CN111116896A - Dehydrorosin polyether surfactant, Pickering high internal phase emulsion and preparation method thereof - Google Patents
Dehydrorosin polyether surfactant, Pickering high internal phase emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention provides a dehydrogenated rosin polyether surfactant and a preparation method thereof, and a Pickering high internal phase emulsion is prepared by using the dehydrogenated rosin polyether surfactant and inorganic particles. The preparation method of the Pickering high internal phase emulsion comprises the steps of firstly dispersing the dehydrogenated rosin polyether surfactant and inorganic particles into an aqueous solution to obtain a water phase with the mass concentration of the dehydrogenated rosin polyether surfactant being 0.01-1% and the mass concentration of the inorganic particles being 0.18-1.5%; then adding an oil phase with the volume fraction of 75-90 percent relative to the water phase into the water phase, and shearing and emulsifying to obtain the emulsion. The dehydrogenated rosin polyether surfactant is mixed with nano or micron inorganic particles, hydrogen bond action is generated between the surfactant and the nano or micron inorganic particles, the surfaces of the inorganic particles are subjected to hydrophobic modification, a dissipation attraction force exists, and stable Pickering high internal phase emulsion can be constructed under low concentration.
Description
Technical Field
The invention belongs to the technical field of emulsion preparation, and particularly relates to a dehydrorosin polyether surfactant, a Pickering high internal phase emulsion and a preparation method thereof.
Background
High internal phase emulsions are emulsions in which the internal phase (dispersed phase) accounts for more than 74% by volume, and have attracted considerable attention in the fields of food, cosmetics, medicines, materials, oil extraction, environmental protection, and the like. Because the high internal phase emulsion contains higher internal phase content, the system viscosity is higher, the high internal phase emulsion has the property of being similar to gel, if the continuous phase contains polymerizable monomers, the template function of the polymerized monomers can be utilized to prepare porous polymer materials, and the materials have a large number of applications in the aspects of catalysis, adsorption separation, filter membrane materials, drug delivery, sensing materials and the like due to the high specific surface area. However, the construction of the traditional high internal phase emulsion needs a large amount of petroleum-based surfactant (5-50 wt%) (Soft Matter,2007,3, 1525-1529; Macromol. RapidCommun.,2005,26, 1289-1293), the high concentration of the surfactant has potential harm to the environment, and it is difficult to find a proper surfactant to prevent the phase inversion of the formed high internal phase emulsion under the high internal phase condition.
Recently, a great deal of attention has been paid to the formation of Pickering high internal phase emulsions using inorganic particles to stabilize the high internal phase emulsion. The inorganic particles can be irreversibly adsorbed on an oil-water interface in the emulsion, the high adsorption energy of the inorganic particles enables emulsion droplets not to be easily merged, and the emulsion has higher stability compared with a surfactant used alone. But due to the general inorganic particles (e.g. SiO)2、TiO2、ZnO、Al2O3Etc.) has strong hydrophilicity, is difficult to be adsorbed on an oil-water interface,therefore, unmodified inorganic particles are difficult to form stable Pickering high internal phase emulsions at low concentrations.
In order to solve the above problems, researchers have tried to modify the hydrophilicity and hydrophobicity of inorganic particles through covalent bonds or non-covalent modifications (j. concrete. food chem.,2019,67, 3423-.
Disclosure of Invention
The invention aims to solve the problem that inorganic particles are difficult to form stable high internal phase emulsion under low concentration in the prior art, provides a dehydrogenated rosin polyether surfactant and a preparation method thereof, and prepares Pickering high internal phase emulsion by utilizing the dehydrogenated rosin polyether surfactant and the inorganic particles together, so that stable Pickering high internal phase emulsion can be formed under low inorganic particle concentration.
The structural formula of the dehydrogenated rosin polyether surfactant provided by the invention is as follows:
wherein n is more than or equal to 8 and less than or equal to 46.
