CN114854432B - Intelligent emulsion based on dynamic covalent bonds and preparation method thereof - Google Patents
Intelligent emulsion based on dynamic covalent bonds and preparation method thereof Download PDFInfo
- Publication number
- CN114854432B CN114854432B CN202210573952.7A CN202210573952A CN114854432B CN 114854432 B CN114854432 B CN 114854432B CN 202210573952 A CN202210573952 A CN 202210573952A CN 114854432 B CN114854432 B CN 114854432B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- oil
- intelligent
- covalent bonds
- active system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/28—Aminocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a dynamic co-based methodAn intelligent emulsion with valence bond and a preparation method thereof belong to the field of colloid and interface chemistry. The invention utilizes an amphiphilic surface active system to cooperate with Al 2 O 3 The particles stabilize oil-in-dispersion emulsion, alkaline adjusts FA-AA of 'strong polarity', intelligent conversion of the compound from 'amphiphilicity' to 'strong polarity' and conversion of the emulsion from 'emulsion formation' to 'non-emulsion formation' are realized, and the conversion can be circulated for four times. Meanwhile, the detection of ultraviolet absorbance is carried out on the oil phase after the first demulsification, so that the Bola compound cannot remain in the oil phase, and the recovery and the reutilization of a certain amount of surfactant can be realized. This feature has important roles in the fields of oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil exploitation, cosmetics, food science, etc.
Description
Technical Field
The invention belongs to the field of colloid and interface chemistry, and particularly relates to an intelligent emulsion based on dynamic covalent bonds and a preparation method thereof.
Background
In recent years, the antenna of smart technology extends to the chemical field, and surfactants and surface-active nanoparticles with stimulus response properties also become research hotspots in the fields of surfactants and colloids. Under certain external stimulus, the structures of the functional compounds are reversibly changed, so that the functional compounds are reversibly converted between surface activity and no surface activity, and further the microscopic property and macroscopic property of the system are affected. Therefore, the system performance can be intelligently regulated, and the recycling of resources can be realized, so that the system has a great application prospect.
Intelligent emulsions are one such application. Emulsions are well known as a typical liquid-liquid dispersion system and have been widely used in civil and industrial applications. Although emulsions are thermodynamically unstable, most emulsions may be kept kinetically stable by emulsifiers or emulsion stabilizers. Depending on the type of emulsifier used, emulsions are generally classified as conventional emulsions stabilized by surfactant molecules or polymers; a Pickering emulsion stabilized by a surfactant and oppositely charged nanoparticles; and novel emulsions-oil-in-dispersion emulsions stabilized by surfactants and identically charged nanoparticles. Among them, conventional emulsions generally require a surfactant at a concentration higher than its critical micelle concentration cmc, and Pickering emulsions require a surfactant at a lower concentration (about 0.1 cmc), but they are difficult to break. Compared with the conventional emulsion and Pickering emulsion, the oil-in-dispersion emulsion has the advantages of low content of used particles (the minimum content can be 0.0001 wt.%), low concentration of used surfactant (0.001 cmc), long-term stability, simpler demulsification and the like.
In addition, the reported intelligent oil-in-dispersion emulsion can realize the recycling of resources, but the supported intelligent surfactant often has the problems of complex synthesis process, low conversion rate, no green synthesis process and the like, and greatly limits the application of the intelligent oil-in-dispersion emulsion in the fields of petroleum exploitation, cosmetics, food science and the like.
Therefore, the research and preparation of the green sustainable intelligent oil-in-dispersion emulsion are of great significance.
