CN111450721A - Preparation method of multifunctional integrated Pickering emulsion - Google Patents
Preparation method of multifunctional integrated Pickering emulsion Download PDFInfo
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Abstract
The invention discloses a preparation method of multifunctional integrated Pickering emulsion, which comprises the following steps: mixing and dispersing the multifunctional integrated Pickering particle emulsifier and a solvent A to prepare a dispersion liquid A; mixing the dispersion liquid A with an oil phase, and preparing the multifunctional integrated Pickering emulsion in an emulsifying mode; the multifunctional integrated Pickering particle emulsifier is prepared from gas-phase silica particles, an amino silane coupling agent and a hydrophobic alkyl silane coupling agent in a mass ratio of 5: 2-9: 0.5-5. The multifunctional integrated Pickering emulsion prepared by the invention has good long-term stability and CO2Responsive emulsion-break cyclicity, emulsifying, stabilizing and CO2The responsiveness is integrated, and the chromatographic separation effect which can occur in the storage and use process is avoided.
Description
Technical Field
The invention relates to the technical field of preparation of fine chemical products. More particularly, relates to a preparation method of multifunctional integrated Pickering emulsion.
Background
The Pickering emulsion is formed by stabilizing two immiscible liquids by adsorbing solid particles on a liquid-liquid two-phase interface, is more stable compared with the traditional surfactant, has the advantages of low toxicity, higher stability, low cost and environmental friendliness, and is widely applied to various fields such as cosmetics, foods, crude oil exploitation, sewage treatment, biomedicine and the like.
In general, different types of Pickering emulsions can be prepared in a manner similar to that used to prepare classical surfactant emulsions by dispersing hydrophobic or hydrophilic particles in an oil or water phase and then adding the corresponding water or oil phase to the mixture, and emulsifying the mixture under high speed homogenization or sonication to obtain the corresponding Pickering emulsion, when relatively hydrophilic particles are used, an oil-in-water Pickering emulsion, and when relatively hydrophobic particles are used, a water-in-oil Pickering emulsion is obtained.]The Pickering emulsion is stabilized by using short-chain aliphatic amine and L ammonium particles together, and the stability of the emulsion is regulated by regulating the concentration of the short-chain aliphatic amine, Jiang et al (Jiang, J.; Zhu, Y.; Cui, Z.; Binks, B.P. Switchabelpfelizer emulsion is hydrogenated in situ with a movable surfactant, Angew.chem.int.Ed.2013,52, 12373-12376.]The silicon dioxide particles and the surfactant dodecyl dimethyl acetamidine are used for jointly stabilizing the surfactant with CO2Responsive Pickering emulsion L iang et al [ L iang, C.; L iu, Q.; Xu, Z2-responsive particles.ACS Appl.Mater.Interfaces 2014,6,6898–6904.]Will have CO2Responsive N, N-dimethylacetamide decimal fractionSub-grafted on silica particles to stabilize CO2Responsive Pickering emulsion, professor Liuxue Peak of university in south Jiangnan [ Y.Zhang, S.Guo, W.Wu, Z.Qin, X. L iu2-triggered Pickeringemulsion based on silica nanoparticles and tertiary amine with longhydrophobic tails.Langmuir 2016,32,11861-11867.]And professor j.jiang, y.ma, z.cui, b.p.binks.pickering emulsions responsive to CO2/N2and light dualstimuli at ambient temperature.Langmuir,2016,32,8668-8675.]A compound system is respectively constructed by utilizing a novel surfactant and nano silicon dioxide particles and is used for preparing responsive Pickering emulsion, so that the performance of the emulsion is accurately controlled. In patent CN 106582431A, nano silicon dioxide and CO are used2/N2A room temperature response emulsifier is prepared by a switch type surfactant composite system, and the obtained emulsifier has high stability and can realize CO at room temperature2The emulsion breaking and re-emulsifying functions of the switch emulsion.
In the above documents, some complex systems of surfactants, polymers and nanoparticles are mostly adopted, and the multi-component mixed complex has the problem of 'chromatographic separation' or stable failure in the application process, because the adsorption effect of the surfactants or polymers on rocks is determined by the composition of the surfactants or polymers, and in the complex process, the adsorption effect of different surfactants on rocks is different, so that the effect of the complex system and the oil displacement efficiency are influenced.
In order to solve the chromatographic separation effect of a surfactant or a polymer, the invention provides a preparation method of a multifunctional integrated Pickering emulsion, which realizes the emulsification of different oil phases and water phases, the stabilization of the Pickering emulsion and the CO emulsion2/N2Cycle response characteristics at room temperature.
Disclosure of Invention
The invention aims to provide a preparation method of a multifunctional integrated Pickering emulsion.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of multifunctional integrated Pickering emulsion comprises the following steps:
mixing and dispersing the multifunctional integrated Pickering particle emulsifier and a solvent A to prepare a dispersion liquid A;
mixing the dispersion liquid A and an oil phase, and preparing the multifunctional integrated Pickering emulsion in an emulsifying mode;
the multifunctional integrated Pickering particle emulsifier is prepared from gas-phase silica particles, an amino silane coupling agent and a hydrophobic alkyl silane coupling agent in a mass ratio of 5: 2-9: 0.5-5.
Preferably, the concentration of the multifunctional integrated Pickering particle emulsifier in the dispersion liquid A is 0.25mg/m L-10 mg/m L.
Preferably, the solvent a comprises deionized water or brine.
Preferably, the concentration of the saline water is 0.01 mol/L-5 mol/L.
Preferably, the brine is an aqueous sodium chloride solution.
Preferably, the volume ratio of the oil phase to the dispersion liquid A is (20-80): 20-80); more preferably 1: 1.
Preferably, the oil phase comprises at least one of alkanes, cycloalkanes, hydrocarbon mineral oils, esters, vegetable oils, and petroleum oils; further, the oil phase includes at least one of ethyl acetate, toluene, methylene chloride, petroleum ether, n-hexane, cyclohexane, and crude oil.
Preferably, the emulsification means comprises at least one of manual shaking, ultrasonic emulsification, shear emulsification and high pressure shear emulsification.
Preferably, the primary particle size of the fumed silica particles is 4nm to 200nm, and the BET specific surface area of the fumed silica particles is 50m2/g～400m2/g。
Preferably, the amino silane coupling agent is a C4-C20 linear or branched primary amine or secondary amine or tertiary amine silane coupling agent containing 1-10 amino groups.
Preferably, the amino silane coupling agent is diethylenetriaminopropyltrimethoxysilane, butylpropylamino-triethoxysilane, diethylaminomethyltrimethoxysilane or tris (2-aminoethyl) propylaminotrimethoxysilane.
Preferably, the hydrophobic alkyl silane coupling agent is a C3-C20 linear or branched chain saturated alkyl silane coupling agent.