The preparation method of the dehydrogenated rosin polyether surfactant provided by the invention comprises the following steps:
(1) mixing the dehydrogenated rosin with an acylating agent and then carrying out an acylation reaction to obtain an acylated rosin;
(2) polyethylene glycol (PEG) and an initiator are added into the acylated rosin to carry out polymerization reaction to obtain the dehydrogenated rosin polyether surfactant.
The synthetic route of the reaction is as follows:
wherein n is more than or equal to 8 and less than or equal to 46.
Further, the molecular weight of the polyethylene glycol is 400-2000, preferably 400, 800, 1000, 1500 and 2000.
Further, in the step (1), the temperature of the acylation reaction is 25-45 ℃. Preferably, the acylation reaction time is 5-10 h.
Further, the mole ratio of the dehydrogenated rosin to the acylating agent is 10: (10-11).
Further, the acylating agent is selected from any one of oxalyl chloride, thionyl chloride and phosphorus trichloride.
Further, in the step (2), the polymerization reaction temperature is 40-60 ℃. Preferably, the polymerization reaction time is 5-14 h.
Further, the mole ratio of the dehydrogenated rosin to the polyethylene glycol is 10: (10-11).
Further, the initiator is selected from any one of Triethylamine (TEA), pyridine and imidazole.
The invention also discloses a preparation method of the Pickering high internal phase emulsion by using the dehydroabietic polyether surfactant and inorganic particles together, namely the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles, which comprises the following steps:
1) dispersing a dehydrogenated rosin polyether surfactant and inorganic particles into an aqueous solution to obtain a water phase with the mass concentration of the dehydrogenated rosin polyether surfactant being 0.01-1% and the mass concentration of the inorganic particles being 0.18-1.5%;
2) adding an oil phase with the volume fraction of 75-90% relative to the water phase into the water phase, and shearing and emulsifying to obtain the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles.
Further, the particle size of the inorganic particles is 10nm to 3 μm.
Further, the inorganic particles are selected from any one of silicon oxide, zinc oxide, titanium oxide, and aluminum oxide.
Further, the oil phase is selected from at least one of n-hexane, n-heptane, n-decane, n-hexadecane, toluene, liquid paraffin, and ethyl acetate.
Further, the emulsifying and shearing rotating speed is 15000-25000 rpm, and the emulsifying time is preferably 2-4 min.
The dehydroabietic polyether surfactant disclosed by the invention has a hydrogen bond effect with hydrophilic groups (such as hydroxyl) on inorganic particles, and simultaneously carries out hydrophobic modification on the surfaces of the inorganic particles, so that the inorganic particles are easily distributed on an oil-water interface of the emulsion, and the stability of the Pickering high internal phase emulsion is facilitated; meanwhile, a dissipative attraction acting force exists between the rosin polyether surfactant and the inorganic particles, and the acting force is helpful for the accumulation of the inorganic particles on an oil-water interface in the emulsion, so that the Pickering high internal phase emulsion has long-term stability.
Based on the interaction between the dehydroabietic polyether surfactant and the inorganic particles, the dehydroabietic polyether surfactant can form a stable Pickering high-internal phase emulsion with low-concentration nano-or even micron-sized inorganic particles under low concentration, wherein the mass concentration of the dehydroabietic polyether surfactant is as low as 0.01%, and the mass concentration of the inorganic particles is as low as 0.18%; while the internal phase has a volume fraction of up to 90%.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a dehydrogenated rosin polyether surfactant of example 1;
FIG. 2 is an infrared spectrum of a dehydrorosin polyether surfactant and a dehydrorosin synthesized by using polyethylene glycols of different molecular weights in examples 1 to 4;
FIG. 3 is a gamma-logc curve of the dehydrogenated rosin polyether surfactant of examples 1-4;
FIG. 4 shows the volume fractions of example 1 are a: 75%, b: 80%, c: 85% and d: macroscopic photographs of a Pickering high internal phase emulsion stabilized with dehydroabietic polyether inorganic particles at 90% n-hexadecane;
FIG. 5 shows the volume fractions of example 1 are a: 75%, b: 80%, c: 85% and d: confocal microscope and common optical microscope pictures of a Pickering high internal phase emulsion stabilized with dehydroabietic polyether inorganic particles under 90% n-hexadecane conditions;
FIG. 6 is a stress-scanned viscoelasticity curve of a Pickering high internal phase emulsion stabilized by dehydroabietic polyether inorganic particles in example 1 with n-hexadecane at 75%, 80%, 85% and 90% volume fractions, respectively;
fig. 7 is a viscoelastic plot of frequency scans of a Pickering high internal phase emulsion stabilized by dehydroabietic polyether inorganic particles under n-hexadecane conditions at 75%, 80%, 85% and 90% volume fractions for example 1, respectively.