Disclosure of Invention
Technical problem
The conventional emulsion has the defects of higher use concentration (more than or equal to cmc), shorter stabilizing time, residual surfactant in an oil phase after demulsification and the like; pickering emulsion has the problems of high content of nanoparticles (0.1-3 wt.%) and difficult demulsification. Accordingly, the present invention seeks to provide a smart oil-in-dispersion emulsion based on dynamic covalent bonds, solving the above-mentioned problems. The oil-in-dispersion emulsion is composed of cationic surfactant H + AA (switchable between "amphiphilic" and "strongly polar") and equally charged Al 2 O 3 The particles are synergistic and stable, and the method has the advantages of simple and convenient operation, green operation process, good emulsion stability, low use concentration of nano particles and surfactant, easy demulsification, recycling and the like. The introduction of dynamic covalent bond makes the surfactant capable of intelligently converting between amphiphilicity and strong polarity, and the surface is in acid conditionActive agent (H) + AA) remain amphiphilic, having surface activity; under alkaline conditions, the surfactant and the other substance form Bola compounds (FA-AA), which exhibit "strong polarity", lose surface activity, and dissolve in water. The whole process can be circulated for a plurality of times, intelligent conversion of 'amphiphilicity' and 'strong polarity' is realized, and the surfactant is always in the aqueous solution, so that the recovery and the reutilization are convenient.
Technical proposal
The invention utilizes a surface active system (H) based on dynamic covalent bonds + AA and FA), the surfactant system having "amphiphilicity" as compared to the same charged Al 2 O 3 The particle action synergistically stabilizes the oil-in-dispersion emulsion, n-decane is selected as an oil phase, and the oil-in-dispersion emulsion can be prepared by homogenizing for 2min at the rotating speed of 11000 r/min. Then alternately adding acid and alkali, H + AA and FA form a "strongly polar" Bola compound FA-AA in alkaline environment, which cannot be combined with Al due to its strong hydrophilicity 2 O 3 The particles together stabilize the emulsion; thus, the surface-active particles can be switched between "amphiphilic" and "strongly polar", i.e. "surface-active" and "surface-inactive". And (5) continuing acid-base regulation, and circularly converting. In addition, FA plays a considerable role during this cycle, not only imparting stimulus response properties to the surfactant, but also being critical to the system being cycled.
The first object of the invention is to provide a novel intelligent oil-in-dispersion emulsion based on dynamic covalent bonds, which is prepared by a method comprising the steps of mixing an aqueous phase, an oil phase, a surfactant system and hydrophilic Al 2 O 3 Mixing the granules to obtain emulsion; the surface active system is composed of a component H + AA. FA composition:
wherein n=7 to 9, and x is Cl or Br.
In one embodiment of the invention, the molar ratio of the two components in the surfactant system is 1:1.
In one embodiment of the invention, a process for preparing a surface-active system is described as follows:
reacting amino alkyl acid AA and FA under alkaline condition at normal temperature to form covalent bond to obtain FA-AA; then FA-AA is subjected to the action of acid HX to obtain a surfactant system; the surface active system can be recovered again under the alkaline action to obtain FA-AA, thereby realizing the reuse of the surface active system.
In one embodiment of the invention, AA in the method is a primary amine-containing compound that forms a dynamic covalent bond with an aldehyde group at ambient temperature and is negatively charged under alkaline conditions.
In one embodiment of the invention, FA in the method is a compound that contains a benzene ring, forms a dynamic covalent bond with a primary amine at normal temperature, and is negatively charged under alkaline conditions.
In one embodiment of the invention, the alkaline pH in the process is from 10 to 13, preferably from 11 to 12.
In one embodiment of the invention, the reaction temperature in the process is ambient temperature.
In one embodiment of the invention, the reaction time in the process is ≡30min to ensure sufficient reaction.
In one embodiment of the invention, the reaction conditions in the process are stirring.
In one embodiment of the invention, fA-AA in the method has a relatively strong hydrophilicity.
In one embodiment of the invention, the acidic pH in the process is in the range of 3 to 5.
In one embodiment of the invention, H in the method + AA is a surfactant.
In one embodiment of the invention, the surfactant system achieves a smart response by:
in one embodiment of the invention, the pH of the base is from 10 to 13, preferably from 11 to 12; the pH value of the acid is 3-5.
In one embodiment of the invention, hydrophilic Al 2 O 3 The mass concentration of the particles relative to the water phase is 0.005-3%.
In one embodiment of the invention, the concentration of the surface-active system, calculated as FA, relative to the aqueous phase is from 0.06 to 10mmol/L.