Preferably, the hydrophobic alkylsilane coupling agent is n-dodecyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-hexyltrimethoxysilane, n-octadecyltrimethoxysilane, or propyltriethoxysilane.
Preferably, the preparation method of the multifunctional integrated Pickering particle emulsifier comprises the following steps:
mixing fumed silica particles with a solvent B, and performing ultrasonic dispersion to obtain a dispersion liquid B;
under the protection of inert gas or nitrogen, mixing the dispersion liquid B, an amino silane coupling agent and a hydrophobic alkyl silane coupling agent to obtain a reaction liquid, heating the reaction liquid to react to obtain a reaction product, separating the reaction product to obtain solid particles, cleaning the solid particles, and drying to obtain the multifunctional integrated Pickering particle emulsifier. The invention uses chemical grafting modification to graft an amino silane coupling agent and a hydrophobic silane coupling agent on the surface of silicon dioxide particles in one step by a one-pot method.
Preferably, the step of drying the fumed silica particles before mixing the fumed silica particles with the solvent further comprises: drying the fumed silica particles for 0.5 to 12 hours at the temperature of between 80 and 150 ℃.
Preferably, the time of ultrasonic dispersion is 5-30 min; the time of the ultrasonic dispersion depends on the particle size of the fumed silica particles and can be adjusted according to actual conditions.
Preferably, the concentration of the gas-phase silica particles in the dispersion liquid B is 5 g/L-50 g/L.
Preferably, the concentration of the amino silane coupling agent in the reaction liquid is 1 g/L-50 g/L.
Preferably, the concentration of the hydrophobic alkylsilane coupling agent in the reaction solution is 1 g/L-50 g/L.
Preferably, the solvent B is anhydrous toluene.
Preferably, the inert gas is argon.
Preferably, the heating reaction temperature is 80-110 ℃, and the heating reaction time is 2-12 h.
Preferably, the reaction product is separated by centrifugation.
Preferably, the washing of the solid particles specifically includes washing the solid particles twice with toluene and acetone, respectively.
The multifunctional integrated Pickering emulsion prepared by the invention is of an oil-in-water type, has high salt resistance, has salt concentration of 0.01-5 mol/L, has long-term standing stability, can be placed for more than 6 months, has centrifugal stability, can be stabilized for more than 1 hour at a centrifugal speed of 4000rpm, and can adjust the water contact angle of an emulsifier to be between 40-80 degrees by the proportion of the amino silane coupling agent and the hydrophobic alkyl silane coupling agent.
The invention has the following beneficial effects:
(1) the multifunctional integrated Pickering emulsion prepared by the invention has good long-term stability and CO2Responsive emulsion-break cyclicity, emulsifying, stabilizing and CO2The responsiveness is integrated, and the possible chromatographic separation effect in the storage and use process is avoided, so that the method has important application value in the related application fields of tertiary oil recovery, emulsion polymerization, wastewater treatment, cosmetics, food and the like;
(2) the multifunctional integrated Pickering emulsion prepared by the invention has long-term storage stability and high-speed centrifugal stability, and avoids oil-water phase separation of the emulsion in the storage and use processes, so that the multifunctional integrated Pickering emulsion has important application value in related application fields of tertiary oil recovery, emulsion polymerization, cosmetics, food, textile printing and dyeing and the like;
(3) the multifunctional integrated Pickering particle emulsifier in the raw materials adopted by the multifunctional integrated Pickering emulsion prepared by the invention can be prepared in one step by a one-pot method, the preparation method is simple and convenient, and the obtained emulsifier has good emulsifying property, stability and CO2Response performance.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a structural schematic diagram of the multifunctional integrated Pickering particle emulsifier provided by the invention.
Fig. 2 shows an appearance schematic diagram of the multifunctional integrated Pickering particulate emulsifier prepared in example 1.
FIG. 3 shows a transmission electron micrograph of the multifunctional integrated Pickering particulate emulsifier prepared in example 2.
Fig. 4 shows a schematic of the water contact angle of the multifunctional integrated Pickering particulate emulsifier prepared in example 3.
Fig. 5 shows a schematic of the water contact angle of the multifunctional integrated Pickering particulate emulsifier prepared in example 4.
Fig. 6 shows the appearance and microscopic representation of the multifunctional integrated Pickering emulsion prepared in example 5.
Fig. 7 shows the appearance and microscopic representation of the salt tolerance of the multifunctional integrated Pickering emulsion prepared in example 6.
Fig. 8 shows the appearance and microscopic representation of the salt tolerance of the multifunctional integrated Pickering emulsion prepared in example 7.
Fig. 9 shows an appearance diagram of the long-term storage stability of the multifunctional integrated Pickering emulsion prepared in example 8.
Figure 10 shows a schematic of the centrifugal stability of the multifunctional integrated Pickering emulsion prepared in example 9.
Figure 11 shows a schematic of the centrifugal stability of the multifunctional integrated Pickering emulsion prepared in example 10.
FIG. 12 shows a comparative schematic of the multi-functional integrated Pickering emulsions of different oil phases prepared in example 16.
FIG. 13 shows a comparative schematic of the multifunctional integrated Pickering emulsions obtained in different emulsification modes prepared in example 17.
Fig. 14 shows a schematic of the long-term shelf stability of the multifunctional integrated Pickering emulsion prepared in example 18.
FIG. 15 shows CO for the multifunctional integrated Pickering emulsion prepared in example 192/N2A graph of cyclic responsiveness.
FIG. 16 is a schematic diagram showing the passage of the multifunctional integrated Pickering emulsion prepared in example 20 through a silica sand chromatography column.
FIG. 17 is a graph showing the results of viscosity tests before and after passing through a silica sand column for multiple times for the multifunctional integrated Pickering emulsion prepared in example 20.
Fig. 18 shows a schematic of the water contact angle of the single amine-functionalized Pickering particulate emulsifier prepared in comparative example 1.
Figure 19 shows a schematic of the water contact angle of a single hydrophobic alkyl functionalized Pickering particulate emulsifier prepared in comparative example 2.
Fig. 20 shows a schematic appearance of the single amine-functionalized Pickering emulsion prepared in comparative example 3.
Fig. 21 shows a schematic appearance of a single hydrophobic alkyl functionalized Pickering emulsion prepared in comparative example 4.
Fig. 22 shows a schematic appearance of Pickering emulsion prepared in example 21.
