CN111450771A - Multifunctional integrated Pickering particle emulsifier and preparation method thereof - Google Patents
Multifunctional integrated Pickering particle emulsifier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multifunctional integrated Pickering particle emulsifier and a preparation method thereof. The multifunctional integrated Pickering particle emulsifier comprises fumed silica particles, and an amino silane coupling agent and a hydrophobic alkyl silane coupling agent which are respectively grafted on the surfaces of the fumed silica particles; wherein the mass ratio of the fumed silica particles to the amino silane coupling agent to the hydrophobic alkyl silane coupling agent is 5: 2-9: 0.5-5. The invention also provides a preparation method of the multifunctional integrated Pickering particle emulsifier. The multifunctional integrated Pickering particle emulsifier prepared by the invention has good emulsifying property, stability and CO2Response performance.
Description
Technical Field
The invention relates to the technical field of preparation of fine chemical products. More particularly relates to a multifunctional integrated Pickering particle emulsifier and a preparation method thereof.
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.
At present, a composite system of blending nanoparticles and a surfactant or a polymer is used for preparing Pickering emulsion. Such as Binks professor topic group [ B.P.Binks, M.Kirkland, J.A.Rodrigues.Origin of stability of aqueous foams in nanoparticles-surfactant mixtures, 2008,4, 2373-.]The group of subjects taught by the university of southern China's dynasty Yang [ S.Zou, Y.Yang, H. L iu, C.Wang.synchronous stabilization and structural structures of Pickering high-internal phase emulsions by nanoparticles and surfactants, colloids and surfaces A: Physicochem. Eng.applications, 2013,436, 1-9.]The synergy of hydrophobic nano silicon dioxide particles and nonionic surfactant is researched, and a compound system of the particles is utilized to construct a high internal phase Pickering emulsion with adjustable structure, which is Kim et al of the university of Hanyang of Korea [ G.J. L ee, H.A.son, J.W.Cho, S.K.Choi, H.T.Kim, J.W.Kim.Stabilization of Pickering emulsions by generating complex colloidal alloys, J.Cold Interface Sci.,2014,413, 100-105).]The nano particles are compounded with polymer polyvinyl alcohol (PVA), when the proportion of the PVA to the nano particles is lower, good emulsion stability can be obtained, and the professor of Liuxue Feng of the university of Jiangnan [ Y.Zhang, S.Guo, W.Wu, Z.Qin, X. L iu. CO2-triggered Pickering emulsion based on silica nanoparticles and tertiary aminewith long hydrophobic tails.Langmuir 2016,32,11861-11867.]And professor j.jiang, y.ma, z.cui, b.p.binks.pickering emulsions responsive to CO2/N2andlight 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 CN106582431A, nano-silica and CO are adopted2/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 multifunctional integrated Pickering particle emulsifier and a preparation method thereof.
Disclosure of Invention
One purpose of the invention is to provide a multifunctional integrated Pickering particle emulsifier.
The invention also aims to provide a preparation method of the multifunctional integrated Pickering particle emulsifier.
In order to achieve the purpose, the invention adopts the following technical scheme:
a multifunctional integrated Pickering particle emulsifier comprises fumed silica particles, and an amino silane coupling agent and a hydrophobic alkyl silane coupling agent which are respectively grafted on the surfaces of the fumed silica particles; wherein the mass ratio of the fumed silica particles to the amino silane coupling agent to the hydrophobic alkyl silane coupling agent is 5: 2-9: 0.5-5.
Preferably, the fumed silica particles have a primary particle size of 4nm to 200nm, and the fumed silica particles have a primary particle size of 4nm to 200nmThe BET specific surface area of the 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.
As another aspect of the invention, the invention also provides a preparation method of the multifunctional integrated Pickering emulsifier, which comprises the following steps:
mixing fumed silica particles and a solvent, and performing ultrasonic dispersion to obtain a dispersion liquid;
under the protection of inert gas or nitrogen, mixing the dispersion liquid, the amino silane coupling agent and the 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.