In one embodiment of the invention, the oil phase comprises any one or more of the following: n-decane, toluene, glyceryl tricaprylate.
The invention further aims to apply the intelligent oil-in-dispersion emulsion based on the dynamic covalent bond to the fields of oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil exploitation, cosmetics, food science and the like.
Advantageous effects
The invention utilizes an amphiphilic surface active system to cooperate with Al 2 O 3 The particles form stable oil-in-dispersion emulsions, the alkalinity is adjusted to "strongly polar" FA-AA, the compound is not surface active and does not cooperate with Al 2 O 3 The particles stabilize oil-in-dispersion emulsion, thereby realizing intelligent conversion of the compound from 'amphiphilicity' to 'strong polarity' and conversion of the emulsion from 'milk formation' to 'non-milk formation', and the conversion can be circulated for four times. Meanwhile, the detection of ultraviolet absorbance is carried out on the oil phase after the first demulsification, so that the Bola compound cannot remain in the oil phase, and the recovery and the reutilization of a certain amount of surfactant can be realized. This property is used in oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil exploitation, cosmetics and food scienceHas important functions in the fields of the like.
Drawings
FIG. 1 is an ESI-MS spectrum of a Bola compound FA-AA.
FIG. 2 shows the Bola compound FA-AA 1 H NMR spectrum (60 mm, ph=12.00, d) 2 O)。
FIG. 3 is a diagram of (A) FA-AA, (B) AA and (C) FA 1 Comparison of H NMR spectra (60 mm, ph=12.00, d 2 O)。
FIG. 4 is a comparison of FT-IR spectra of (A) FA-AA, (B) AA and (C) FA (pH=12.00).
FIG. 5 shows surfactant H + AA (AA) 1 HNMR spectra (60 mm, ph=4.00, dmso).
FIG. 6 is a nano Al 2 O 3 (a) SEM images, (b) TEM images, (c) Zeta potential versus pH images, and (d) particle size images of the particles.
FIG. 7 is a graph of individual nano Al 2 O 3 Photograph of the appearance of a particle (0.01 wt.%) stable n-decane/water (3 mL/3 mL) emulsion relative to the aqueous phase.
FIG. 8 is 0.01wt.% nano Al 2 O 3 Particles and different concentrations of H + Photographs of the (A and B) appearance and (C) micrographs of the AA-stabilized n-decane/water oil-in-dispersion emulsion. Wherein A is photographed immediately after milk beating, and (B and C) is photographed after the milk is stabilized for 24 hours.
FIG. 9 is a flow chart of the emulsion stimulus response. HCl and NaOH were added for switching: (a) initial solution, (b) n-decane was added and homogenized for 2min, (c) the oil phase was separated off and acidified by addition of HCl, (d) fresh n-decane was added and homogenized for 2min.
FIG. 10 is 0.01wt.% nano Al 2 O 3 Particles with 0.6mM H + Photographs of (A) appearance and (B) micrographs of AA stabilized oil-in-dispersion emulsions. The on or off cycle is performed by adding HCl and NaOH.
FIG. 11 is a nano Al 2 O 3 Granules and surfactant H + Mechanism diagram of AA stabilized intelligent oil-in-dispersion emulsion.
Fig. 12 is a graph of absorbance versus wavelength scan (ph=12.00) for aqueous solutions of different concentrations FA-AA; (b) Absorbance-concentration standard curve (ph=12.00) at 296nm for different concentrations of FA-AA aqueous solutions.
Detailed Description
The emulsion appearance photo is taken by a digital camera or a mobile phone; the emulsion micrograph was taken using a super depth of field three-dimensional microscope from Kidney Co., ltd, with a lower light source, magnification of 250-2500 times, and test temperature of 25 ℃.
