention has the following advantages: the ZIF template used in the first place is preferably one or more of ZIF-5, ZIF-7, ZIF-8, ZIF-12, ZIF-67 and ZIF-L. The ZIF template is easily removed by acid solution etching. And secondly, the mesoporous Janus nanosheet is more beneficial to the stability of the emulsion, and the mesoporous structure has larger specific surface area, thereby being beneficial to increasing the contact area of two-phase substances and accelerating the substance transmission. And finally, the hydrophilicity and hydrophobicity of one side of the mesoporous Janus nanosheet emulsifier polymer has pH response characteristics, the hydrophilicity and hydrophobicity of the polymer can be controlled by regulating and controlling the pH value, and the controllable emulsification-demulsification process is further realized, so that the recycling and the reutilization of the mesoporous Janus nanosheet emulsifier are facilitated.
In the invention, the experiment of the mesoporous Janus nanosheet emulsifier with pH responsiveness for emulsifying the oil-water mixed solution shows that: (the specific experimental process is shown in the effect test example), the mesoporous Janus nanosheet emulsifier obtained by the invention can be uniformly dispersed in water phase and oil phase solutions, and has good amphiphilic performance; when the structure of the hydrophobic group in the mesoporous Janus nanosheet is similar to that of the oil phase solution, the obtained emulsion is smaller in droplet size and more stable.
In the invention, the pH responsiveness experiment of the mesoporous Janus nanosheet emulsifier with pH responsiveness shows that: (the specific experimental process is shown in the effect test example) when the pH value of the system is 7 or 12, the nano sheets are deposited at the bottom of the bottle due to the fact that one side of the polymer in the mesoporous Janus nano sheets is hydrophobic, emulsion is broken to separate oil from water, namely the pH value is regulated and controlled to achieve the emulsification-de-emulsification process.
In the present invention, 4- (chloromethyl) phenyltrimethoxysilane was used in order to introduce a benzyl chloride initiating group having ATRP reactivity to graft a polymer having pH responsiveness by ATRP polymerization. Experiments show that 4- (chloromethyl) phenyltrimethoxysilane adopted by the invention is successfully modified on core-shell structure nanoparticles (ZIF @ mSiO)2) mSiO of2The outer side of the layer has extremely high selectivity and good effect.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the mesoporous Janus nanosheet emulsifier with pH responsiveness disclosed by the invention can control the hydrophilicity and hydrophobicity of a polymer (polymer with pH responsiveness) on one side by regulating the pH value, and the pH value is regulated to realize a controllable emulsification-demulsification process, so that the mesoporous Janus nanosheet emulsifier is favorably recycled and reused.
2. The mesoporous Janus nanosheet emulsifier with pH responsiveness disclosed by the invention has a rich nano mesoporous structure and a larger specific surface area. When used as an emulsifier, the emulsifier greatly increases the contact area of reaction, is beneficial to improving the emulsification efficiency, and has small dosage and high emulsification speed.
3. The mesoporous Janus nanosheet emulsifier with pH responsiveness is of a sheet structure, and the nanosheet emulsifier can be anchored on an oil-water emulsion interface, so that the stability of the emulsion is improved.
4. The mesoporous Janus nanosheet emulsifier with pH responsiveness can be recycled, liquid drops with the size equivalent to that of the initial emulsion can be obtained after 5 times of emulsification-demulsification, and the pH value can be regulated and controlled to realize rapid demulsification.
Drawings
Fig. 1 is a synthetic schematic diagram of a mesoporous Janus nanosheet emulsifier with pH responsiveness prepared by the present invention.
FIG. 2 is an SEM image of a solid template ZIF-67 prepared by the present invention.
FIG. 3 is a TEM image of a solid template ZIF-67 prepared by the present invention.
FIG. 4 is a ZIF-67@ mSiO solid prepared in accordance with the present invention2SEM image of core-shell nanoparticles.
FIG. 5 is a ZIF-67@ mSiO solid prepared in accordance with the present invention2TEM images of core-shell nanoparticles.
FIG. 6 is a diagram of mSiO prepared according to the invention2Mesoporous nanosheet pair N2Adsorption-desorption curve of (d).
FIG. 7 is a diagram of mSiO prepared according to the present invention2The aperture distribution map of the mesoporous nano sheet.
FIG. 8 is a ZIF-67@ mSiO solid prepared in accordance with the present invention2And ZIF-67@ mSiO2Zeta potential contrast plot of Cl.
FIG. 9 is HO-mSiO prepared according to the present invention2EDS picture of-Cl mesoporous nano-sheet.
FIG. 10 is a HO-mSiO prepared in accordance with the present invention2SEM image of P2VP mesoporous nanosheet.