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 5min to 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 fumed silica particles in the dispersion is from 5 g/L to 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 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 emulsion prepared by the multifunctional integrated Pickering particle emulsifier 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 be adjusted to have a water contact angle of 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 particle emulsifier prepared by the invention has good emulsifying property, stability and CO2Response performance, emulsification of different oil-water phases, stabilization of Pickering emulsion and emulsion CO2/N2The cyclic response characteristic at room temperature;
(2) the emulsion prepared from the multifunctional integrated Pickering particle emulsifier 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 system can be used for tertiary oil recovery, emulsion polymerization and wastewaterHas important application value in the relevant application fields of treatment, cosmetics, food and the like;
(3) the emulsion prepared from the multifunctional integrated Pickering particle emulsifier 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;
(4) the multifunctional integrated Pickering particle emulsifier prepared by the invention is prepared by one-pot one-step reaction of raw materials, the preparation method is simple and convenient, and the emulsifying property of the obtained emulsifier is excellent;
(5) the preparation method of the multifunctional integrated Pickering particle emulsifier provided by the invention introduces CO on the surface of fumed silica particles by a chemical grafting method2Amine-based surface modifier with response, acid-base response and emulsification performance and hydrophobic surface modifier with auxiliary stability, thereby obtaining the product with emulsification, stability and CO2Responsive multifunctional integrated nanoparticles.
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 drying oven at 100 ℃ 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, to which 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical technology Co., Ltd., purity 95 wt%) and 0.5g of n-dodecyltrimethoxysilane (Shanghai Bailingwicco chemical technology Co., Ltd., purity 95 wt%) were added to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ for 12 hours under nitrogen atmosphere 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 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 limited, 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-bottom flask, and dispersed uniformly by sonication at room temperature and 50kHz frequency for 10 minutes to obtain a dispersion, to which was added 0.5g of diethylenetriaminopropyltrimethoxysilane (shanghai tatatan technologies, ltd., purity 95 wt%) and 0.1g of n-hexadecyltrimethoxysilane (shanghai bailing wilford science, ltd., purity 95 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ and under nitrogen atmosphere for 12 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 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 aqueous dispersion of the sample powder is taken on a copper mesh, and after drying at room temperature, transmission electron microscope tests are carried out, and the result is shown in figure 3, and figure 3 is the 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, charged with 20m L of dry toluene in a 50m L round bottom flask, sonicated at room temperature and 50kHz frequencyDispersing the mixture evenly for 10 minutes to obtain a dispersion liquid, adding 0.9g of diethylenetriaminopropyltrimethoxysilane (Shanghai Meclin Biochemical technology Co., Ltd., purity of 95 wt%) and 0.05g of n-octyltrimethoxysilane (Shanghai Meclin Biochemical technology Co., Ltd., purity of 97 wt%) into the dispersion liquid to obtain a reaction liquid, reacting the reaction liquid in an oil bath at the temperature of 110 ℃ and a nitrogen environment for 2 hours to obtain a reaction product, centrifugally separating the reaction product to obtain solid particles, respectively cleaning the solid particles twice by using toluene and acetone, and drying in vacuum at normal 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(iv)/g, Evonik chemical Co., Ltd., Aerosil300, AR) was dried in a vacuum oven at 110 ℃ for 1 hour, charged together with 20m L anhydrous toluene into a 50m L round-bottomed flask, and dispersed uniformly by sonication at room temperature and 50kHz for 10 minutes to obtain a dispersion, to which 0.3g of diethylenetriaminopropyltrimethoxysilane (Shanghai Merland Biotech Co., Ltd., purity: 95 wt%) and 0.5g of n-hexadecyltrimethoxysilane (Shanghai Tantake technology) were addedLimited company, the purity is 95 wt%) to obtain a reaction solution, reacting the reaction solution in an oil bath at the temperature of 110 ℃ for 12 hours in a nitrogen environment to obtain a reaction product, centrifugally separating the reaction product to obtain solid particles, respectively cleaning the solid particles twice by using toluene and acetone, and drying in vacuum at normal 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 DI water to prepare a 10mg/m L aqueous dispersion, 5m L toluene was added, the oil phase was in the same volume as the aqueous dispersion, and the multifunctional integrated Pickering emulsion was prepared by shearing emulsification with a homogenizer (15000rpm, 2min), and was a stable oil-in-water Pickering emulsion which was sealed and left at room temperature for one week, and the appearance and microscopic image thereof were photographed, and the result is 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 10mg/m L aqueous dispersion, 5m L toluene was added, the oil phase was in the same volume as the aqueous dispersion, and the multifunctional integrated Pickering emulsion was prepared by shearing emulsification with a homogenizer (15000rpm, 2min), and the stable oil-in-water type Pickering emulsion was left 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 NaCl solution with the concentration of 5.0 mol/L to prepare aqueous dispersion with the concentration of 10mg/m L, 5m L toluene is added, the oil phase and the aqueous dispersion have the same volume, and the multifunctional integrated Pickering emulsion is prepared by a homogenizer shearing emulsification mode (15000rpm, 2min), wherein the Pickering emulsion is stable oil-in-water Pickering emulsion, the emulsion is sealed and placed at room temperature for one week, and an appearance diagram and a microscopic diagram are taken, so that the result is shown in figure 7, figure 8 is an appearance and a microscopic diagram of the salt resistance performance of the multifunctional integrated Pickering emulsion prepared in example 7, and from figures 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 mol/355.0 mol/L, which shows that the tolerable salt resistance system can be high.
Example 8
The embodiment provides a preparation method of a multifunctional integrated Pickering emulsion, which comprises the following steps:
20mg of the multifunctional integrated Pickering particulate emulsifier powder prepared in example 4 was dissolved in 5M L of deionized water to prepare an aqueous dispersion having a concentration of 4mg/M L, 5M L of cyclohexane was added, and the oil phase and the aqueous dispersion were in the same volume, and the multifunctional integrated Pickering emulsion was prepared by shearing and emulsifying the aqueous dispersion with a homogenizer (15000rpm, 2min) and was a stable oil-in-water Pickering emulsion sealed and left to stand at room temperature for various periods of time, as a result, as shown in FIG. 9, FIG. 9 is an external view showing the long-term standing stability of the multifunctional integrated Pickering emulsion prepared in example 8. from FIG. 9, the emulsion left to stand at room temperature was 0d (emulsion breaking fresh prepared sample), 6M (left to stand at room temperature for 6 months), 12M (left to stand at room temperature for 12 months), the freshly prepared emulsion had a high emulsification rate of about 73%, and when left to stand at room temperature for 6 months, had a certain volatility due to the oil phase left to stand, the emulsion decreased in volume, accordingly, the emulsion had a decreased rate, which was reduced by about 48%, and thus, the total volume of the emulsion was not decreased, and thus, which the emulsion left to stand was found to have a good value.
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 an aqueous dispersion with the concentration of 3mg/m L, 5m L toluene is added, the oil phase and the aqueous dispersion have 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 Pickering emulsion which is centrifuged at 4000rpm for 30min on a high-speed centrifuge, the state of the emulsion is observed, no oil phase separation is observed, and the result is shown in figure 10, figure 10 is a schematic diagram of the centrifugal stability of the multifunctional integrated Pickering emulsion prepared in example 9, figure 10 shows that the emulsion is not broken and the volume of the emulsion is not changed basically when the multifunctional integrated Pickering emulsion is centrifuged at 4000rpm for 30min on the high-speed centrifuge, which shows that the emulsion system can endure at least 30min 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 dissolved in 5m L deionized water to prepare aqueous dispersions with the concentration of 1mg/m L, 5m L toluene is added into the two groups of aqueous dispersions respectively, the oil phase and the aqueous dispersions 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 type Pickering emulsion, the emulsion state is observed by centrifuging at 8000rpm for 60 min on a high-speed centrifuge, and a very small amount of oil phase is separated out, so that the result is shown in figure 11, figure 11 is a schematic diagram of the centrifugal stability of the multifunctional integrated Pickering emulsion prepared in the example 10, figure 11 shows that the emulsion state is observed by centrifuging at 8000rpm for 60 min on the high-speed centrifuge, a small amount of oil phase is separated out on the upper layer, a small amount of aqueous phase is separated out on the lower layer, the emulsion rate is reduced, but the emulsion is not compact, the emulsion is more broken and the droplet size is more uniform and tends to show that the high-speed centrifugal aging is 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)2(iv)/g, Evonik chemical Co., Ltd., 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-bottomed flask, dispersed uniformly by sonication at room temperature and 50kHz for 10 minutes to obtain a dispersion, and then 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical technology Co., Ltd., purity 95% by weight) was added to the dispersion) And 0.5g of n-dodecyl trimethoxy silane (Shanghai Tantake technology, Ltd., purity of 95 wt%) to obtain a reaction solution, reacting the reaction solution in an oil bath at 100 ℃ for 6 hours in a nitrogen environment to obtain a reaction product, centrifugally separating the reaction product to obtain solid particles, respectively cleaning the solid particles twice with toluene and acetone, and performing vacuum drying at normal 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.