Fig. 23 shows a schematic appearance of Pickering emulsion prepared in example 22.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil380, which is a fumed silica particle (primary particle diameter 7nm, BET specific surface area 380 m)2(g, Evonik chemical Co., Ltd., Aerosil380, AR) was dried in a vacuum oven at 100 ℃ for 1 hour, and20m L anhydrous toluene is added into a 50m L round bottom flask together, the mixture is subjected to ultrasonic treatment at room temperature and 50kHz frequency for 10 minutes to be uniformly dispersed to obtain a dispersion liquid B, 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical technology Co., Ltd., purity of 95 wt%) and 0.5g of n-dodecyltrimethoxysilane (Shanghai Bailingwei chemical technology Co., Ltd., purity of 95 wt%) are added into the dispersion liquid B to obtain a reaction liquid, the reaction liquid reacts for 12 hours in an oil bath at the temperature of 110 ℃ and a nitrogen environment to obtain a reaction product, the reaction product is subjected to centrifugal separation to obtain solid particles, the solid particles are respectively washed twice by toluene and acetone, and the solid particles are subjected to vacuum drying at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier.
The multifunctional integrated Pickering particle emulsifier prepared by the embodiment has the average hydraulic particle size of 220 +/-50 nm and is white powder. The structure of the multifunctional integrated Pickering particle emulsifier is shown in the attached drawing 1, and the structural schematic diagram of the multifunctional integrated Pickering particle emulsifier is shown in the drawing 1. The appearance is shown in attached figure 2, and figure 2 is an appearance schematic diagram of the multifunctional integrated Pickering particle emulsifier prepared in example 1. As can be seen from FIG. 2, the macroscopic properties and color of the particles before and after modification are unchanged.
Example 2
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil200 (primary particle size 14nm, BET specific surface area 200 m) as fumed silica particles2(g, Evonik chemical Co., Ltd., Aerosil200, AR) was dried in a vacuum oven at 110 ℃ for 1 hour, added together with 20m L anhydrous toluene to a 50m L round-bottomed flask, and dispersed uniformly by sonication at room temperature and a frequency of 50kHz for 10 minutes to obtain dispersion B, to which were added 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Tantan technology Co., Ltd., purity 95 wt%) and 0.1g of n-hexadecyltrimethoxysilane (Shanghai Bailingwei technology Co., Ltd., purity 95 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ under nitrogen atmosphere for 12 hours to obtain a reaction product, which was reacted to obtain a reaction productAnd (3) carrying out centrifugal separation on the mixture to obtain solid particles, respectively washing the solid particles twice by using toluene and acetone, and carrying out vacuum drying for 12 hours at normal temperature to obtain the multifunctional integrated Pickering particle emulsifier.
The average particle hydraulic diameter of the multifunctional integrated Pickering granular emulsifier prepared in this example is 220 +/-50 nm, the obtained sample is white powder, a drop of dispersion liquid B and dispersion liquid A of the sample powder is placed on a copper net, and after drying at room temperature, transmission electron microscope tests are carried out, and the results are shown in figure 3, and figure 3 is a transmission electron microscope image of the multifunctional integrated Pickering granular emulsifier prepared in example 2. As can be seen in fig. 3, the microscopic morphology of the particles remained unchanged before and after modification.
Example 3
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil50 as Aerosil particles (primary particle size 20nm, BET specific surface area 50 m)2(g, Evonik chemical Co., Ltd., Aerosil50, AR) was dried in a vacuum oven at 110 ℃ for 1 hour, added together with 20m L of anhydrous toluene to a 50m L round-bottom flask, and dispersed uniformly by sonication at room temperature and 50kHz for 10 minutes to obtain a dispersion B, to which were added 0.9g of diethylenetriaminopropyltrimethoxysilane (Shanghai Merland Biochemical Co., Ltd., purity 95 wt%) and 0.05g of n-octyltrimethoxysilane (Shanghai Merland Biochemical Co., Ltd., purity 97 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ and nitrogen atmosphere for 2 hours to obtain a reaction product, which was centrifuged to obtain solid particles, and the solid particles were washed twice with toluene and acetone, respectively, and vacuum dried at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier.
The average hydraulic particle size of the particles of the multifunctional integrated Pickering particle emulsifier prepared in the embodiment is 220 +/-50 nm, and the obtained sample is white powder. The water contact angle of the powder sample was measured by using an infrared tablet press, and the result is shown in fig. 4, and fig. 4 is a schematic diagram of the water contact angle of the multifunctional integrated Pickering particulate emulsifier prepared in example 3. As can be seen from fig. 4, the water contact angle is 42 °, the particles are relatively hydrophilic, which is caused by the low content of alkyl chain components when fumed silica particles are integrally modified, and the particle surface is mainly occupied by relatively hydrophilic amine groups; on the other hand, the particles have strong hydrophilicity, but can still better play a role in stabilizing an oil-water two-phase system to form a stable emulsion.
Example 4
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil300 (primary particle size 10nm, BET specific surface area 300 m) as fumed silica particles2(g, Evonik chemical Co., Ltd., Aerosil300, AR) was dried in a vacuum oven at 110 ℃ for 1 hour, added together with 20m L anhydrous toluene to a 50m L round-bottom flask, and ultrasonically dispersed at room temperature and 50kHz for 10 minutes to obtain a dispersion B, to which 0.3g of diethylenetriaminopropyltrimethoxysilane (Shanghai Merland Biochemical technology Co., Ltd., purity 95 wt%) and 0.5g of n-hexadecyltrimethoxysilane (Shanghai Tantake technology Co., Ltd., purity 95 wt%) were added to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ and nitrogen atmosphere for 12 hours to obtain a reaction product, which was centrifugally separated to obtain solid particles, and the solid particles were washed twice with toluene and acetone, respectively, and vacuum dried at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier.
The average hydraulic particle size of the particles of the multifunctional integrated Pickering particle emulsifier prepared in the embodiment is 220 +/-50 nm, and the obtained sample is white powder. The water contact angle of the powder sample was measured by tabletting with an infrared tabletting machine, and the result is shown in fig. 5, and fig. 5 is a schematic diagram of the water contact angle of the multifunctional integrated Pickering granular emulsifier prepared in example 4. As can be seen from fig. 5, the water contact angle is 75 °, the contact angle is close to 90 °, but still hydrophilic particles, because the fumed silica particles are integrally modified with a higher content of alkyl chain component, and the particle surface contains a larger amount of hydrophobic alkyl groups, so that the contact angle of the hydrophilic silica particles is increased; the contact angle may be greater than 90 degrees with continued increase in the hydrophobic alkyl chain component content. On the other hand, the oil-water two-phase system stabilized by the particles can form a stable oil-in-water emulsion. The contact angles of the multifunctional integrated Pickering particle emulsifier obtained in the above examples 3 and 4 are 42 degrees and 75 degrees, respectively, and when the water contact angle of the prepared particle is between the two (42 degrees and 75 degrees), the oil-in-water type Pickering emulsion with good stability can be obtained.