FIG. 11 is HO-mSiO prepared according to the present invention2TEM image of mesoporous nanoplates of P2 VP.
FIG. 12 is a pH responsive C18-mSiO prepared in accordance with the present invention2TEM image of mesoporous Janus nanosheet emulsifier P2 VP.
FIG. 13 is a mSiO prepared according to the invention2、HO-mSiO2-Cl、C18-mSiO2-ir contrast map of P2 VP.
FIG. 14 is a pH responsive C18-mSiO prepared in accordance with the present invention2-P2VP dispersion pattern of mesoporous Janus nanosheet emulsifier in deionized water, toluene and n-decane.
FIG. 15 is a pH responsive C18-mSiO prepared in accordance with the present invention2-optical microscopy, emulsion and emulsion breaking of an oil/water emulsion (the oil phase is toluene) formed by the P2VP mesoporous Janus nanosheet emulsifier.
FIG. 16 is a pH responsive C18-mSiO prepared in accordance with the present invention2An optical microscope picture, an emulsion picture and a demulsification picture of an oil/water emulsion (the oil phase is n-decane) formed by the P2VP mesoporous Janus nanosheet emulsifier.
FIG. 17 is a pH responsive C18-mSiO prepared in accordance with the present invention2-dispersion profile of P2VP mesoporous Janus nanosheet emulsifier in deionized water at pH 3 and pH 7. Note that: different pH-responsive polymers have different dissociation constants (pKa), with pKa (P2VP) around 3 and pKa (pdmaema) around 8. When the pH of the deionized water>At pKa, the polymer is deprotonated and hydrophobic; when the pH is higher<At pKa, the polymer is protonated and hydrophilic.
FIG. 18 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-dispersion of PDMAEMA mesoporous Janus nanosheet emulsifier in deionized water, toluene and n-decane.
FIG. 19 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-optical microscopy, emulsion and demulsification of an oil/water emulsion (the oil phase is toluene) formed by PDMAEMA mesoporous Janus nanosheet emulsifier.
FIG. 20 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2An optical microscope picture, an emulsion picture and a demulsification picture of an oil/water emulsion (the oil phase is n-decane) formed by the PDMAEMA mesoporous Janus nanosheet emulsifier.
FIG. 21 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-dispersion profile of PDMAEMA mesoporous Janus nanosheet emulsifier in deionized water at pH 7 and pH 12.
FIG. 22 shows a tool made in accordance with the present inventionpH responsive C18-mSiO2And (3) carrying out 5 times of emulsification-demulsification on the P2VP mesoporous Janus nanosheet emulsifier by circulation, and then obtaining an optical microscope image, an emulsion image and a demulsification image of an oil/water emulsion image (the oil phase is n-decane).
FIG. 23 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2And (3) circulating the PDMAEMA mesoporous Janus nanosheet emulsifier for 5 times of emulsification-demulsification to obtain an optical microscopic image, an emulsion image and a demulsification image of an oil/water emulsion image (the oil phase is toluene).
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
A mesoporous Janus nanosheet emulsifier with pH responsiveness is prepared by the following steps: firstly, under the action of a surfactant, the sol-gel action of methyl orthosilicate (TMOS) is combined, and the surface of a zeolite imidazole ester framework material (ZIF) is coated with mesoporous SiO2Layer (mSiO)2) Obtaining the core-shell structure nano-particles (ZIF @ mSiO)2). Then 4- (chloromethyl) phenyltrimethoxysilane is used for modifying core-shell structure nano particles (ZIF @ mSiO)2) mSiO of2Layer to obtain ZIF @ mSiO having ATRP reactivity2-Cl, removing the surfactant by acetone extraction and obtaining HO-mSiO after etching the ZIF template by acid solution2-Cl mesoporous nanosheets. Followed by grafting of a pH responsive polymer to HO-mSiO by ATRP polymerization2mSiO of-Cl mesoporous nano-sheet2-Cl side to obtain HO-mSiO2-polymeric mesoporous nanoplatelets. Finally adopting hydrophobic silane coupling agent to carry out HO-mSiO2Carrying out hydrophobic modification on the inner side (-OH side) of the polymer mesoporous nanosheet to obtain a mesoporous Janus nanosheet emulsifier with pH responsiveness.
Preferably, the surfactant is a surfactant with a pore-forming effect; preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 (PEO)20-PPO70-PEO20) Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer F127 (PEO)106-PPO70-PEO106) One or more of Sodium Dodecyl Sulfate (SDS), polyvinylpyrrolidone (PVP) and 1-alkyl-3-methylimidazole (CnMIM).
Preferably, the Zeolitic Imidazolate Framework (ZIF) is a solid particle, preferably one or more of ZIF-5, ZIF-7, ZIF-8, ZIF-12, ZIF-67, ZIF-L.