Example 1:
the synthetic route for the Bola compound FA-AA is as follows:
equal molar amounts of FA and AA (10 mmol), and 2-fold molar amounts of NaOH were added to a 100mL volumetric flask, and the volume was fixed using ultrapure water. The pH of the system was then adjusted to 12.00 using a 2M sodium hydroxide solution, magnetons were added and stirred for half an hour to ensure the reaction was complete. Finally, an aqueous solution of FA-AA constructed by dynamic covalent bonds was obtained. ESI-MS of FA-AA, 1 h NMR and FT-IR spectra as shown in FIGS. 1-4.
Similarly, the substitution of 11-aminoundecanoic acid for 10-aminodecanoic acid and 12-aminododecanoic acid, respectively, gives the corresponding Bola compounds 10-FA-AA and 12-FA-AA.
Example 2: preparation of surface-active systems
10mmol of 11-aminoundecanoic acid was added to a 100mL volumetric flask, and the volume was fixed using ultrapure water. Then adjusting pH of the system to 4.00 with 2M hydrochloric acid solution, adding magneton, stirring for half an hour to ensure complete protonation, to obtain surfactant 11-H + Aqueous AA solution. The surfactant is 1 H NMR is shown in FIG. 5.
Similarly, the corresponding surfactant 10-H can be obtained by replacing 11-aminoundecanoic acid with 10-aminononanoic acid and 12-aminododecanoic acid, respectively + AA and 12-H + AA。
Respectively 10-H + AA、11-H + AA and 12-H + Compounding AA with equimolar FA to obtain phaseA corresponding surface-active system.
Example 3: nano Al 2 O 3 Surface Activity test of particles
0.003g of commercial nano Al is weighed in a 10mL glass bottle 2 O 3 Particles (primary particle diameter about 13nm, specific surface area S) BET About 85-115m 2 /g, SEM and TEM see FIG. 6), 3mL of ultrapure water was added and the particles were then uniformly dispersed (0.01 wt.%) using an ultrasonic disperser. Adding 3mL of n-decane into a glass bottle, homogenizing and emulsifying for 2min at 11000r/min by using a high shear homogenizer, wherein stable emulsion cannot be obtained, as shown in FIG. 7, indicating that the commercial nano Al is used 2 O 3 The particles are not surface active.
Example 4: preparation of Oil-in-dispersion emulsion
Weighing 0.003g of nano Al 2 O 3 The particles were ultrasonically dispersed in 3mL of a surfactant system of different concentrations (calculated as FA, the relative concentrations of the aqueous phase were 0.03mM, 0.06mM, 0.1mM, 0.3mM, 0.6mM, 1.0mM, 3.0mM, 6.0mM, respectively), 3mL of n-decane was added, and after homogenizing and emulsifying with a high shear homogenizer for 2 minutes, a stable O/W type oil-in-dispersion emulsion was obtained, as shown in FIG. 8. The emulsion can be placed for at least more than one month, and no emulsion separation or demulsification phenomenon occurs, which shows that the obtained oil-in-dispersion emulsion has very good stability.
Example 5: pH stimulus-response Property of Oil-in-dispersion emulsion
To facilitate the experiment, the test was performed according to the procedure of fig. 9.
0.01wt.% of nano Al 2 O 3 The particles were studied on the basis of 0.3mM FA-AA. Weighing 0.003g of nano Al 2 O 3 The particles were sonicated in a 0.3mM FA-AA solution (pH=12.00), 7mL of n-decane was added, and homogenized with a high shear homogenizer for 2min, failing to form a stable oil-in-dispersion emulsion. Separating oil phase from the upper layer, adding 50 μl of 20mM HCl solution into lower layer water phase, adding 3mL of fresh n-decane, homogenizing with high shear homogenizer for 2min to form stable O/W type oil-in-dispersion emulsion, and homogenizingThe solution was placed in a incubator at 25℃and allowed to stand for 24 hours to examine its stability. 4 cycles can be achieved by alternating NaOH and HCl addition, as shown in fig. 10. The mechanism diagram is shown in fig. 11.