Example 5
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
50mg of the multifunctional integrated Pickering granular emulsifier powder prepared in example 2 was dissolved in 5m L of deionized water to prepare dispersion B, dispersion A having a concentration of 10mg/m L, 5m L of toluene was added, and the same volume of the oil phase as that of the dispersion B, dispersion A was obtained by shearing emulsification with a homogenizer (15000rpm, 2min) to prepare the multifunctional integrated Pickering emulsion which was a stable oil-in-water type Pickering emulsion sealed and left standing at room temperature for one week, and the appearance and microscopic image thereof were photographed, and the results are shown in FIG. 6.
Example 6
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
50mg of the multifunctional integrated Pickering granular emulsifier powder prepared in example 2 was dissolved in 5m L NaCl solution of 0.5 mol/L to prepare dispersion B A of 10mg/m L, 5m L toluene was added, and the same volume of oil phase as the above dispersion B A was added to prepare the multifunctional integrated Pickering emulsion by shearing emulsification with a homogenizer (15000rpm, 2min), which was a stable oil-in-water type Pickering emulsion sealed and allowed to stand at room temperature for one week, and the appearance and microscopic image thereof were photographed, and the result is shown in FIG. 7.
Example 7
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
50mg of the multifunctional integrated Pickering particle emulsifier powder prepared in example 2 is dissolved in 5Ml of NaCl solution with the concentration of 5.0 mol/L to prepare dispersion B dispersion A with the concentration of 10mg/m L, 5m L toluene is added, the oil phase and the dispersion B dispersion A take the same volume, and the multifunctional integrated Pickering emulsion is prepared by a homogenizer shearing emulsification mode (15000rpm, 2min), wherein the Pickering emulsion is a stable oil-in-water type Pickering emulsion which is sealed and placed for one week at room temperature, and an appearance diagram and a microscopic diagram are taken, so that the multifunctional integrated Pickering emulsion prepared in example 7 has the appearance of salt resistance and is a schematic diagram of a microscope, and from the diagrams 6, 7 and 8, the integrated particles can stabilize the two-phase interface of the water phase and the oil phase to form a stable emulsion system, and the tolerable salt concentration can be between 0.5 mol/L, and the tolerable salt resistance system can be illustrated.
Example 8
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering emulsion prepared in example 4, in which 20mg of the above-mentioned powder was dissolved in 5M L of deionized water to prepare dispersion B, dispersion A having a concentration of 4mg/M L, was added with 5M L of cyclohexane, and the oil phase was in the same volume as the above-mentioned dispersion B, and was prepared by shearing emulsification with a homogenizer (15000rpm, 2min) to obtain the multifunctional integrated Pickering emulsion, which was a stable oil-in-water Pickering emulsion sealed and left to stand at room temperature for a different time, and then the appearance was photographed, the results are shown in FIG. 9, FIG. 9 is a schematic diagram showing the long-term standing stability of the multifunctional integrated Pickering emulsion prepared in example 8, FIG. 9 shows that the emulsion prepared in the Pickering emulsion room temperature was 0d (newly prepared sample), 6M (room temperature standing for 6 months), 12M (room temperature standing for 12 months), the emulsion prepared in fresh form had a high emulsification rate of about 73%, and when left to stand at room temperature for 6 months, the emulsion had a reduced volatility of the organic phase, and thus the emulsion was not reduced in volume by 48 months, and the total volume of the emulsion was reduced by 48 months.
Example 9
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
15mg of the multifunctional integrated Pickering particle emulsifier powder prepared in example 1 is dissolved in 5m L deionized water to prepare a dispersion B dispersion A with the concentration of 3mg/m L, 5m L toluene is added, the oil phase has the same volume as the dispersion A of the dispersion B, and the multifunctional integrated Pickering emulsion is prepared by a homogenizer shear emulsification mode (15000rpm, 2min), wherein the Pickering emulsion is a stable oil-in-water Pickering emulsion which is centrifuged at 4000rpm for 30 minutes on a high-speed centrifuge, and the emulsion state is observed, and no oil phase separation is found, so that the result is shown in figure 10, and figure 10 is a schematic diagram of the centrifugal stability of the multifunctional integrated Pickering emulsion prepared in example 9, and figure 10 shows that the emulsion is centrifuged at 4000rpm for 30 minutes on a demulsification high-speed centrifuge, the emulsion has no phenomenon and the emulsion volume is basically unchanged, which indicates that the emulsion system can endure at least 30 minutes at 4000rpm and has good centrifugal stability.
Example 10
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering particle emulsifier powders prepared in the examples 2 and 3 are respectively dissolved in 5m L deionized water by 5mg to prepare a dispersion B dispersion A with the concentration of 1mg/m L, 5m L toluene is respectively added into the two groups of dispersions B dispersion A, the oil phase and the dispersion B dispersion A have the same volume, and the multifunctional integrated Pickering emulsion is prepared by a homogenizer shearing emulsification method (15000rpm, 2min), wherein the Pickering emulsion is a stable oil-in-water Pickering emulsion, the emulsion state is observed by centrifuging the multifunctional integrated Pickering emulsion prepared in the example 10 at 8000rpm for 60 minutes on a high-speed centrifuge, and a small amount of oil phase is separated out on the upper layer, a small amount of water phase is separated out on the lower layer, the emulsion breaking rate is reduced, but no emulsion breaking phenomenon occurs, the emulsion size becomes more fine and the high-speed centrifugal aging effect can be realized.
Example 11
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil380, which is a fumed silica particle (primary particle diameter 7nm, BET specific surface area 380 m)2Evonik Chemicals, Inc., Aerosil380, AR) was dried in a vacuum oven at 100 ℃ for 6 hours, added together with 20m L anhydrous toluene to a 50m L round-bottom flask, and ultrasonically dispersed at room temperature and 50kHz for 10 minutes to obtain dispersion B, to which was added 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical technology Co., Ltd., purity 95 wt%) and 0.5g of n-dodecyltrimethoxysilane (Shanghai Tantake technology Co., Ltd., purity 95 wt%) to obtain a reaction solution, which was reacted at 100 ℃ in an oil bath and under nitrogen atmosphere for 6 hours to obtain a reaction product, which was centrifugally separated to obtain solid particles, and the solid particles were washed twice with toluene and acetone, respectively, and vacuum dried at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier.
Example 12
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of fumed silicaParticulate Aerosil200 (primary particle size 14nm, BET specific surface area 200 m)2Evonik chemical Co., Ltd., Aerosil200, AR) was dried in a vacuum oven at 100 ℃ for 6 hours, added together with 100m L anhydrous toluene to a 250m L round-bottom flask, and dispersed by sonication at room temperature and 50kHz for 10 minutes to obtain dispersion B, to which was added 0.5g of butylaminopropyltriethoxysilane (Shanghai hundred shun biosciences Co., Ltd.) and 0.1g of n-hexyltrimethoxysilane (Shanghai hundred shun biosciences Co., Ltd., purity 97 wt%) to obtain a reaction solution, which was reacted at 110 ℃ for 12 hours in a nitrogen atmosphere to obtain a reaction product, which was centrifuged to obtain solid particles, and the solid particles were washed twice with toluene and acetone, respectively, and vacuum-dried at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier.
Example 13
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil50 as Aerosil particles (primary particle size 20nm, BET specific surface area 50 m)2(g, Evonik chemical Co., Ltd., Aerosil50, AR) was dried in a vacuum oven at 150 ℃ for 0.5 hour, and was added to a 50m L round bottom flask together with 10m L of anhydrous toluene, and was uniformly dispersed by sonication at room temperature and 50kHz for 10 minutes to obtain a dispersion B, and then 0.2g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical Co., Ltd., purity 95 wt%) and 0.1g of n-dodecyltrimethoxysilane (Shanghai Bailingwei chemical Co., Ltd., purity 95 wt%) were added to the dispersion B to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ under nitrogen atmosphere for 2 hours to obtain a reaction product, which was centrifuged to obtain solid particles, and the solid particles were washed with toluene and acetone respectively twice, and vacuum dried at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifierThe average hydraulic particle size of the multifunctional integrated Pickering particle emulsifier prepared in the embodiment is 220 +/-50 nm, and the obtained sample is white powder.
Example 14
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil300 (primary particle size 10nm, BET specific surface area 300 m) as fumed silica particles2Evonik chemical Co., Ltd., Aerosil300, AR) was dried in a vacuum oven at 110 ℃ for 3 hours, added together with 45m L anhydrous toluene to a 150m L round-bottomed flask, and ultrasonically dispersed at room temperature and 50kHz for 10 minutes to obtain dispersion B, to which was added 0.2g of diethylaminomethyltrimethoxysilane (Shanghai Mirey chemical Co., Ltd., purity 95 wt%) and 0.1g of n-octadecyltrimethoxysilane (Shanghai Michelin Biotech Co., Ltd., purity 90 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ for 2 hours under nitrogen atmosphere to obtain a reaction product, which was centrifuged to obtain solid particles, and the solid particles were washed twice with toluene and acetone, respectively, and vacuum dried at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier, which had an average particle diameter of 220. + -. 50nm and a white powder sample.
Example 15
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil50 as Aerosil particles (primary particle size 20nm, BET specific surface area 50 m)2(g, Evonik chemical Co., Ltd., Aerosil50, AR) was dried in a vacuum oven at 120 ℃ for 1 hour, added together with 10m L of dry toluene to a 50m L round-bottomed flask, and dispersed uniformly by sonication at room temperature and 50kHz for 10 minutes to obtain a dispersion B, and 0.2g of tris (2-aminoethyl) propylaminyltrimethoxysilane (Shanghai Tantake technology Co., Ltd., purity: Shanghai Tantake technology Co., Ltd., purity: 1 g) was added to the dispersion B90 wt%) and 0.1g of propyltriethoxysilane (Shanghai Meclin Biotech Co., Ltd., purity of 98 wt%) to obtain a reaction solution, reacting the reaction solution in an oil bath at 110 ℃ for 2h under a nitrogen environment to obtain a reaction product, centrifuging the reaction product to obtain solid particles, respectively cleaning the solid particles twice with toluene and acetone, and vacuum-drying at normal temperature for 12h to obtain the multifunctional integrated Pickering particle emulsifier. The average hydraulic particle size of the particles of the multifunctional integrated Pickering particle emulsifier prepared in the embodiment is 220 +/-50 nm, and the obtained sample is white powder.
Example 16
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering particle emulsifier prepared in the example 11 is dissolved in deionized water to prepare a dispersion liquid B dispersion liquid A with the concentration of 2mg/m L, different oil phases (comprising ethyl acetate, toluene, dichloromethane, petroleum ether, n-hexane, cyclohexane and crude oil) are respectively added, the oil phase and the dispersion liquid A of the dispersion liquid B are in the same volume, and the multifunctional integrated Pickering emulsion is prepared in a homogenizer shearing emulsification mode (15000rpm, 2min), so that the result is shown in the attached figure 12, and the figure 12 is a schematic diagram of the multifunctional integrated Pickering emulsion with different oil phases prepared in the example 16.
Wherein, ethyl acetate: the polarity is high, and the oil-water interfacial tension between the water-soluble polymer and the water is low (6.8 dyn/cm); toluene: one of the most commonly used organic solvents, the CO of the resulting emulsion2The responsiveness is the best. Dichloromethane: is an oil phase with a density higher than that of water. Petroleum ether: the mixture has a low boiling point and a low surface tension (15.5-18.4 dyn/cm), but has a high oil-water interfacial tension (49.0-51.1 dyn/cm) with water. Cyclohexane: the polarity is low, and the oil-water interfacial tension between the water-soluble polymer and the water is high (50.0 dyn/cm); the emulsion obtained has the best stability. Petroleum: is aComplex multicomponent systems, very high viscosity. The multifunctional integrated Pickering particle emulsifier can emulsify a two-phase system of the multifunctional integrated Pickering particle emulsifier and water, and has potential practical application value.
Example 17
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering particle emulsifier prepared in example 12 was dissolved in deionized water to prepare dispersion B and dispersion A with a concentration of 1mg/m L, and the multifunctional integrated Pickering emulsion was prepared by different emulsification methods (shaking by hand (5min), high-pressure shearing (80psi, 10min), ultrasonic emulsification (440kW, 10min), homogenizer shearing emulsification (15000rpm, 2min)) using the same volume of toluene and the dispersion A of the dispersion B, and the results are shown in FIG. 13, where FIG. 13 is a schematic diagram of the multifunctional integrated Pickering emulsion prepared in example 17 in different emulsification methods.
Shear emulsification, high-pressure homogenization and ultrasound are common methods for preparing emulsion, but the three preparation methods all require strong external mechanical force or energy input so as to break liquid into small liquid drops to achieve the emulsification effect; the integrated particles in the invention have good emulsifying capacity, and can form emulsion with good stability under the action of low-energy manual shaking. As can be seen from fig. 13, the size of the droplets of the emulsion obtained by manual shaking was visually recognizable, and the droplet size was significantly higher than the emulsions obtained by the other three methods; the emulsion prepared by ultrasonic emulsification is the most exquisite, the average diameter of the liquid drop is the smallest, the average diameter of the emulsion liquid drop obtained by high-speed shearing and high-pressure homogenization is similar, and the size of the emulsion liquid drop prepared by high-pressure homogenization is more uniform compared with that of the emulsion prepared by high-pressure shearing emulsification. The emulsions obtained in the four modes are of the same type and are all of the oil-in-water type. The ultrasonic emulsification has the best effect, the high-pressure homogenization is performed for the second time, and the shearing emulsification is the worst of the three emulsification modes. The results in fig. 13 show that the multifunctional integrated Pickering particle emulsifier obtained by the invention has strong emulsifying capacity, can realize better emulsifying performance under the action of low-energy emulsification (manual shaking), is beneficial to the practical application of the multifunctional integrated Pickering particle emulsifier in different processes, and achieves the purpose of the invention.