Preferably, the particle size of the ZIF solid template particle is 200-800nm, preferably 300-600nm, and more preferably 400-500 nm.
Preferably, the acid in the acid solution etching is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Preferably, the concentration of the acid solution is 0.05 to 6mol/L, preferably 0.1 to 4mol/L, and more preferably 0.15 to 3 mol/L.
Preferably, the polymer with pH responsiveness is selected from one or more of poly (dimethylamino ethyl methacrylate) (PDMAEMA), poly (2-vinylpyridine) (P2VP), poly (2-morpholinoethyl methacrylate) (PMEMA) and poly (vinyl imidazole) (PVI).
Preferably, the hydrophobic silane coupling agent is selected from one or more of Octadecyltrimethoxysilane (ODTMS), octyltrimethoxysilane, Phenyltriethoxysilane (PETS), 4-fluorophenyltrimethoxysilane.
Preferably, the mass ratio of the added zeolite imidazolate framework material (ZIF), the surfactant and the added methyl orthosilicate (TMOS) is 1:0.5-3: 0.1-2; preferably 1:0.8-2.5: 0.3-1.5; more preferably 1:1 to 2:0.5 to 1.
Preferably, the core-shell structured nanoparticle (ZIF @ mSiO)2) And 4- (chloromethyl) phenyltrimethoxysilane are added in a mass ratio of 1:0.3-2, preferably 1:0.5-1.5, more preferably 1: 0.8-1.2.
Preferably, the HO-mSiO2The mass ratio of the added amounts of the-Cl mesoporous nanosheets, the catalyst, the ligand and the monomer is 1:0.05-0.5:0.1-0.5:1-5, preferably 1:0.08-0.4:0.15-0.4:1.5-4, and more preferably 1:0.1-0.3:0.2-0.3: 1.8-3.
Preferably, the HO-mSiO2The mass ratio of the added amounts of the polymer mesoporous nanosheet and the hydrophobic silane coupling agent is 1:0.5-3, preferably 1:0.8-2.5, and more preferably 1: 1-2.
Example 1
A preparation method of a mesoporous Janus nanosheet emulsifier with pH responsiveness (FIG. 1 is a synthetic schematic diagram of the mesoporous Janus nanosheet emulsifier with pH responsiveness prepared by the invention) comprises the following steps:
(1) core-shell structured nanoparticles (ZIF-67@ mSiO)2) The preparation of (1):
weighing ZIF-67200 mg and PVP 250mg as surfactant, placing into a 250mL single-mouth bottle, adding 80mL ethanol, and ultrasonically dispersing for 20 min; then adding 400 mu L of 6mol/L NaOH aqueous solution to adjust the pH value of the system to 10, and ultrasonically mixing for 2 min; then, 150. mu.L of a 30% (v/v) ethanol solution of TMOS was added thereto every 30min, and the mixture was stirred at room temperature for 18 hours. After completion of the reaction, the reaction mixture was centrifuged, and n was usedEthanol:nWater (W)Sequentially and respectively ultrasonically washing an alcohol-water mixed solution and an ethanol solution with the ratio of 1:1 for 3 times, and finally drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the core-shell nano-particles ZIF-67@ mSiO2。
FIG. 2 is an SEM image of a solid template ZIF-67 prepared by the present invention.
FIG. 3 is a TEM image of a solid template ZIF-67 prepared by the present invention.
FIG. 4 is a ZIF-67@ mSiO solid prepared in accordance with the present invention2SEM image of core-shell nanoparticles.
FIG. 5 is a ZIF-67@ mSiO solid prepared in accordance with the present invention2TEM images of core-shell nanoparticles.
FIG. 6 is a diagram of mSiO prepared according to the invention2Mesoporous nanosheet pair N2Adsorption-desorption curve of (d).
FIG. 7 is a diagram of mSiO prepared according to the present invention2The aperture distribution map of the mesoporous nano sheet.
(2)HO-mSiO2Preparation of-Cl mesoporous nanosheets:
weighing 200mg of ZIF-67@ mSiO2Core-shell nano-particles are ultrasonically dispersed in 40mL of toluene solvent, 200 mu L of 4- (chloromethyl) phenyltrimethoxysilane is added,ultrasonically dispersing uniformly, performing reflux reaction in an oil bath kettle at 100 ℃ for 10 hours, cooling to room temperature after the reaction is finished, performing centrifugal separation, washing for 3 times by adopting methylbenzene to remove incompletely reacted 4- (chloromethyl) phenyltrimethoxysilane, and then placing in a vacuum drying oven to dry for 12 hours at the temperature of 60 ℃ to obtain ZIF-67@ mSiO with ATRP reaction activity2-Cl; after the surface active agent is removed by acetone extraction, 1mol/L hydrochloric acid solution is adopted to etch ZIF-67, and HO-mSiO is obtained2-Cl mesoporous nanosheets.
FIG. 8 is a ZIF-67@ mSiO solid prepared in accordance with the present invention2And ZIF-67@ mSiO2Zeta potential contrast plot of Cl.
FIG. 9 is HO-mSiO prepared according to the present invention2EDS picture of-Cl mesoporous nano-sheet.
(3)HO-mSiO2Preparation of P2VP mesoporous nanosheets:
weighing 150mg HO-mSiO2adding-Cl mesoporous nanosheets, 25mg of CuBr, 50 mu L of PMDETA and 0.4g of 2-VP into a polymerization tube containing 10mL of methanol; then half opening the polymerization tube, introducing nitrogen for 30min, freezing with liquid nitrogen, vacuumizing for 10min, and thawing; then circularly freezing-unfreezing for 3 times, and sealing the tube in a vacuum state; the polymerization tube was then heated to 60 ℃ for 12 h. Opening a sealed tube after the reaction is finished, stopping the reaction after contacting air, centrifugally separating, washing for 3 times by adopting methanol, and then drying for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain HO-mSiO2-P2VP mesoporous nanoplatelets.
FIG. 10 is a HO-mSiO prepared in accordance with the present invention2SEM image of P2VP mesoporous nanosheet.
FIG. 11 is HO-mSiO prepared according to the present invention2TEM image of mesoporous nanoplates of P2 VP.
(4) C18-mSiO with pH responsiveness2Preparation of P2VP mesoporous Janus nanosheet emulsifier:
weighing HO-mSiO2100mg of P2VP mesoporous nanosheet and 100 mu L of Octadecyltrimethoxysilane (ODTMS) are dispersed in 20mL of toluene solvent by ultrasonic; then carrying out reflux reaction for 10h in an oil bath kettle at 100 ℃; after the reaction was completed, it was naturally cooled to room temperature, centrifuged, and washed with toluene 3 times to remove incompletely reacted eighteenAlkyltrimethoxysilane (ODTMS) to give a C18-mSiO with a hydrophilic polymer P2VP on one side and a hydrophobic octadecyl group on the other side with pH responsiveness2And (4) drying a P2VP mesoporous Janus nanosheet emulsifier for later use.
FIG. 12 is a pH responsive C18-mSiO prepared in accordance with the present invention2TEM image of mesoporous Janus nanosheet emulsifier P2 VP.
FIG. 13 is a mSiO prepared according to the invention2、HO-mSiO2-Cl、C18-mSiO2-ir contrast map of P2 VP.
Example 2
(1) Core-shell structured nanoparticles (ZIF-8@ mSiO)2) The preparation of (1):
weighing ZIF-8200 mg and SDS 200mg of surfactant, placing into a 250mL single-mouth bottle, adding 80mL ethanol, and performing ultrasonic dispersion for 20 min; then adding 500 mu L of 5mol/L KOH aqueous solution to adjust the pH value of the system to 11, and ultrasonically mixing for 2 min; then, 120. mu.L of a 30% (v/v) ethanol solution of TMOS was added thereto every 40min, and the mixture was stirred at room temperature for 20 hours. After completion of the reaction, the reaction mixture was centrifuged, and n was usedEthanol:nWater (W)Sequentially and respectively ultrasonically washing an alcohol-water mixed solution and an ethanol solution with the ratio of 1:1 for 3 times, and finally drying in a vacuum drying oven at the temperature of 70 ℃ for 10 hours to obtain the core-shell nano-particles ZIF-8@ mSiO2。
(2)HO-mSiO2Preparation of-Cl mesoporous nanosheets:
weighing 200mg of ZIF-8@ mSiO2Ultrasonically dispersing core-shell nano particles in 40mL of toluene solvent, adding 180 mu L of 4- (chloromethyl) phenyltrimethoxysilane, ultrasonically dispersing the core-shell nano particles uniformly, performing reflux reaction in an oil bath kettle at the temperature of 80 ℃ for 12 hours, cooling to room temperature after the reaction is finished, performing centrifugal separation, washing for 3 times by using toluene to remove the incompletely reacted 4- (chloromethyl) phenyltrimethoxysilane, and then placing the core-shell nano particles in a vacuum drying oven to dry for 10 hours at the temperature of 70 ℃ to obtain ZIF-8 mSiO with ATRP reaction activity2-Cl; after the surface active agent is removed by acetone extraction, the ZIF-8 is etched by adopting 0.5mol/L sulfuric acid solution to obtain HO-mSiO2-Cl mesoporous nanosheets.
(3)HO-mSiO2Mesoporous (PDMAEMA)Preparing a nano sheet:
weighing 150mg HO-mSiO2adding-Cl mesoporous nanosheets, 25mg of CuBr, 50 mu L of PMDETA and 0.5g of DMAEMA into a polymerization tube containing 10mL of methanol; then half opening the polymerization tube, introducing argon gas for 40min, freezing with liquid nitrogen, vacuumizing for 10min, and thawing; then circularly freezing-unfreezing for 3 times, and sealing the tube in a vacuum state; the polymerization tube was then heated to 60 ℃ for 14 h. Opening a sealed tube after the reaction is finished, stopping the reaction after contacting air, centrifugally separating, washing for 3 times by adopting methanol, and then drying for 10 hours at the temperature of 70 ℃ in a vacuum drying oven to obtain HO-mSiO2-PDMAEMA mesoporous nanoplatelets.
(4) phenyl-mSiO with pH responsiveness2Preparation of PDMAEMA mesoporous Janus nanosheet emulsifier:
weighing HO-mSiO2100mg of PDMAEMA mesoporous nanosheet and 90 mu L of Phenyltriethoxysilane (PETS) are ultrasonically dispersed in 20mL of toluene solvent; then carrying out reflux reaction for 12h in an oil bath kettle at the temperature of 80 ℃; after the reaction is finished, naturally cooling to room temperature, centrifugally separating, washing for 3 times by toluene to remove incompletely reacted Phenyltriethoxysilane (PETS) to obtain the phenyl-mSiO with pH responsiveness, one side of which is a hydrophilic polymer PDMAEMA and the other side is a phenyl hydrophobic group2-PDMAEMA mesoporous Janus nanosheet emulsifier, and drying for later use.
Example 3
Example 1 was repeated except that the surfactant was a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 (PEO)20-PPO70-PEO20)。
Example 4
Example 1 was repeated except that the Zeolitic Imidazolate Framework (ZIF) was ZIF-L.
Example 5
Example 2 was repeated except that the polymer having pH responsiveness was poly (2-morpholinoethyl methacrylate) (PMEMA).
Example 6
Example 2 was repeated except that the hydrophobic silane coupling agent was 4-fluorophenyl trimethoxysilane.
Effect test example 1
4mg of the pH responsive C18-mSiO prepared in example 12Dispersing a P2VP mesoporous Janus nanosheet emulsifier in 2mL of deionized water with pH of 3 and an oil phase solution respectively, and observing the dispersion condition; then, 10mg of the mesoporous Janus nanosheets are added into an oil-water mixed solution, the mixed solution is stirred for 1min at the rotating speed of 12000rpm to form an emulsion, the size of the emulsion droplet is calculated through an optical microscope to evaluate the stability of the emulsion, and the influence of the type of the oil phase on the emulsification effect is researched. The result shows that the mesoporous Janus nanosheet emulsifier obtained by the invention can be uniformly dispersed in water phase and oil phase solutions, and has good amphiphilic performance; when the structure of the hydrophobic molecule in the mesoporous Janus nanosheet is similar to that of the oil phase solution, the obtained emulsion is smaller in droplet size and more stable.
To study its pH responsiveness, we regulated the pH with NaOH aqueous solution, specifically: respectively taking 4mg of the mesoporous Janus nanosheet emulsifier, dispersing in 2mL of deionized water with the pH value of 3 and the pH value of 7, and observing the dispersion condition; then, a certain amount of aqueous NaOH solution was added to the resulting stable emulsion to adjust pH to 7, and after magnetic stirring for a while, the state of the emulsion was observed. The result shows that when the pH value is 7, the nano sheets are deposited at the bottom of the bottle due to deprotonation and hydrophobicity of the P2VP side in the mesoporous Janus nano sheets, emulsion breaking is performed on the emulsion to separate oil from water, and the controllable emulsification-demulsification process is realized by regulating and controlling the pH value.
FIG. 14 is a pH responsive C18-mSiO prepared in accordance with the present invention2-P2VP dispersion pattern of mesoporous Janus nanosheet emulsifier in deionized water, toluene and n-decane.
FIG. 15 is a pH responsive C18-mSiO prepared in accordance with the present invention2-optical microscopy, emulsion and emulsion breaking of an oil/water emulsion (the oil phase is toluene) formed by the P2VP mesoporous Janus nanosheet emulsifier.
FIG. 16 is a pH responsive C18-mSiO prepared in accordance with the present invention2An optical microscope picture, an emulsion picture and a demulsification picture of an oil/water emulsion (the oil phase is n-decane) formed by the P2VP mesoporous Janus nanosheet emulsifier.