Example 6: emulsifying Properties of different surfactants
Referring to example 3, 0.003g of nano Al was weighed out 2 O 3 The particles are dispersed in 3mL of 0.3mM surface active system by ultrasonic, 3mL of n-decane is added, and after homogenizing and emulsifying for 2min by a high shear homogenizer, stable O/W type oil-in-dispersion emulsion is obtained. Replacement of surfactant only for 10-H + AA (n=7) and 12-H + AA (n=9), the other conditions were unchanged, resulting in the corresponding oil-in-dispersion emulsion. The emulsion thus obtained was left at room temperature, and its stability was measured. Referring to example 5, pH response performance was tested by adjusting pH. The performance results of the resulting emulsions are shown in Table 1.
TABLE 1 results of emulsifying Properties of different surfactants
Example 7: detection of residual surfactant in oil phase
The detection was performed using an ultraviolet spectrophotometer, and as shown in FIG. 12, the maximum absorption wavelength and absorbance at the maximum absorption wavelength of different concentrations of FA-AA were detected. As can be seen from FIG. 12 (a), fA-AA has two maximum absorption wavelengths, and since the absorption intensity of the E1 band is large, the absorbance is not easily controlled to be within 1, and thus the maximum absorption wavelength (lambda) in the E2 absorption band is selected max =296 nm) was used as the experimental basis. Then, an absorbance-concentration standard curve is drawn from the absorbance of different concentrations FA-AA at this absorption wavelength (fig. 12 (b)). The equation of the fitted curve is y= 1.7333x, variance r 2 ＝0.9995。
The oil phase separated by the first demulsification was collected, and the ultraviolet absorbance was measured, and the test results are shown in table 2.
TABLE 2 fresh n-decane and UV absorbance of n-decane isolated after each demulsification
The absorbance of the separated oil phase was 0.012, which means that 2.3% of the FA was lost, which also involves a possible excess of FA or incomplete reaction of FA with AA, although this also illustrates to some extent that more than 97% of FA-AA was returned to the aqueous phase to effect surfactant H + Recovery and reuse of AA.
Claims (9)
1. A method for preparing intelligent emulsion based on dynamic covalent bonds is characterized in that an aqueous phase, an oil phase, a surface active system and hydrophilic Al 2 O 3 Mixing the particles uniformly to obtain emulsion, namely oil-in-dispersion emulsion;
the surface active system is composed of a component H + AA. FA composition:
wherein n=8, x is Cl or Br;
a method for preparing a surface active system, said method comprising:
reacting amino alkyl acid AA and FA under alkaline condition at normal temperature to form covalent bond to obtain FA-AA; then FA-AA is subjected to the action of acid HX to obtain a surfactant system; the surface active system can be recovered again under the alkaline action to obtain FA-AA for repeated use; the acid HX adjusts the acid pH value to 3-5.
2. The method of claim 1, wherein hydrophilic Al 2 O 3 The mass concentration of the particles relative to the water phase is 0.005-3%.
3. The process according to claim 1, wherein the concentration of the surface-active system, calculated as FA, relative to the aqueous phase is from 0.06 to 10mmol/L.
4. The method of claim 1, wherein the oil phase comprises any one or more of: n-decane, toluene, glyceryl tricaprylate.
5. The method of claim 1, wherein the molar ratio of the two components in the surfactant system is 1:1.
6. A smart emulsion based on dynamic covalent bonds prepared by the method of any one of claims 1-5.
7. The intelligent emulsion based on dynamic covalent bonds according to claim 6, characterized in that the surface-active system achieves intelligent response of the emulsion by:
8. the intelligent emulsion based on dynamic covalent bonds according to claim 7, characterized in that the alkaline pH is between 10 and 13; the pH value of the acidity is 3-5.