Example 12
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 particles2Evonik 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 a dispersion, 0.5g of butylaminopropyltriethoxysilane (Shanghai Baishu bioscience Co., Ltd.) and 0.1g of n-hexyltrimethoxysilane (Shanghai Baishu bioscience Co., Ltd., purity 97 wt%) were added to the dispersion to obtain a reaction solution, and the reaction solution 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)2G, Evonik chemical limited, Aerosil50, AR) was dried in a vacuum oven at 150 ℃ for 0.5 hour, added with 10m 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, to which was added 0.2g of diethylenetriaminopropyltrimethoxysilane (shanghai mcolin biochemical science limited, purity 95 wt%) and 0.1g of n-dodecyltrimethoxysilane (shanghai bailing scientific limited, purity 95 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ and under 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, which was obtained as a white powder having an average particle size of 220 ± 50 nm.
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 drying 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 a dispersion, to which were added 0.2g of diethylaminomethyltrimethoxysilane (Shanghai Michelle chemical Co., Ltd., purity of 95 wt%) and 0.1g of n-octadecyltrimethoxysilane (Shanghai Michelin bioscience Ltd., purity of 90 wt%) 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 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 emulsifierThe average hydraulic particle size of the particles of the particle emulsifier is 220 +/-50 nm, and the obtained sample is white powder.
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 limited, Aerosil50, AR) was dried in a vacuum oven at 120 ℃ for 1 hour, added together with 10m L of anhydrous toluene to a 50m L round-bottom flask, and dispersed uniformly by sonication at room temperature and 50kHz frequency for 10 minutes to obtain a dispersion, to which were added 0.2g of tris (2-aminoethyl) propylaminotrimethoxysilane (shanghai tai tamac technology limited, purity 90 wt%) and 0.1g of propyltriethoxysilane (shanghai mcolin bioscience limited, purity 98 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ and a 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.
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 aqueous dispersion 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 phases and the aqueous dispersion have the same volume, the multifunctional integrated Pickering emulsion is prepared in a homogenizer shearing emulsification mode (15000rpm, 2min), and the result is shown in the attached figure 12, wherein the figure 12 is a schematic diagram of the multifunctional integrated Pickering emulsion with different oil phases prepared in the example 16, and as can be seen from the attached figure 12, the multifunctional integrated Pickering particle emulsifier prepared in the invention has the capability of stabilizing a two-phase system formed by different oil phases and water, has universal emulsification capability, and achieves the purpose of the invention.
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 a complex multi-component system and has 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 emulsion prepared in example 12 was dissolved in deionized water to prepare an aqueous dispersion with a concentration of 1mg/m L, and the same volume of toluene and the aqueous dispersion were subjected to different emulsification methods (shaking by hand (5min), high-pressure shearing (80psi, 10min), ultrasonic emulsification (440kW, 10min), homogenizer shearing emulsification (15000rpm, 2min)) to prepare the multifunctional integrated Pickering emulsion, and the results are shown in FIG. 13, where FIG. 13 is a schematic diagram of the multifunctional integrated Pickering emulsion obtained in the different emulsification methods prepared in example 17.
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 saline dispersion with concentration of 5mg/m L, toluene and the saline dispersion with the same volume are taken, and the multifunctional integrated Pickering emulsion is prepared by a homogenizer shearing emulsification mode (15000rpm, 2min), and is placed at room temperature for different time (1 day, 6 months and 14 months), so that the result is 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 of the emulsion on the micro side tends to become larger and the fraction of the emulsion on the macro side tends to decrease with the extension of the placing time, the total volume decreases due to oil phase volatilization caused by long-term placing, the emulsion is not greatly changed on the macro side and the micro side after being placed for 6 months, and the emulsion breaking phenomenon does not occur after being placed for a long time, and the emulsion breaking phenomenon still exists after being placed for a long time, thus the multifunctional integrated Pickering emulsion obtained by the invention is good in view.
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 an aqueous dispersion with a concentration of 0.5mg/m L, the same volume of toluene and the aqueous dispersion were added to prepare the multifunctional integrated Pickering emulsion by shearing and emulsifying with a homogenizer (15000rpm, 2min), and CO was added to 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, where FIG. 15 is CO of the multifunctional integrated Pickering emulsion prepared in example 192/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 reagent2Responsive implementation(ii) a 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 an aqueous dispersion with a concentration of 2.5mg/m L, the same volume of toluene and the aqueous dispersion is taken to prepare the multifunctional integrated Pickering emulsion by a homogenizer shearing emulsification method (15000rpm, 2min), the emulsion is passed through a self-filled quartz sand column, the first time, the amount of the emulsion is lost due to non-wetting of the quartz sand column, but the emulsion is not broken, the emulsion passes through the quartz sand column for multiple times, the process can be circulated for multiple times, the volume of the emulsion is basically unchanged, and the viscosity of the emulsion is basically unchanged, the result is shown in figures 16 and 17, figure 16 is a schematic diagram of the situation 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 multiple times of passing through the quartz sand column, figure 17 is a diagram of a schematic diagram of a viscosity test result that the multifunctional integrated Pickering emulsion prepared in example 20, the multifunctional integrated Pickering emulsion passes through the quartz sand column before and after the quartz sand column, the silica column, the first time, the viscosity of the multifunctional integrated Pickering emulsion is reduced by the quartz sand column, and the invention is also can be shown in figure 16.
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 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 a dispersion, 0.5g of diethylenetriaminopropyltrimethoxysilane (Shanghai Michelin Biochemical technology Co., Ltd., purity 95 wt%) was added to the dispersion 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 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, charged together with 20m L anhydrous toluene into a 50m L round-bottomed flask, dispersed uniformly by sonication at room temperature and 50kHz for 30 minutes to give a dispersion, and 0.5g of n-hexyltrimethoxysilane (Shanghai Bailingwei chemical Co., Ltd., purity: 95% by weight) was added to the dispersion to give a reaction liquid,the reaction solution reacts for 12 hours in an oil bath at the temperature of 110 ℃ and under the nitrogen environment to obtain a reaction product, the reaction product is centrifugally separated to obtain solid particles, the solid particles are respectively washed twice by toluene and acetone, and the solid particles are dried for 12 hours in vacuum at normal temperature to obtain 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 a 10mg/m L aqueous dispersion, 5m L toluene was added, the oil phase was in the same volume as the aqueous dispersion, 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 type emulsion having poor 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 mono hydrophobic alkyl functionalized Pickering particulate emulsifier powder prepared in comparative example 2 was dissolved in 5m L DI water to give a 10mg/m L aqueous dispersion, 5m L toluene was added, the same volume of oil phase as the above aqueous dispersion was added, and the mono hydrophobic alkyl was prepared by shear emulsification with a homogenizer (15000rpm, 