Example 18
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering particle emulsifier prepared in example 13 is dissolved in NaCl aqueous solution of 5.0 mol/L to prepare salt dispersion B dispersion A with the concentration of 5mg/m L, toluene and the salt dispersion B dispersion A with the same volume are taken to prepare the multifunctional integrated Pickering emulsion through a homogenizer shearing emulsification mode (15000rpm, 2min), and the multifunctional integrated Pickering emulsion is placed at room temperature for different time (1 day, 6 months and 14 months), so that the result is as shown in figure 14, figure 14 is a schematic diagram of the long-term placing stability of the multifunctional integrated Pickering emulsion prepared in example 18, figure 14 shows that the emulsion droplet size tends to become larger in a micro scale and the emulsion fraction tends to decrease in a macro scale along with the prolonging of the placing time, the total volume decreases due to volatilization of an oil phase caused by long-term placing, the emulsion has little change in a macro scale and a micro scale after 6 months of placing, and no demulsification phenomenon appears, and the emulsion still exists after 14 months of placing, thus the multifunctional integrated Pickering emulsion obtained by the invention has good stability.
Example 19
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering particle emulsifier prepared in example 14 was dissolved in deionized water to prepare a dispersion B dispersion A having a concentration of 0.5mg/m L, the same volume of toluene and the dispersion B dispersion A were taken and prepared into the multifunctional integrated Pickering emulsion by shearing and emulsifying with a homogenizer (15000rpm, 2min), and CO was introduced into the emulsion2After 15min, the Pickering emulsion is demulsified to form an upper and a lower layered oil-water two-phase; then introducing N into the oil-water two phases2After 30min, the Pickering emulsion reforms, and the process can be cycled many times. The results are shown in FIG. 15, and FIG. 15 shows example 19 CO of multifunctional integrated Pickering emulsion prepared by the method2/N2A graph of cyclic responsiveness. As can be seen in FIG. 15, CO was bubbled into the freshly prepared emulsion2After 15min, the emulsion layer on the upper phase gradually becomes clear, the multifunctional integrated Pickering particle emulsifier falls off from the interface of the oil phase and the water phase and enters the water phase on the lower layer, so that the water phase becomes turbid, the emulsion is broken, and the oil phase and the water phase are separated; this process is due to the amine groups on the integral particles on the CO2Under the action of protonation, the hydrophilicity of the particles is enhanced, and the particles are separated from the oil-water interface and enter the water phase. Subsequently, N is introduced into the system2After 30min, CO in the system2Is gradually covered by N2The amine group protonated on the removed, multifunctional integral Pickering particulate emulsifier is N2Deprotonation is carried out under the action, the multifunctional integrated Pickering particle emulsifier recovers the emulsifying capacity again, the oil-water two-phase interface can be stabilized again, and at the moment, the emulsion is formed again. Likewise, the CO is recirculated2And N2The oil-water two-phase system can be circulated for many times between emulsion breaking and emulsification. The above results show that the multifunctional integrated Pickering particle emulsifier obtained by the invention has CO2/N2Cyclic responsiveness; the method can effectively control the emulsification and emulsion breaking processes, and only green and environment-friendly CO is used when emulsion breaking is needed without adding any chemical reagent2A responsive implementation; and CO2/N2The gas is easy to remove from the system, does not change the components of the original system, and has excellent practical value.
Example 20
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
the multifunctional integrated Pickering emulsion prepared in example 15 is dissolved in deionized water to prepare a dispersion B dispersion A with a concentration of 2.5mg/m L, the same volume of toluene and the dispersion B dispersion A are taken to prepare the multifunctional integrated Pickering emulsion through a homogenizer shearing emulsification mode (15000rpm, 2min), the emulsion is passed through a self-filled quartz sand column, firstly, the emulsion is not wetted, the emulsion quantity is lost, but the emulsion is not broken, the emulsion passes through the quartz sand column for a plurality of times, the process can be circulated for a plurality of times, the emulsion volume is basically unchanged, and the emulsion viscosity is basically unchanged, and the result is shown in figures 16 and 17, figure 16 is a schematic diagram of the condition that the multifunctional integrated Pickering emulsion prepared in example 20 passes through a quartz sand chromatographic column, figure 17 is a viscosity test result of the multifunctional integrated Pickering emulsion prepared in example 20 before and after the multifunctional integrated Pickering emulsion passes through the quartz sand column for a plurality of times, figure 17 is a diagram of a quartz sand chromatographic column simulation of rock formation by using the quartz sand column, the chromatographic separation effect of the multifunctional integrated Pickering emulsion prepared in example 20, the multifunctional integrated Pickering emulsion before and after passing through the quartz sand column, the multifunctional integrated Pickering emulsion is not wetted quartz sand column, the multifunctional integrated Pickering emulsion system can be shown in figure 16, the invention, the viscosity of the invention, the invention can be shown in the invention, the invention can be used for the invention, the invention has.
Comparative example 1
The comparative example provides a preparation method of a single amino functionalized Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil200 (primary particle size 14nm, BET specific surface area 200 m) as fumed silica particles2/g, Sigma Aldrich, Aerosil200, AR) was dried in a vacuum oven at 110 ℃ for 12 hours, added together with 20m L of anhydrous toluene to a 50m L round-bottom flask, dispersed uniformly by sonication at room temperature and 50kHz for 30 minutes to give dispersion B, 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical technology Co., Ltd., purity: 95 wt%) was added to dispersion B to give a reaction solution, the reaction solution was reacted in an oil bath at 110 ℃ and under nitrogen for 12 hours to give a reaction product, the reaction product was centrifuged to give solid particles, and the solid particles were washed with toluene and acetone, respectivelyAnd (3) carrying out vacuum drying on the bulk particles twice at normal temperature for 12 hours to obtain the single amino functionalized Pickering particle emulsifier.
The average hydraulic particle size of the single amino functionalized Pickering particle emulsifier prepared by the comparative example is 220 +/-50 nm, and the obtained sample is white powder. The water contact angle of the powder samples was measured using an infrared tablet press and is shown in fig. 18, which is a graphical representation of the water contact angle of the single amine-functionalized Pickering particulate emulsifier prepared in comparative example 1. As can be seen from fig. 18, the water contact angle is 36 °. The fumed silica particles are modified by single amine functional groups, and the surfaces of the particles are occupied by hydrophilic amine groups.