FIG. 17 is a drawing of the present inventionPrepared C18-mSiO with pH responsiveness2-dispersion profile of P2VP mesoporous Janus nanosheet emulsifier in deionized water at pH 3 and pH 7.
Effect test example 2
5mg of the pH-responsive phenyl-mSiO prepared in example 22Respectively dispersing a PDMAEMA mesoporous Janus nanosheet emulsifier in 2mL of deionized water with the pH value of 7 and an oil phase solution, and observing the dispersion condition; then, 10mg of the mesoporous Janus nanosheets are added into an oil-water mixed solution, the mixed solution is stirred for 1min at the rotating speed of 12000rpm to form an emulsion, the size of the emulsion droplet is calculated through an optical microscope to evaluate the stability of the emulsion, and the influence of the type of the oil phase on the emulsification effect is researched. The result shows that the mesoporous Janus nanosheet emulsifier obtained by the invention can be uniformly dispersed in water phase and oil phase solutions, and has good amphiphilic performance; when the structure of the hydrophobic molecule in the mesoporous Janus nanosheet is similar to that of the oil phase solution, the obtained emulsion is smaller in droplet size and more stable.
To study its pH responsiveness, we regulated the pH by aqueous KOH, specifically: respectively taking 5mg of the mesoporous Janus nanosheet emulsifier, dispersing in 2mL of deionized water with the pH value of 7 and the pH value of 12, and observing the dispersion condition; then, a certain amount of an aqueous KOH solution was added to the resulting stable emulsion to adjust the pH to 12, and after magnetic stirring for a while, the state of the emulsion was observed. The result shows that when the pH value is 12, the nano sheets are deposited at the bottom of the bottle due to deprotonation and hydrophobicity of the PDMAEMA side in the mesoporous Janus nano sheets, emulsion breaking is performed on the emulsion to separate oil from water, and the controllable emulsification-demulsification process is realized by regulating and controlling the pH value.
FIG. 18 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-dispersion of PDMAEMA mesoporous Janus nanosheet emulsifier in deionized water, toluene and n-decane.
FIG. 19 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-optical microscopy, emulsion and demulsification of an oil/water emulsion (the oil phase is toluene) formed by PDMAEMA mesoporous Janus nanosheet emulsifier.
FIG. 20 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-PDMAEAn optical microscope picture, an emulsion picture and a demulsification picture of an oil/water emulsion (the oil phase is n-decane) formed by the MA mesoporous Janus nanosheet emulsifier.
FIG. 21 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2-dispersion profile of PDMAEMA mesoporous Janus nanosheet emulsifier in deionized water at pH 7 and pH 12.
The C18-mSiO with pH responsiveness prepared in the embodiment 1 of the invention2And after the P2VP mesoporous Janus nanosheet emulsifier is circularly emulsified for 5 times and is demulsified, liquid drops with the size equivalent to that of the initial emulsion can still be obtained, and the quick demulsification can still be realized by regulating the pH value. phenyl-mSiO with pH responsiveness prepared in example 2 of the invention2After the-PDMAEMA mesoporous Janus nanosheet emulsifier is emulsified for 5 times and de-emulsified, liquid drops with the size equivalent to that of the initial emulsion can be obtained, and the pH value can be regulated and controlled to still achieve rapid de-emulsification.
FIG. 22 is a pH responsive C18-mSiO prepared according to the present invention2And (3) carrying out 5 times of emulsification-demulsification on the P2VP mesoporous Janus nanosheet emulsifier by circulation, and then obtaining an optical microscope image, an emulsion image and a demulsification image of an oil/water emulsion image (the oil phase is n-decane).
FIG. 23 is a pH responsive phenyl-mSiO prepared in accordance with the present invention2And (3) circulating the PDMAEMA mesoporous Janus nanosheet emulsifier for 5 times of emulsification-demulsification to obtain an optical microscopic image, an emulsion image and a demulsification image of an oil/water emulsion image (the oil phase is toluene).

Claims (10)

1. A mesoporous Janus nanosheet emulsifier with pH responsiveness is prepared by the following steps: firstly, under the action of a surfactant, the sol-gel action of methyl orthosilicate (TMOS) is combined, and the surface of a zeolite imidazole ester framework material (ZIF) is coated with mesoporous SiO2Layer (mSiO)2) Obtaining the core-shell structure nano-particles (ZIF @ mSiO)2) (ii) a Then 4- (chloromethyl) phenyl trimethoxy silane is grafted on core-shell structure nano particles (ZIF @ mSiO)2) mSiO of2On the outer side of the layer to obtain ZIF @ mSiO with ATRP reaction activity2-Cl; after the surfactant is removed by extraction, the ZIF template is etched by acid solutionObtaining HO-mSiO2-Cl mesoporous nanoplatelets; followed by grafting of a pH responsive polymer to HO-mSiO by ATRP polymerization2mSiO of-Cl mesoporous nano-sheet2-Cl side to obtain HO-mSiO2-a polymeric mesoporous nanoplatelet; finally adopting hydrophobic silane coupling agent to carry out HO-mSiO2Carrying out hydrophobic modification on the inner side (-OH side) of the polymer mesoporous nanosheet to obtain a mesoporous Janus nanosheet emulsifier with pH responsiveness.
2. The emulsifier according to claim 1, characterized in that: the surfactant is a surfactant with a pore-forming effect; preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 (PEO)20-PPO70-PEO20) Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer F127 (PEO)106-PPO70-PEO106) One or more of Sodium Dodecyl Sulfate (SDS), polyvinylpyrrolidone (PVP) and 1-alkyl-3-methylimidazole (CnMIM); and/or
The zeolite imidazolate framework material (ZIF) is solid particles, preferably one or more of ZIF-5, ZIF-7, ZIF-8, ZIF-12, ZIF-67 and ZIF-L; preferably, the particle size of the ZIF solid template particle is 200-800nm, preferably 300-600nm, and more preferably 400-500 nm; and/or
The acid in the acid solution etching is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; preferably, the concentration of the acid solution is 0.05 to 6mol/L, preferably 0.1 to 4mol/L, and more preferably 0.15 to 3 mol/L.
3. The emulsifier according to claim 1 or 2, characterized in that: the polymer with pH responsiveness is selected from one or more of poly (dimethylamino ethyl methacrylate) (PDMAEMA), poly (2-vinylpyridine) (P2VP), poly (2-morpholinoethyl methacrylate) (PMEMA) and polyvinyl imidazole (PVI); and/or
The hydrophobic silane coupling agent is selected from one or more of octadecyl trimethoxy silane (ODTMS), octyl trimethoxy silane, phenyl triethoxy silane (PETS) and 4-fluorophenyl trimethoxy silane.
4. A method of preparing the pH-responsive mesoporous Janus nanosheet emulsifier of any one of claims 1-3, the method comprising the steps of:
1) coating mesoporous SiO on the surface of a zeolite imidazole ester framework material (ZIF) under the pore-forming action of a surfactant and the sol-gel action of methyl orthosilicate (TMOS)2Layer (mSiO)2) Obtaining the core-shell structure nano-particles (ZIF @ mSiO)2)；
2) Grafting 4- (chloromethyl) phenyltrimethoxysilane to the core-shell structure nanoparticles (ZIF @ mSiO) obtained in the step 1) by utilizing the protection effect of a ZIF template2) mSiO of2On the outer side of the layer to obtain ZIF @ mSiO with ATRP reaction activity2-Cl; after the surfactant is removed by extraction, the ZIF template is etched by acid solution to obtain HO-mSiO2-Cl mesoporous nanoplatelets;
3) grafting a polymer having pH responsiveness to the HO-mSiO obtained in step 2) by ATRP polymerization in the presence of a catalyst and a ligand2mSiO of-Cl mesoporous nano-sheet2-Cl side to obtain HO-mSiO2-a polymeric mesoporous nanoplatelet;
4) the HO-mSiO obtained in the step 3) is treated by a hydrophobic silane coupling agent2Carrying out hydrophobic modification on the inner side (-OH side) of the polymer mesoporous nanosheet to obtain a mesoporous Janus nanosheet emulsifier with pH responsiveness.
5. The method of claim 4, wherein: in the step 1), the mass ratio of the added zeolite imidazole ester framework material (ZIF), the surfactant and the added methyl orthosilicate (TMOS) is 1:0.5-3: 0.1-2; preferably 1:0.8-2.5: 0.3-1.5; more preferably 1:1-2: 0.5-1; and/or
In step 2), the core-shell structured nanoparticle (ZIF @ mSiO)2) And 4- (chloromethyl) phenyltrimethoxysilane are added in a mass ratio of 1:0.3-2, preferably 1:0.5-1.5, more preferably 1: 0.8-1.2; and/or
In step 3), the HO-mSiO2The mass ratio of the added amounts of the-Cl mesoporous nanosheets, the catalyst, the ligand and the monomer is 1:0.05-0.5:0.1-0.5:1-5, preferably 1:0.08-0.4:0.15-0.4:1.5-4, and more preferably 1:0.1-0.3:0.2-0.3: 1.8-3; and/or
In step 4), the HO-mSiO2The mass ratio of the added amounts of the polymer mesoporous nanosheet and the hydrophobic silane coupling agent is 1:0.5-3, preferably 1:0.8-2.5, and more preferably 1: 1-2.