2min)The appearance of the Pickering emulsion was photographed and the emulsion was a water-in-oil emulsion, and the results are shown in FIG. 21. Although the emulsion has better emulsification effect, the emulsion does not contain CO because the single alkyl functionalized particle emulsifier is used2And (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) 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, and dispersed uniformly by sonication at room temperature and 50kHz for 30 minutes to obtain a dispersion, to which were added 0.05g of diethylenetriaminopropyltrimethoxysilane (Shanghai Tatan Co., Ltd., purity 95 wt%) and 0.5g of n-hexadecyltrimethoxysilane (Shanghai Bailingwei Co., Ltd., purity 95 wt%) to obtain a reaction solution, which was reacted in an oil bath at 110 ℃ under nitrogen atmosphere for 24 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 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, and added together with 20m L anhydrous toluene to a 50m L round-bottomed flask, and the mixture was ultrasonically dispersed at room temperature and 50kHz for 30 minutes to obtain a dispersion, and then 0.5g of diethylenetriaminopropyltrimethoxysilane (shanghai tatatan technologies, ltd., purity 95 wt%) and 0.5g of n-hexadecyltrimethoxysilane (shanghai bailing wilford technologies, ltd., purity 95 wt%) were added to the dispersion to obtain a reaction solution, and the reaction solution was reacted at 50 ℃ for 48 hours in a nitrogen atmosphere to obtain a reaction product, and the reaction product 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 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 (11)
1. The multifunctional integrated Pickering particle emulsifier is characterized by comprising fumed silica particles, and an amino silane coupling agent and a hydrophobic alkyl silane coupling agent which are respectively grafted on the surfaces of the fumed silica particles; wherein the mass ratio of the fumed silica particles to the amino silane coupling agent to the hydrophobic alkyl silane coupling agent is 5: 2-9: 0.5-5.
2. The multifunctional integrated Pickering particle emulsifier according to claim 1, wherein the fumed silica particles have a primary particle size of 4-200 nm, and a BET specific surface area of 50m2/g～400m2/g。
3. The multifunctional integrated Pickering particle emulsifier 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.
4. The multifunctional integrated Pickering particle emulsifier according to claim 3, wherein the amino silane coupling agent is diethylenetriaminopropyltrimethoxysilane, butylpropylamino-triethoxysilane, diethylaminomethyltrimethoxysilane or tris (2-aminoethyl) propylaminotrimethoxysilane.
5. The multifunctional integrated Pickering particle emulsifier according to claim 1, wherein the hydrophobic alkyl silane coupling agent is a C3-C20 linear or branched chain saturated alkyl silane coupling agent.
6. The multifunctional integrated Pickering particulate emulsifier according to claim 5, wherein the hydrophobic alkylsilane coupling agent is n-dodecyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-hexyltrimethoxysilane, n-octadecyltrimethoxysilane, or propyltriethoxysilane.
7. A preparation method of the multifunctional integrated Pickering particle emulsifier as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
mixing fumed silica particles and a solvent, and performing ultrasonic dispersion to obtain a dispersion liquid;
under the protection of inert gas or nitrogen, mixing the dispersion liquid, the amino silane coupling agent and the 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.
8. The preparation method of the multifunctional integrated Pickering particle emulsifier according to claim 7, wherein the step of drying the fumed silica particles is further included before mixing the fumed silica particles with the solvent, and specifically includes: drying the fumed silica particles for 0.5 to 12 hours at the temperature of between 80 and 150 ℃.
9. The preparation method of the multifunctional integrated Pickering particle emulsifier as claimed in claim 7, wherein the concentration of gas-phase silica particles in the dispersion liquid is 5 g/L-50 g/L, the concentration of an amino silane coupling agent in the reaction liquid is 1 g/L-50 g/L, and the concentration of a hydrophobic alkyl silane coupling agent in the reaction liquid is 1 g/L-50 g/L.
10. The preparation method of the multifunctional integrated Pickering granular emulsifier according to claim 7, wherein the solvent is anhydrous toluene.
11. The preparation method of the multifunctional integrated Pickering granular emulsifier according to claim 7, wherein the heating reaction temperature is 80-110 ℃, and the heating reaction time is 2-12 h.
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