Comparative example 2
The comparative example provides a method for preparing a single hydrophobic alkyl functionalized Pickering particulate emulsifier, comprising the steps of:
0.5g of Aerosil200 (primary particle size 14nm, BET specific surface area 200 m) as fumed silica particles2/g, Sigma Aldrich, Aerosil200, AR) was dried in a vacuum oven at 110 ℃ for 12 hours, added together with 20m L anhydrous toluene to a 50m L round bottom flask, dispersed uniformly by sonication at room temperature and 50kHz for 30 minutes to give dispersion B, 0.5g of n-hexyltrimethoxysilane (Shanghai Bailingwei science Co., Ltd., purity 95 wt%) was added to the dispersion B to give a reaction solution, the reaction solution was reacted in an oil bath at 110 ℃ for 12 hours under nitrogen to give a reaction product, the reaction product was centrifuged to give solid particles, and the solid particles were washed twice with toluene and acetone, respectively, and vacuum dried at room temperature for 12 hours to give the single hydrophobic alkyl functionalized Pickering particle emulsifier.
The single hydrophobic alkyl functionalized Pickering particulate emulsifier prepared in this comparative example had a mean hydrodynamic particle size of 220. + -.50 nm, and the sample was a white powder. The water contact angle of the powder samples was measured using an infrared tablet press and the results are shown in figure 19, which is a schematic representation of the water contact angle of the single hydrophobic alkyl functionalized Pickering particulate emulsifier prepared in comparative example 2. As can be seen from fig. 19, the water contact angle is 121 °, and the particles are changed from hydrophilic to hydrophobic due to the surface of the fumed silica particles being occupied by hydrophobic alkyl groups after the particles are modified with a single alkyl functional group.
Comparative example 3
The comparative example provides a method for preparing a single amine functionalized Pickering emulsion, comprising the steps of:
50mg of the single amino functionalized Pickering granular emulsifier powder prepared in comparative example 1 was dissolved in 5m L DI water to prepare dispersion B dispersion A with a concentration of 10mg/m L, 5m L toluene was added, the same volume of oil phase as the above dispersion B dispersion A was obtained, and the single amino functionalized Pickering emulsion was prepared by shearing emulsification with a homogenizer (15000rpm, 2min), and the appearance thereof was photographed, and the emulsion was an oil-in-water emulsion, which was poor in emulsification, and the results are shown in FIG. 20.
Comparative example 4
This comparative example provides a method of preparing a single hydrophobic alkyl functionalized Pickering emulsion, comprising the steps of:
50mg of the single hydrophobic alkyl functionalized Pickering particulate emulsifier powder prepared in comparative example 2 was dissolved in 5m L of deionized water to prepare dispersion B, dispersion A having a concentration of 10mg/m L, 5m L of toluene was added, the oil phase was in the same volume as the above dispersion B, dispersion A was prepared by shearing emulsification with a homogenizer (15000rpm, 2min) to obtain the single hydrophobic alkyl functionalized Pickering emulsion, which was a water-in-oil emulsion and showed the result as shown in FIG. 212And (4) responsiveness.
Example 21
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil200 (primary particle size 14nm, BET specific surface area 200 m) as fumed silica particles2/g, Sigma Aldrich, Aerosil200, AR) were dried in a vacuum drying cabinet at 110 ℃Adding the mixture and 20m L anhydrous toluene into a 50m L round-bottom flask together, performing ultrasonic treatment at room temperature and 50kHz frequency for 30 minutes to uniformly disperse the mixture to obtain a dispersion liquid B, adding 0.05g of diethylenetriaminopropyltrimethoxysilane (Shanghai Tantainetechnology Co., Ltd., purity of 95 wt%) and 0.5g of n-hexadecyltrimethoxysilane (Shanghai Bailingwei technology Co., Ltd., purity of 95 wt%) into the dispersion liquid B to obtain a reaction liquid, reacting the reaction liquid in an oil bath at the temperature of 110 ℃ and under a nitrogen environment for 24 hours to obtain a reaction product, performing centrifugal separation on the reaction product to obtain solid particles, respectively cleaning the solid particles twice with toluene and acetone, and performing vacuum drying at room temperature for 12 hours to obtain the multifunctional integrated Pickering particle emulsifier.
The multifunctional integrated Pickering particle emulsifier prepared in the embodiment has strong hydrophobicity, cannot stabilize a toluene-water system to form Pickering emulsion, and the result is shown in figure 22.
The results show that although the multifunctional integral Pickering particle emulsifier can be obtained by the present example, a stable Pickering emulsion cannot be obtained.
Example 22
The embodiment provides a preparation method of a multifunctional integrated Pickering particle emulsifier, which comprises the following steps:
0.5g of Aerosil200 (primary particle size 14nm, BET specific surface area 200 m) as fumed silica particles2(g, Sigma Aldrich, Aerosil200, AR) was dried in a vacuum oven at 110 ℃ for 12 hours, charged together with 20m L of anhydrous toluene into a 50m L round-bottomed flask, and dispersed uniformly by sonication at room temperature and 50kHz for 30 minutes to give dispersion B, to which were added 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Tatan Co., Ltd., purity 95 wt%) and 0.5g of n-hexadecyltrimethoxysilane (Shanghai Bailingwei Co., Ltd., purity 95 wt%) to give a reaction solution which was reacted in an oil bath at 50 ℃ under nitrogen atmosphere for 48 hours to give a reaction product, which was centrifuged to give solid particles, and the solid particles were washed twice with toluene and acetone, respectively, at room temperatureAnd (4) drying for 12 hours in vacuum to obtain the multifunctional integrated Pickering particle emulsifier.
The multifunctional integrated Pickering particle emulsifier prepared in the embodiment can emulsify a toluene-water system to form Pickering emulsion, but the emulsion can be broken after being placed for 24 hours, the volume of the emulsion is reduced dramatically, namely the long-term stable Pickering emulsion cannot be realized, and the result is shown in figure 23.
The results show that although the multifunctional integral Pickering particle emulsifier can be obtained by the present example, a stable Pickering emulsion cannot be obtained.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (13)
1. A preparation method of multifunctional integrated Pickering emulsion is characterized by comprising the following steps:
mixing and dispersing the multifunctional integrated Pickering particle emulsifier and a solvent A to prepare a dispersion liquid A;
mixing the dispersion liquid A with an oil phase, and preparing the multifunctional integrated Pickering emulsion in an emulsifying mode;
the multifunctional integrated Pickering particle emulsifier is prepared from gas-phase silica particles, an amino silane coupling agent and a hydrophobic alkyl silane coupling agent in a mass ratio of 5: 2-9: 0.5-5.
2. The preparation method of the multifunctional integrated Pickering emulsion according to claim 1, wherein the solvent A comprises deionized water or saline, preferably the concentration of the saline is 0.01 mol/L-5 mol/L.