FIG. 8 is a photomicrograph of Pickering high internal phase emulsions stabilized with inorganic particles of dehydroabietic polyether as in examples 2-4
FIG. 9 is an optical microscope photograph of Pickering high internal phase emulsions stabilized with inorganic particles of dehydroabietic polyether of examples 2-4;
wherein DP-400, DP-800, DP-1000, DP-1500 and DP-2000 respectively represent the molecular weights of polyethylene glycol used for synthesizing the dehydrogenated rosin polyether surfactant, and are respectively 400, 800, 1000, 1500 and 2000.
Detailed Description
The invention prepares a dehydrogenated rosin polyether surfactant by polymerizing dehydrogenated rosin and polyethylene glycol, and uses the dehydrogenated rosin polyether surfactant and inorganic particles together for preparing Pickering high internal phase emulsion which can be stable under the conditions of low dehydrogenated rosin polyether surfactant concentration and low inorganic particle concentration and has an internal phase with a very high volume ratio. The technical scheme of the invention is further illustrated by the following specific examples.
Example 1
This example prepares a dehydrorosin polyether surfactant and combines it with silica particles to make a Pickering high internal phase emulsion.
The preparation method of the dehydrogenated rosin polyether surfactant comprises the following steps:
(1) and mixing the dehydrogenated rosin with an acylating agent, and then carrying out acylation reaction to obtain the acylated rosin.
Specifically, 3g (10mmol) of dehydrorosin was dissolved in dichloromethane, 1.40g (11mmol) of oxalyl chloride was added dropwise, acylation reaction was carried out at 45 ℃ for 5 hours, and after completion of the reaction, the reaction system was subjected to reduced pressure distillation to remove excess oxalyl chloride, to obtain an acylated rosin.
(2) Polyethylene glycol and an initiator are added into the acylated rosin to carry out polymerization reaction to obtain the dehydrogenated rosin polyether surfactant.
Specifically, the acylated rosin in the step (1) is dissolved in 50mL of dichloromethane, 11mmol of polyethylene glycol (Mn ═ 800) and 1.11g (11mmol) of triethylamine are added, polymerization reaction is carried out at 40 ℃ for 12h, and finally the mixture is purified by column chromatography to obtain the dehydrorosin polyether surfactant.
The synthetic route of the reaction is as follows:
The method for preparing the Pickering high internal phase emulsion by using the dehydroabietic polyether surfactant comprises the following steps:
1) dispersing the dehydrogenated rosin polyether surfactant and the inorganic particles into an aqueous solution to obtain a water phase with the mass concentration of the dehydrogenated rosin polyether surfactant being 0.01-1% and the mass concentration of the inorganic particles being 0.18-1.5%.
Specifically, a dehydrogenated rosin polyether surfactant having a mass fraction (referring to a mass fraction in an aqueous phase) of 0.1% and 1 μm silica inorganic particles having a mass fraction of 0.54% were dispersed in an aqueous solution to form an aqueous phase.
2) Adding an oil phase with the volume fraction of 75-90% relative to the water phase into the water phase, and shearing and emulsifying to obtain the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles.