6. The method of claim 5, wherein: the step 1) is specifically as follows: weighing zeolite imidazole ester framework material (ZIF) and surfactant in proportion, and ultrasonically dispersing in a solution (such as ethanol solution); then adjusting the system to be alkaline (for example, adjusting the pH value to 9-13, preferably 10-12 by using an alkaline solution; preferably, the alkaline solution is sodium hydroxide or potassium hydroxide), and uniformly mixing by ultrasonic; adding TMOS ethanol solution for several times (such as 1-8 times, preferably 2-5 times; each time interval is 10-60min, preferably 20-40min), and stirring (such as magnetically stirring at room temperature for 8-24h, preferably 12-18 h); after the reaction is finished, centrifugal separation is carried out, and an alcohol-water mixed solution (preferably n) is adopted in sequenceEthanol:nWater (W)1:1 mixed solution), ultrasonic washing with ethanol for 1-5 times (preferably 2-4 times), and drying (such as drying in vacuum oven at 40-80 deg.C for 8-24 hr, preferably at 50-70 deg.C for 10-18 hr); obtaining the core-shell structure nano-particles (ZIF @ mSiO)2)。
7. The method of claim 6, wherein: the step 2) is specifically as follows: weighing the core-shell structure nanoparticles (ZIF @ mSiO) obtained in the step 1) in proportion2) Adding into organic solvent (such as toluene solution), adding 4- (chloromethyl) phenyl trimethoxy silane, ultrasonically dispersing uniformly, and heating for reflux reaction (the reaction temperature is 60-120 deg.C, preferably 80-110 deg.C, more preferably 90-100 deg.C); the reaction time is 3-24h, preferably 5-18h, and more preferably 8-12 h); after completion of the reaction, it is cooled (e.g., naturally cooled to room temperature), centrifuged, and washed (e.g., washing with a toluene solution 1)-5 times, preferably 2-4 times), drying (e.g. drying in a vacuum oven at 50-120 ℃ for 6-24h, preferably at 60-100 ℃ for 8-18h) to obtain ZIF @ mSiO having ATRP reactivity2-Cl; after removing the surfactant by acetone extraction for 2-5 times (preferably 3 times, each time preferably 24 hours), etching the ZIF template by using an acid solution (such as 0.05-6mol/L, preferably 0.1-4mol/L, more preferably 0.15-3mol/L hydrochloric acid solution) to obtain HO-mSiO2-Cl mesoporous nanosheets.
8. The method of claim 7, wherein: the step 3) is specifically as follows: weighing the HO-mSiO obtained in the step 2) according to the proportion2Adding the-Cl mesoporous nanosheets, a catalyst (preferably CuBr), a ligand (preferably PMDETA), a monomer and a solvent (preferably a methanol solution) into a polymerization tube; introducing protective gas (such as nitrogen or helium or argon, preferably nitrogen) for 10-60min (preferably 20-50min, more preferably 30-40min), freezing with liquid nitrogen, vacuumizing, thawing, repeating freezing-thawing operation for 1-5 times (preferably 2-4 times), and sealing under vacuum; then, heating for reaction (the reaction temperature is 30-80 ℃, preferably 40-70 ℃, more preferably 50-60 ℃, the reaction time is 5-18h, preferably 8-15h, more preferably 10-12 h); after the reaction is completed, the sealed tube is opened, centrifuged, washed (for example, 1-5 times, preferably 2-3 times, by using a methanol solution), dried (for example, dried in a vacuum drying oven at 40-80 ℃ for 8-24h, preferably at 50-70 ℃ for 10-15h) to obtain HO-mSiO2-polymeric mesoporous nanoplatelets.
9. The method of claim 8, wherein: the step 4) is specifically as follows: weighing the HO-mSiO obtained in the step 3) according to the proportion2Ultrasonically dispersing a polymer mesoporous nanosheet and a hydrophobic silane coupling agent in an organic solvent (preferably a toluene solution); then heating to carry out reflux reaction (the reaction temperature is 60-120 ℃, preferably 80-110 ℃, more preferably 90-100 ℃, the reaction time is 3-18h, preferably 5-15h, more preferably 8-12 h); after the reaction is completed, cooling (e.g., natural cooling to room temperature), centrifugal separation, washing (e.g., 1 to 5 times with a toluene solution,preferably 2-4 times), thus obtaining the mesoporous Janus nanosheet emulsifier with pH responsiveness.
10. Use of a mesoporous Janus nanosheet emulsifier having pH-responsiveness of any one of claims 1 to 3 or prepared according to the method of any one of claims 4 to 9, wherein: the mesoporous Janus nanosheet emulsifier with pH responsiveness is used for regulating and controlling the pH value to realize a controllable emulsification-demulsification process.
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