3. The preparation method of the multifunctional integrated Pickering emulsion according to claim 1, wherein the concentration of the multifunctional integrated Pickering particle emulsifier in the dispersion liquid A is 0.25mg/m L-10 mg/m L, and the volume percentage of the oil phase to the dispersion liquid A is 20-80: 20-80.
4. The method of claim 1, wherein the oil phase comprises at least one of alkanes, cycloalkanes, hydrocarbon mineral oils, esters, vegetable oils, and petroleum.
5. The method of claim 1, wherein the emulsification comprises at least one of manual shaking, ultrasonic emulsification, shear emulsification, and high pressure shear emulsification.
6. The method for preparing the multifunctional integrated Pickering emulsion according to claim 1, wherein the primary particle size of the fumed silica particles is 4-200 nm, and the BET specific surface area of the fumed silica particles is 50m2/g～400m2/g。
7. The preparation method of the multifunctional integrated Pickering emulsion according to claim 1, wherein the amino silane coupling agent is a C4-C20 linear or branched primary amine, secondary amine or tertiary amine silane coupling agent containing 1-10 amino groups; preferably, the amino silane coupling agent is diethylenetriaminopropyltrimethoxysilane, butylaminopropyltriethoxysilane, diethylaminomethyltrimethoxysilane or tris (2-aminoethyl) propylaminotrimethoxysilane.
8. The preparation method of the multifunctional integrated Pickering emulsion according to claim 1, wherein the hydrophobic alkyl silane coupling agent is a C3-C20 linear or branched chain saturated alkyl silane coupling agent; preferably, the hydrophobic alkylsilane coupling agent is n-dodecyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-hexyltrimethoxysilane, n-octadecyltrimethoxysilane, or propyltriethoxysilane.
9. The preparation method of the multifunctional integrated Pickering emulsion according to any one of claims 1-8, wherein the preparation method of the multifunctional integrated Pickering particle emulsifier comprises the following steps:
mixing fumed silica particles with a solvent B, and performing ultrasonic dispersion to obtain a dispersion liquid B;
under the protection of inert gas or nitrogen, mixing the dispersion liquid B, an amino silane coupling agent and a hydrophobic alkyl silane coupling agent to obtain a reaction liquid, heating the reaction liquid to react to obtain a reaction product, separating the reaction product to obtain solid particles, cleaning the solid particles, and drying to obtain the multifunctional integrated Pickering particle emulsifier.
10. The method for preparing the multifunctional integrated Pickering emulsion according to claim 9, further comprising a step of drying the fumed silica particles before mixing the fumed silica particles with the solvent, specifically comprising: drying the fumed silica particles for 0.5 to 12 hours at the temperature of between 80 and 150 ℃.
11. The preparation method of the multifunctional integrated Pickering emulsion as claimed in claim 9, wherein the concentration of gas-phase silica particles in the dispersion liquid B is 5 g/L-50 g/L, the concentration of amino silane coupling agent in the reaction liquid is 1 g/L-50 g/L, and the concentration of hydrophobic alkyl silane coupling agent in the reaction liquid is 1 g/L-50 g/L.
12. The method for preparing the multifunctional integrated Pickering emulsion according to claim 9, wherein the solvent B is anhydrous toluene.
13. The preparation method of the multifunctional integrated Pickering emulsion according to claim 9, wherein the heating reaction temperature is 80-110 ℃, and the heating reaction time is 2-12 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113506508A (en) * | 2021-08-07 | 2021-10-15 | 河北师范大学 | Super-hydrophobic physical unclonable structural color anti-counterfeiting label and preparation method thereof |
| CN113578190A (en) * | 2021-09-02 | 2021-11-02 | 四川冠山科技有限公司 | Switch Pickering emulsion with stable low-concentration particles and preparation method thereof |
| CN113930265A (en) * | 2021-09-29 | 2022-01-14 | 华中科技大学 | Emulsion, application thereof and method for preparing emulsion by using nano-particles to emulsify biomass pyrolysis oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070439A (en) * | 2007-06-12 | 2007-11-14 | 武汉理工大学 | Method for preparing hydrophobic silicon dioxide |
| CN102131733A (en) * | 2008-08-22 | 2011-07-20 | 瓦克化学股份公司 | Aqueous dispersions of hydrophobic silicic acids |
| CN108456571A (en) * | 2018-05-10 | 2018-08-28 | 江南大学 | The preparation of stimuli-responsive oil-in-water type Pickering lotions |
| CN109852359A (en) * | 2018-12-29 | 2019-06-07 | 浙江海洋大学 | A kind of Pickering lotion and preparation method thereof for heavy crude reservoir |
| CN110041459A (en) * | 2019-04-23 | 2019-07-23 | 中国科学院长春应用化学研究所 | A kind of O/W/O multiple emulsion, preparation method and application |
-
2020
- 2020-04-01 CN CN202010250157.5A patent/CN111450721A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070439A (en) * | 2007-06-12 | 2007-11-14 | 武汉理工大学 | Method for preparing hydrophobic silicon dioxide |
| CN102131733A (en) * | 2008-08-22 | 2011-07-20 | 瓦克化学股份公司 | Aqueous dispersions of hydrophobic silicic acids |
| CN108456571A (en) * | 2018-05-10 | 2018-08-28 | 江南大学 | The preparation of stimuli-responsive oil-in-water type Pickering lotions |
| CN109852359A (en) * | 2018-12-29 | 2019-06-07 | 浙江海洋大学 | A kind of Pickering lotion and preparation method thereof for heavy crude reservoir |
| CN110041459A (en) * | 2019-04-23 | 2019-07-23 | 中国科学院长春应用化学研究所 | A kind of O/W/O multiple emulsion, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 兰永强等: "《分离生物乙醇用渗透汽化复合膜》", 31 July 2016, 厦门大学出版社 * |
| 李溪溪等: "CO2响应性颗粒乳化剂的制备及其乳化性能研究", 《中国胶粘剂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113506508A (en) * | 2021-08-07 | 2021-10-15 | 河北师范大学 | Super-hydrophobic physical unclonable structural color anti-counterfeiting label and preparation method thereof |
| CN113578190A (en) * | 2021-09-02 | 2021-11-02 | 四川冠山科技有限公司 | Switch Pickering emulsion with stable low-concentration particles and preparation method thereof |
| CN113578190B (en) * | 2021-09-02 | 2022-07-19 | 四川冠山科技有限公司 | Switch Pickering emulsion with stable low-concentration particles and preparation method thereof |
| CN113930265A (en) * | 2021-09-29 | 2022-01-14 | 华中科技大学 | Emulsion, application thereof and method for preparing emulsion by using nano-particles to emulsify biomass pyrolysis oil |
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Application publication date: 20200728 |