Specifically, n-hexadecane as an oil phase was added to the aqueous phase in step 1) in a volume fraction of 75% relative to the aqueous phase, and the mixture of the oil phase and the aqueous phase was emulsified for 3min using an IKA T18 high speed shearing machine at a rotation speed of 15000rpm to obtain a Pickering high internal phase emulsion in which the dehydroabietyl polyether inorganic particles were stabilized.
Keeping other conditions unchanged, and adjusting the volume fraction of the n-hexadecane to 80%, 85% or 90% to prepare the corresponding Pickering high internal phase emulsion with stable dehydrogenated rosin polyether inorganic particles.
Example 2
This example prepares a dehydrorosin polyether surfactant and combines it with zinc oxide particles to make a Pickering high internal phase emulsion.
The preparation method of the dehydrogenated rosin polyether surfactant comprises the following steps:
(1) 3g (10mmol) of dehydrogenated rosin is dissolved in dichloromethane, 1.40g (11mmol) of oxalyl chloride is added dropwise, acylation reaction is carried out at 35 ℃ for 8h, and after the reaction is finished, the reaction system is subjected to reduced pressure distillation to remove excessive oxalyl chloride, so as to obtain the acylated rosin.
(2) And (2) dissolving the acylated rosin in the step (1) in 50mL of dichloromethane, adding 11mmol of polyethylene glycol (Mn ═ 400) and 1.11g (11mmol) of triethylamine, carrying out polymerization reaction at 50 ℃ for 10h, and finally purifying by a column to obtain the dehydrorosin polyether surfactant.
The chemical formula of the obtained dehydrogenated rosin polyether surfactant is as follows:
The method for preparing the Pickering high internal phase emulsion by using the dehydroabietic polyether surfactant comprises the following steps:
1) a dehydrogenated rosin polyether surfactant with a mass fraction (mass fraction in the aqueous phase) of 0.01% and 1 μm zinc oxide inorganic particles with a mass fraction of 0.18% were dispersed in an aqueous solution to form an aqueous phase.
2) Adding n-hexadecane with the volume fraction of 85 percent relative to the water phase into the water phase in the step 1) as an oil phase, and emulsifying the mixture of the oil phase and the water phase for 2min by using an IKA T18 high-speed shearing machine at the rotating speed of 20000rpm to obtain the Pickering high internal phase emulsion with stable dehydroabietyl polyether inorganic particles.
Example 3
This example prepares a dehydrorosin polyether surfactant and combines it with titanium oxide particles to make a Pickering high internal phase emulsion.
The preparation method of the dehydrogenated rosin polyether surfactant comprises the following steps:
(1) 3g (10mmol) of dehydrogenated rosin is dissolved in dichloromethane, 1.40g (11mmol) of oxalyl chloride is added dropwise, acylation reaction is carried out at 25 ℃, the reaction time is 10 hours, and after the reaction is finished, the reaction system is subjected to reduced pressure distillation to remove excessive oxalyl chloride, so as to obtain the acylated rosin.
(2) And (2) dissolving the acylated rosin in the step (1) in 50mL of dichloromethane, adding 11mmol of polyethylene glycol (Mn 1000) and 1.11g (11mmol) of triethylamine, carrying out polymerization reaction at 60 ℃ for 7h, and finally purifying by a column to obtain the dehydrorosin polyether surfactant.
The chemical formula of the obtained dehydrogenated rosin polyether surfactant is as follows:
The method for preparing the Pickering high internal phase emulsion by using the dehydroabietic polyether surfactant comprises the following steps:
1) a dehydrogenated rosin polyether surfactant with a mass fraction (mass fraction in the aqueous phase) of 1% and 3 μm titanium oxide inorganic particles with a mass fraction of 1.5% were dispersed in an aqueous solution to form an aqueous phase.
2) Adding normal hexane with the volume fraction of 85% relative to the water phase into the water phase in the step 1) as an oil phase, and emulsifying the mixture of the oil phase and the water phase for 4min by using an IKA T18 high-speed shearing machine at the rotating speed of 20000rpm to obtain the Pickering high-internal-phase emulsion with stable dehydroabietic polyether inorganic particles.
Example 4
This example prepares a dehydroabietic polyether surfactant and combines it with alumina particles to make a Pickering high internal phase emulsion.
The preparation method of the dehydrogenated rosin polyether surfactant comprises the following steps:
(1) 3g (10mmol) of dehydrogenated rosin is dissolved in dichloromethane, 1.40g (11mmol) of oxalyl chloride is added dropwise, acylation reaction is carried out at 25 ℃, the reaction time is 10 hours, and after the reaction is finished, the reaction system is subjected to reduced pressure distillation to remove excessive oxalyl chloride, so as to obtain the acylated rosin.
(2) And (2) dissolving the acylated rosin in the step (1) in 50mL of dichloromethane, adding 11mmol of polyethylene glycol (Mn is 1500) and 1.11g (11mmol) of triethylamine, carrying out polymerization reaction at 60 ℃ for 7h, and finally purifying by a column to obtain the dehydrorosin polyether surfactant.
The chemical formula of the obtained dehydrogenated rosin polyether surfactant is as follows:
If other preparation conditions are kept unchanged, the molecular weight of the polyethylene glycol is replaced by 2000, and the dehydrogenated rosin polyether surfactant with n of 43-46 can be prepared.
The method for preparing the Pickering high internal phase emulsion by using the dehydroabietic polyether surfactant comprises the following steps:
1) a dehydrogenated rosin polyether surfactant with a mass fraction (mass fraction in an aqueous phase) of 1% and 10nm alumina inorganic particles with a mass fraction of 0.018% were dispersed in an aqueous solution to form an aqueous phase.
2) Adding 85% of n-heptane (or n-decane, toluene and liquid paraffin ethyl acetate) relative to the volume fraction of the water phase into the water phase in the step 1) as an oil phase, and emulsifying the mixture of the oil phase and the water phase by using an IKA T18 high-speed shearing machine for 3min at a rotating speed of 25000rpm to obtain the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles.
Characterization and testing were performed on the dehydroabietic polyether surfactant prepared in examples 1 to 4 and the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles, and the results were as follows:
(1) dehydrogenated rosin polyether surfactant performance
The nuclear magnetic hydrogen spectrum of the dehydrogenated rosin polyether surfactant prepared in example 1 is shown in FIG. 1, and the chemical reaction is carried outAt the position of 3.65ppm, is a repeating unit-CH of the polyether surfactant2-CH2The corresponding hydrogen peak on the-O-with a chemical shift of 4.2ppm being the surfactant-COO-CH2The corresponding hydrogen peak above. The infrared spectra of the dehydrorosin polyether surfactant and the dehydrorosin of examples 1 to 4 are shown in fig. 2. FIG. 2 shows that the peak patterns of the dehydro rosin polyether surfactants of examples 1-4 compared to the peak patterns of dehydro rosin were at 1692cm-1The characteristic peak of carbonyl in carboxyl is converted into 1724cm-1Carbonyl peak in ester group. And (5) according to a nuclear magnetic hydrogen spectrum and an infrared spectrogram, the dehydrorosin and the polyethylene glycol are esterified.
The gamma-logc curves of the dehydrogenated rosin polyether surfactants of examples 1-4 dissolved in deionized water are shown in fig. 3, and the critical micelle concentrations and surface tensions are shown in table 1. Fig. 3 and table 1 reflect that as the molecular weight of the dehydroabietic polyether surfactant is increased, the corresponding Critical Micelle Concentration (CMC) is increased and then decreased, and the surface tension γ after reaching the CMC is increasedCMCThe surface tension of the dehydrogenated rosin polyether surfactant can be effectively reduced, and the surface tension of the dehydrogenated rosin polyether surfactant in example 1 is most reduced.
TABLE 1 Critical Micelle Concentration (CMC) and surface tension γ of dehydrorosin polyether surfactantsCMC
| CMC(mmol/L) | γCMC(mN/m) | |
| DP-400 | 0.035 | 38.8 |
| DP-800 | 0.045 | 37.2 |
| DP-1000 | 0.039 | 38.1 |
| DP-1500 | 0.016 | 41.2 |
| DP-2000 | 0.013 | 41.8 |
(2) Pickering high internal phase emulsion stabilized by dehydroabietic polyether inorganic particles
Macro-photographs of Pickering high internal phase emulsions stabilized with dehydroabietic polyether inorganic particles prepared under different volume fractions of n-hexadecane as in example 1 are shown in FIG. 4, and corresponding confocal microscopy (CLSM) and common light microscopy pictures are shown in FIG. 5, wherein a1～a3、b1～b3、c1～c3And d1～d3Is a confocal microscope picture, a4、b4c4And d4Is a common optical microscope picture. As can be seen from fig. 4, as the volume fraction of the internal phase (n-hexadecane) increased from 75% to 90%, the emulsion changed from flowable to gel-like, indicating that the viscosity continued to increase over the course of time. FIG. 5 is a confocal microscope picture in which the internal phase is stained blue with pyrene; the water phase is dyed by rhodamine B and is red, and as can be seen from figure 5, the type of the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles is O/W type, and emulsion droplets are stacked layer by layer, which is also the viscosity of the emulsionFor a large reason.
In addition, the viscoelastic curves of the stress scan and the frequency scan of the Pickering high internal phase emulsion stabilized by dehydroabietic polyether inorganic particles prepared under the condition of different volume fractions of n-hexadecane in example 1 are shown in fig. 6 and fig. 7, respectively. As can be seen in fig. 6, with increasing oil phase fraction, there is a corresponding increase in both G 'and G ", with G' being greater than G" before the crossover point, indicating that the emulsion exhibits elastic characteristics, and G "being greater than G" after the crossover point, indicating that under high stress, the emulsion changes from a gel-like to a flowable fluid, indicating that the emulsion exhibits viscous characteristics. As can be seen from fig. 7, G' is always greater than G "throughout the frequency sweep interval and increases, indicating that the resulting high internal phase emulsion exhibits primarily elastic properties and the emulsion is relatively stable.
In examples 2 to 4, the macro-and microphotographs of Pickering high internal phase emulsions constructed by the dehydroabietic polyether surfactant with different concentrations and different molecular weights and inorganic particles with different types, concentrations and particle sizes are shown in fig. 8 and 9, respectively. From the figure, it can be seen that in the concentration range of 0.01% -1%, the dehydroabietic polyether can form stable Pickering high internal phase emulsion with zinc oxide, aluminum oxide and titanium oxide with different particle sizes and concentrations, which shows that the system has universality. And it was found from the photomicrograph that the emulsions did not differ greatly in particle size and piled up layer by layer.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A dehydrogenated rosin polyether surfactant is characterized in that: the structural formula is as follows:
2. A preparation method of a dehydrogenated rosin polyether surfactant is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the dehydrogenated rosin with an acylating agent and then carrying out an acylation reaction to obtain an acylated rosin;
(2) adding polyethylene glycol and an initiator into the acylated rosin to carry out polymerization reaction to obtain
Wherein n is more than or equal to 8 and less than or equal to 46.
3. The method for preparing a dehydrogenated rosin polyether surfactant as claimed in claim 2, wherein: the molecular weight of the polyethylene glycol is 400-2000.
4. The method for preparing a dehydrogenated rosin polyether surfactant as claimed in claim 2, wherein: in the step (1), the temperature of the acylation reaction is 25-45 ℃.
5. The method for preparing a dehydrogenated rosin polyether surfactant as claimed in claim 2, wherein: in the step (2), the polymerization reaction temperature is 40-60 ℃.
6. A preparation method of Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles is characterized by comprising the following steps: the method comprises the following steps:
1) dispersing the dehydrorosin polyether surfactant and the inorganic particles of claim 1 in water to produce an aqueous phase having a mass concentration of the dehydrorosin polyether surfactant of 0.01% to 1% and a mass concentration of the inorganic particles of 0.18% to 1.5%;
2) adding an oil phase with the volume fraction of 75-90% relative to the water phase into the water phase, and shearing and emulsifying to obtain the Pickering high internal phase emulsion with stable dehydroabietic polyether inorganic particles.
7. The method of preparing a Pickering high internal phase emulsion stabilized with dehydroabietic polyether inorganic particles as claimed in claim 6, wherein: the particle size of the inorganic particles is 10 nm-3 mu m.
8. The method of preparing a Pickering high internal phase emulsion stabilized with dehydroabietic polyether inorganic particles as claimed in claim 7, wherein: the inorganic particles are selected from any one of silicon oxide, zinc oxide, titanium oxide, and aluminum oxide.
9. The method of preparing a Pickering high internal phase emulsion stabilized with dehydroabietic polyether inorganic particles as claimed in claim 6, wherein: the oil phase is at least one selected from n-hexane, n-heptane, n-decane, n-hexadecane, toluene, liquid paraffin and ethyl acetate.
10. A Pickering high internal phase emulsion stabilized by dehydroabietic polyether inorganic particles is characterized in that: prepared by the preparation method of any one of claims 6 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398836A (en) * | 2021-07-08 | 2021-09-17 | 西南石油大学 | Particle-stable high internal phase switching emulsion, preparation method and particle recovery method |
| CN114479520A (en) * | 2021-12-28 | 2022-05-13 | 广东省科学院化工研究所 | Modified inorganic particle, preparation method thereof and application thereof in super-hydrophobic material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02263595A (en) * | 1989-04-04 | 1990-10-26 | Asahi Chem Res Lab Ltd | Flux composition for soldering |
| CN102039099A (en) * | 2010-11-08 | 2011-05-04 | 中国林业科学研究院林产化学工业研究所 | Self-emulsification rosinyl surfactant emulsion and preparation method thereof |
| JP2011245399A (en) * | 2010-05-25 | 2011-12-08 | Mikuni Color Ltd | Dispersant for dispersing sea shell powder, and sea shell powder dispersion |
| CN107281975A (en) * | 2017-03-17 | 2017-10-24 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl polyester macro-molecular surfactant and preparation method |
-
2019
- 2019-12-20 CN CN201911334592.XA patent/CN111116896A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02263595A (en) * | 1989-04-04 | 1990-10-26 | Asahi Chem Res Lab Ltd | Flux composition for soldering |
| JP2011245399A (en) * | 2010-05-25 | 2011-12-08 | Mikuni Color Ltd | Dispersant for dispersing sea shell powder, and sea shell powder dispersion |
| CN102039099A (en) * | 2010-11-08 | 2011-05-04 | 中国林业科学研究院林产化学工业研究所 | Self-emulsification rosinyl surfactant emulsion and preparation method thereof |
| CN107281975A (en) * | 2017-03-17 | 2017-10-24 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl polyester macro-molecular surfactant and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| PETER S. PIISPANEN等: "Synthesis and surface measurements of surfactants derived from dehydroabietic acid", 《JOURNAL OF SURFACTANTS AND DETERGENTS》 * |
| 张雄等: "基于松香聚醚类绿色表面活性剂构建高内相乳液", 《中国化学会第17届胶体与界面化学学术会议论文（摘要）集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398836A (en) * | 2021-07-08 | 2021-09-17 | 西南石油大学 | Particle-stable high internal phase switching emulsion, preparation method and particle recovery method |
| CN114479520A (en) * | 2021-12-28 | 2022-05-13 | 广东省科学院化工研究所 | Modified inorganic particle, preparation method thereof and application thereof in super-hydrophobic material |
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