9. The use of the intelligent emulsion based on dynamic covalent bonds according to claim 6 in the fields of oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil exploitation, cosmetics and food science.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210573952.7A CN114854432B (en) | 2022-05-24 | 2022-05-24 | Intelligent emulsion based on dynamic covalent bonds and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210573952.7A CN114854432B (en) | 2022-05-24 | 2022-05-24 | Intelligent emulsion based on dynamic covalent bonds and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114854432A CN114854432A (en) | 2022-08-05 |
| CN114854432B true CN114854432B (en) | 2023-07-04 |
Family
ID=82638965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210573952.7A Active CN114854432B (en) | 2022-05-24 | 2022-05-24 | Intelligent emulsion based on dynamic covalent bonds and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114854432B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854431B (en) * | 2022-05-24 | 2023-06-13 | 江南大学 | Intelligent Pickering emulsion based on dynamic covalent bonds and preparation method thereof |
| CN114774135B (en) * | 2022-05-24 | 2023-06-13 | 江南大学 | Recyclable surface active system based on dynamic covalent bond |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111514107B (en) * | 2020-04-30 | 2021-12-21 | 江南大学 | Active oxygen response type vesicle and preparation method thereof |
| CN113461576B (en) * | 2021-06-23 | 2022-09-06 | 四川大学 | Dynamic covalent bond-based responsive surfactant and preparation method thereof |
| CN113563208B (en) * | 2021-07-07 | 2022-10-11 | 江南大学 | Emulsion with multiple response performance |
| CN113398836B (en) * | 2021-07-08 | 2023-04-07 | 西南石油大学 | Particle-stabilized high internal phase switching emulsions, methods of making, and methods of recovering particles |
-
2022
- 2022-05-24 CN CN202210573952.7A patent/CN114854432B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114854432A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114854432B (en) | Intelligent emulsion based on dynamic covalent bonds and preparation method thereof | |
| CN103788402B (en) | A kind of carbon quantum dot/hectorite emulsion-stabilizing system and prepare the method for paraffin wax emulsions | |
| CN112675715B (en) | Polyamide nano composite film and preparation method and application thereof | |
| CN110577486A (en) | Rosin-based CO2/N2Response type surfactant and preparation method and application thereof | |
| CN102391416A (en) | Preparation method of porous material based on inorganic nanoparticles for stabilizing high internal phase emulsion | |
| CN112108075B (en) | Pickering emulsifier and preparation method and application thereof | |
| CN114854431B (en) | Intelligent Pickering emulsion based on dynamic covalent bonds and preparation method thereof | |
| CN111889025B (en) | Acid-alkali-resistant salt-resistant super-amphiphilic molecule emulsifier, preparation method thereof and emulsion | |
| Månsson et al. | A microgel-Pickering emulsion route to colloidal molecules with temperature-tunable interaction sites | |
| JP2009057627A (en) | Thick nanocolloidal gold liquid, fine gold particle, and their manufacturing methods | |
| Blin et al. | Hybrid/porous materials obtained from nano-emulsions | |
| Liu et al. | Recyclable surfactant containing a dynamic covalent bond and relevant smart emulsions | |
| KR20130079983A (en) | Zirconium oxide nanoparticles and hydrosol of the same and composition and method for manufacturing zirconium oxide nanoparticles | |
| Wang et al. | Pickering emulsions based on sustainable MIL-101 (Fe)/CNC hybrid nanoparticles for effective photocatalytic degradation of aqueous dyes | |
| CN114774135B (en) | Recyclable surface active system based on dynamic covalent bond | |
| Qian et al. | Effect of synthesis time on morphology of hollow porous silica microspheres | |
| Yang et al. | Scalable synthesis of core–shell microgel particles using a ‘dry water’method | |
| CN108686575B (en) | Composite emulsifier with magnetic response performance | |
| JP2009197142A (en) | Organomodified silica fine particles and manufacturing method for it | |
| JPH0725905A (en) | Microparticle of spherical chitosan and its production | |
| Hajarul et al. | Properties of amorphous silica entrapped isoniazid drug delivery system | |
| CN104138733A (en) | Silica hollow microspheres with through-macropores on surface and preparation method thereof | |
| Wang et al. | Pickering Emulsions and Viscoelastic Solutions Constructed by a Rosin-Based CO2-Responsive Surfactant | |
| Zhang et al. | Self-assembly structural transition of protic ionic liquids and P123 for inducing hierarchical porous materials | |
| Chen et al. | Preparation of silica capsules via an acid-catalyzed sol–gel process in inverse miniemulsions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |