CN109880016B - Method for continuously preparing water-in-oil type high internal phase emulsion and polymer porous material - Google Patents
Method for continuously preparing water-in-oil type high internal phase emulsion and polymer porous material Download PDFInfo
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Abstract
The present invention relates to a process for the continuous preparation of water-in-oil high internal phase emulsions and polymeric porous materials. Taking a solution obtained by dissolving an emulsifier in a hydrophobic monomer as an oil phase; taking an aqueous solution containing electrolyte and an initiator as a water phase; continuously adding the oil phase and the water phase into a double-screw extruder respectively, and fully emulsifying the oil phase and the water phase to form emulsion through the shearing action of the double screws; after the oil phase and the water phase are fully emulsified to form emulsion, the initiator initiates hydrophobic monomers in the emulsion to obtain the porous polymer material with a pore structure and adjustable pore structure morphology. Compared with the prior art, the method is simple and feasible, can be used for continuously producing the high internal phase emulsion, and can obtain the porous material with the special pore structure.
Description
Technical Field
The invention belongs to the technical field of emulsion preparation and porous material preparation, and particularly relates to a method for continuously preparing water-in-oil type high internal phase emulsion and a polymer porous material.
Background
High internal phase emulsions, i.e., emulsions in which the volume fraction of the dispersed phase based on the total volume of the emulsion is greater than or equal to 74.05%. It has been widely used in the fields of food, fuel, oil recovery, cosmetics and porous materials. High internal phase emulsions are typically stabilized by nonionic emulsifiers that comprise 5-50% of the continuous phase. Nanoparticle-stabilized high internal phase emulsions have also been recently reported. High internal phase emulsions are typically prepared by gradually adding the dispersed phase dropwise to the emulsifying continuous phase under the action of a stabilizer. The emulsification method comprises mechanical stirring, magnetic stirring, shearing emulsification, ultrasonic emulsification and the like. However, these emulsification methods are intermittent, i.e. the emulsion is prepared from one kettle or one bottle, which is not favorable for the stability of the emulsion product performance. So far, the continuous large-scale preparation of emulsion has become a difficult problem to be solved urgently in the technical field of emulsion.
In recent years, polymer porous materials prepared by a high internal phase emulsion templating method have attracted considerable interest in a variety of fields, due to their unique pore structure, high porosity, low density, etc., and they can be used not only as low dielectric constant substrates in the microelectronics industry, scaffolds for 3D cell culture in tissue engineering, catalysts in synthetic chemistry, and supports for reactants, etc., but also as templates for the preparation of inorganic porous materials. In the process of preparing the porous material by the high internal phase emulsion template method, the stability of the emulsion and the performance unification among emulsion product batches are very important.
The stability of high internal phase emulsions is a concern and is affected by a number of factors. The influence of emulsion phase components, emulsifier properties and amounts, emulsion dispersed phase volume fraction, preparation temperature, electrolyte concentration, etc. on the formation and stability of emulsions has been reported so far. It has been shown that in order to stabilize high internal phase emulsions, emulsifiers must be able to rapidly adsorb to the liquid-liquid interface, form a firm interfacial film, and effectively reduce the interfacial tension at the two phase interface in the emulsion. The stability of the emulsion is kinetically stable and is stabilized by the repulsive forces between the droplets of the internal phase. Nonionic emulsifiers are generally believed to achieve HIPE stabilization through steric repulsion benefits. When stable water-in-oil high internal phase emulsions are to be prepared, a low hydrophilic-lipophilic balance nonionic emulsifier is generally required, such as sorbitol monooleate (Span80, HLB ═ 4.3) and the like. In addition, electrolytes also play an important role in the stability of high internal phase emulsions. The presence of the electrolyte may reduce the interaction of the emulsifiers with the aqueous solution, thereby increasing the interaction between the emulsifiers and making their arrangement more orderly at the water-oil interface. Therefore, the addition of the electrolyte can enhance the strength of the water-oil interface film, increase the elastic modulus and apparent yield stress of the emulsion and further improve the stability of the emulsion. On the other hand, electrolytes also improve the stability of high internal phase emulsions by reducing the solubility of aqueous solutions in the oil phase, thereby inhibiting the Ostwald ripening effect. Although the research on high internal phase emulsion has been more, the emulsification method is still limited to intermittent production methods such as mechanical stirring, magnetic stirring, shear emulsification, ultrasonic emulsification, etc., which are not favorable for the stability of the properties of the emulsion product, and therefore, continuous large-scale emulsion preparation technology is still under development.
Chinese patent CN102838774B discloses a method for preparing a low-density polymer porous material by taking a water-in-oil type high internal phase emulsion with stable styrene, acrylic acid and methyl methacrylate triblock copolymer macromolecules as a precursor and adopting a physical mode of freeze drying. The method comprises the following steps: adding a triblock copolymer of styrene, acrylic acid and methyl methacrylate into an organic solvent, stirring and dissolving to form a polymer solution, taking the solution as an oil phase, taking an electrolyte aqueous solution with a certain concentration as a water phase, slowly dripping into the oil phase, forming a water-in-oil type high internal phase emulsion with stable polymer macromolecules under the action of mechanical stirring, standing at room temperature for a period of time, directly freezing the emulsion by using liquid nitrogen to fix the appearance, and then freeze-drying to remove water and the organic solvent to form the low-density polymer porous material.
Chinese patent CN102838773B discloses a method for preparing an ultra-low density polymer porous material by using a water-in-oil type high internal phase emulsion stabilized by styrene, acrylic acid and methyl methacrylate triblock copolymer nanoparticles as a precursor and adopting a physical freeze drying mode. The method comprises the following steps: adding electrolyte into the styrene, acrylic acid and methyl methacrylate triblock copolymer nanoparticle aqueous dispersion, stirring and dissolving the electrolyte to obtain a water phase, slowly pouring the water phase into an oil phase, and forming the water-in-oil type high internal phase emulsion under the action of magnetic stirring. After the high internal phase emulsion is allowed to stand at room temperature for a period of time, it is freeze-dried to form a low density polymeric porous material.
Chinese patent CN102391416A discloses a method for obtaining a hydrophilic polymer porous material by using inorganic nano-particle titanium dioxide to stabilize oil-in-water type high internal phase emulsion and using the emulsion as a template for polymerization. The method comprises the following steps: adding water-soluble monomer, water-soluble cross-linking agent, electrolyte and initiator into the aqueous dispersion of nano titanium dioxide, stirring and dissolving, then dripping hydrophobic organic solvent, and stirring to form oil-in-water emulsion. Heating to initiate the monomer reaction in the emulsion to obtain the hydrophilic polymer porous material.
The above three patents are related patents on the preparation of water-in-oil type high internal phase emulsion and the preparation of polymer porous material, which were previously studied by the present inventors, and the emulsification methods of the above three patents are still limited to intermittent production methods, and the continuous large-scale preparation of emulsion is impossible.
On the other hand, since 1935, the same-direction and different-direction twin-screw extruders were first developed by Roberto Colombo and Carlo Pasqutti in Italy for over 80 years, and the twin-screw extruders have been developed and widely used in polymer processing industry and other industries. Although twin screw extrusion has been widely used in the fields of polymer processing and modification, its application in the field of emulsion preparation has not been reported.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art by providing a method for continuously preparing a water-in-oil type high internal phase emulsion and a polymer porous material.
The invention uses a double-screw extruder to realize the continuous preparation of the water-in-oil type high internal phase emulsion and the continuous preparation of the polymer porous material.
The purpose of the invention can be realized by the following technical scheme:
the invention firstly provides a method for preparing water-in-oil type high internal phase emulsion by continuous extrusion, which comprises the following steps:
taking a solution obtained by dissolving an emulsifier in a hydrophobic monomer as an oil phase;
taking an aqueous solution containing electrolyte as an aqueous phase;
and continuously adding the oil phase and the water phase into a feed inlet of a double-screw extruder respectively, fully mixing the water phase and the oil phase through the shearing action of the double screws, emulsifying, and obtaining the water-in-oil type high internal phase emulsion at a discharge port.
Further, the emulsifier is selected from one or more of the following: span80, Span60, polyglycerol alkenyl succinate or hypermer t 96.
Further, the hydrophobic monomer is selected from one or more of the following: styrene, divinylbenzene, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, tetradecyl acrylate, lauryl methacrylate, butyl acrylate, tetradecyl methacrylate, glycidyl methacrylate or ethylene glycol dimethacrylate.
Further, the electrolyte is selected from one or two of sodium chloride or calcium chloride.
Further, the mass fraction of the emulsifier in the oil phase is 5-30%.
Further, the mass fraction of the electrolyte in the water phase is 0.5-3%.
Further, the oil phase and the water phase are mixed according to a volume ratio of 1: 40-1: the ratio of 3 was continuously fed to the twin-screw extruder, respectively.
Further, the screw rotating speed of the double-screw extruder is 50-350 revolutions per minute, and the temperature of the oil phase and the water phase in the double-screw extruder is controlled to be 20-50 ℃, preferably 30-40 ℃.
Further, the water phase also contains an initiator, the initiator is selected from one or two of potassium persulfate or ammonium persulfate, and the using amount of the initiator is 1-3% of the mass of the hydrophobic monomer.
The initiator is added to ensure that the final water-in-oil type high internal phase emulsion contains the initiator, so that under proper initiation conditions, the initiator can be used for initiating the hydrophobic monomer in the emulsion, and further the polymer porous material with a pore structure and adjustable pore structure can be obtained.
The invention also provides a preparation method of the polymer porous material, which comprises the following steps:
taking a solution obtained by dissolving an emulsifier in a hydrophobic monomer as an oil phase;
taking an aqueous solution containing electrolyte and an initiator as a water phase;
continuously adding the oil phase and the water phase into a feed inlet of a double-screw extruder respectively, fully mixing the water phase and the oil phase through the shearing action of double screws, emulsifying, and obtaining the water-in-oil type high internal phase emulsion at a discharge port;
after the oil phase and the water phase are fully emulsified to form emulsion, the initiator initiates hydrophobic monomers in the emulsion to obtain the porous polymer material with adjustable pore structure.
Further, the initiator is selected from one or two of potassium persulfate or ammonium persulfate, and the using amount of the initiator is 1-3% of the mass of the hydrophobic monomer.
Further, the conditions for the initiator to initiate the hydrophobic monomer in the emulsion to obtain the polymer porous material are as follows: heating the obtained emulsion to 60-90 ℃, preferably 70-80 ℃.
And initiating polymerization of hydrophobic monomers in the high internal phase emulsion, reacting to obtain a white solid, washing the solid product by using leaching solvent water, ethanol or a mixture of water and ethanol, and drying to obtain the porous material with a certain pore diameter.
Further, the emulsifier is selected from one or more of the following: span80, Span60, polyglycerol alkenyl succinate or hypermer t 96.
Further, the hydrophobic monomer is selected from one or more of the following: styrene, divinylbenzene, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, tetradecyl acrylate, lauryl methacrylate, butyl acrylate, tetradecyl methacrylate, glycidyl methacrylate or ethylene glycol dimethacrylate.
Further, the electrolyte is selected from one or two of sodium chloride or calcium chloride.
Further, the mass fraction of the emulsifier in the oil phase is 5-30%.
Further, the mass fraction of the electrolyte in the water phase is 0.5-3%.
Further, the oil phase and the water phase are mixed according to a volume ratio of 1: 40-1: the ratio of 3 was continuously fed to the twin-screw extruder, respectively.
Further, the screw rotating speed of the double-screw extruder is 50-350 revolutions per minute, and the temperature of the oil phase and the water phase in the double-screw extruder is controlled to be 20-50 ℃, preferably 30-40 ℃.
The invention continuously obtains the high internal phase emulsion with adjustable dispersed phase droplet size by adjusting the screw rotation speed and the barrel temperature. The method is simple and feasible, is suitable for continuous production, and can obtain the high internal phase emulsion with adjustable dispersed phase droplet size and distribution.
The size of the dispersed phase droplets of the high internal phase emulsion is observed by an optical microscope, the morphology of the bulk polymer porous material is observed by a scanning electron microscope (SEM, S-3400N, JEOL), and the density is measured by a digital display solid densitometer (EDS-300). And respectively measuring the mass and the volume of the block polymer open-pore material by using a balance and a vernier caliper, and calculating the porosity.
The emulsion obtained by the method has controllable properties such as the size of dispersed phase droplets, the pore diameter of the porous material, the density of the porous material and the like.
The invention utilizes the characteristics of the double-screw extruder such as good charging performance, mixing plasticizing performance, extrusion stability and the like, and combines the forward conveying characteristic of the double-screw extruder to the material, and the double-screw extruder is firstly used for the continuous preparation of the emulsion, in particular to the continuous emulsification process of the high internal phase emulsion.
Compared with the prior art, the method is simple and feasible, is suitable for continuously producing the high internal phase emulsion and the polymer porous material thereof, and simultaneously the double-screw extruder can provide sufficient dispersion and distribution mixing, better temperature control and good self-cleaning property, so that the water-in-package type high internal phase emulsion and the polymer porous material prepared by the method have higher quality and better process stability.
Drawings
FIG. 1 is an optical microscope photograph of the emulsion obtained in example 1;
FIG. 2 is a scanning electron micrograph of the porous material obtained in example 1;
FIG. 3 is an optical microscope photograph of the emulsion obtained in example 2;
FIG. 4 is a scanning electron micrograph of the porous material obtained in example 2;
FIG. 5 is an optical microscope photograph of the emulsion obtained in example 3;
FIG. 6 is a scanning electron micrograph of a porous material obtained in example 3;
FIG. 7 is an optical microscope photograph of the emulsion obtained in example 4;
FIG. 8 is a SEM image of the porous material obtained in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
100 g of span80 are weighed out and added to a mixture of 1600 g of styrene and 400 g of divinylbenzene, the resulting organic solution being the oily phase. 300 g of sodium chloride and 100 g of potassium persulfate were weighed into 8000 g of distilled water, and the resulting solution was an aqueous phase. Heating the oil phase and the water phase to 30 ℃ respectively, and then mixing the oil phase and the water phase according to a volume ratio of 1: 3, the mixture is added into a double-screw extruder with the cylinder temperature set at 30 ℃ and the double-screw rotating speed of 350 revolutions per minute through a constant flow pump. After the water phase and the oil phase are sheared by the double screws, the high internal phase emulsion comes out from the discharge port of the extruder. Heating the high internal phase emulsion to 70 ℃, initiating polymerization of monomers in the high internal phase emulsion, reacting to obtain a white solid, washing the solid product with rinsing solvent water, ethanol or a mixture thereof, and drying to obtain the porous material with a certain pore diameter.
The size of the dispersed phase droplets of the high internal phase emulsion was observed by an optical microscope, and the optical microscope image of the high internal phase emulsion obtained in this example is shown in fig. 1, and it can be seen from fig. 1 that the average diameter of the water-separated phase droplets of the emulsion obtained in this example is 48 μm.
The morphology of the porous material is observed by using a scanning electron microscope (SEM, S-3400N, JEOL), the scanning electron microscope image of the porous material obtained in the embodiment is shown in FIG. 2, and the porous material obtained in the embodiment can be obtained by calculation according to FIG. 2, and the pore diameter of the porous material is 47 micrometers.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the porosity was calculated, and the porosity of the porous material obtained in this example was 77%.
Example 2
600 g of span60 is weighed and added into a mixture of 1600 g of 2-hydroxyethyl methacrylate and 400 g of ethylene glycol dimethacrylate, and the obtained organic solution is an oil phase. 300 g of sodium chloride and 300 g of potassium persulfate were weighed into 10000 g of distilled water, and the resulting solution was an aqueous phase. Heating the oil phase and the water phase to 30 ℃ respectively, and then mixing the oil phase and the water phase according to a volume ratio of 1: 4, and adding the mixture into a double-screw extruder with the cylinder temperature set at 30 ℃ and the double-screw rotating speed of 100 revolutions per minute through a constant flow pump. After the water phase and the oil phase are sheared by the double screws, the high internal phase emulsion comes out from the discharge port of the extruder. Heating the high internal phase emulsion to 70 ℃, initiating polymerization of monomers in the high internal phase emulsion, reacting to obtain a white solid, washing the solid product with rinsing solvent water, ethanol or a mixture thereof, and drying to obtain the porous material with a certain pore diameter.
The size of the dispersed phase droplets of the high internal phase emulsion was observed by an optical microscope, and the optical microscope image of the high internal phase emulsion obtained in this example is shown in fig. 3, and it can be seen from fig. 3 that the average diameter of the water-separated phase droplets of the emulsion obtained in this example is 25 μm.
The morphology of the porous material is observed by using a scanning electron microscope (SEM, S-3400N, JEOL), the scanning electron microscope image of the porous material obtained in the embodiment is shown in FIG. 4, and the porous material obtained in the embodiment can be obtained by calculation according to FIG. 4, and the pore diameter of the porous material is 27 micrometers.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the porosity was calculated, and the porosity of the porous material obtained in this example was 82%.
Example 3
200 g of polyglycerol alkenyl succinate and 100 g of Hypermer T96 were weighed into a mixture of 1600 g of 2-ethylhexyl acrylate and 400 g of divinylbenzene, and the resulting organic solution was the oil phase. 200 g of sodium chloride and 300 g of potassium persulfate were weighed into 10000 g of distilled water, and the resulting solution was an aqueous phase. Heating the oil phase and the water phase to 30 ℃ respectively, and then mixing the oil phase and the water phase according to a volume ratio of 1: 40, through a constant flow pump, into a twin-screw extruder with a barrel temperature set at 30 ℃ and a twin-screw speed of 150 rpm. After the water phase and the oil phase are sheared by the double screws, the high internal phase emulsion comes out from the discharge port of the extruder. Heating the high internal phase emulsion to 70 ℃, initiating polymerization of monomers in the high internal phase emulsion, reacting to obtain a white solid, washing the solid product with rinsing solvent water, ethanol or a mixture thereof, and drying to obtain the porous material with a certain pore diameter.
The size of the dispersed phase droplets of the high internal phase emulsion was observed by optical microscopy, and the optical microscopy image of the high internal phase emulsion obtained in this example is shown in FIG. 5, from which FIG. 5 it can be seen that the average diameter of the water-separated phase droplets of the emulsion obtained in this example is 74 microns.
The morphology of the porous material is observed by using a scanning electron microscope (SEM, S-3400N, JEOL), the scanning electron microscope image of the porous material obtained in the embodiment is shown in FIG. 6, and the porous material obtained in the embodiment can be obtained by calculation according to FIG. 6, and the pore diameter of the porous material is 68 micrometers.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the porosity was calculated, and the porosity of the porous material obtained in this example was 96%.
Example 4
400 g of span80 is weighed and added into a mixture of 1600 g of glycidyl methacrylate and 400 g of ethylene glycol dimethacrylate, and the obtained organic solution is an oil phase. 50 g of sodium chloride and 100 g of potassium persulfate were weighed into 10000 g of distilled water, and the resulting solution was an aqueous phase. Heating the oil phase and the water phase to 30 ℃ respectively, and then mixing the oil phase and the water phase according to a volume ratio of 1: 5, the mixture is added into a double-screw extruder with the cylinder temperature set at 30 ℃ and the double-screw rotating speed of 50 revolutions per minute through a constant flow pump. After the water phase and the oil phase are sheared by the double screws, the high internal phase emulsion comes out from the discharge port of the extruder. Heating the high internal phase emulsion to 70 ℃, initiating polymerization of monomers in the high internal phase emulsion, reacting to obtain a white solid, washing the solid product with rinsing solvent water, ethanol or a mixture thereof, and drying to obtain the porous material with a certain pore diameter.
The size of the dispersed phase droplets of the high internal phase emulsion was observed by an optical microscope, and the optical microscope image of the high internal phase emulsion obtained in this example is shown in fig. 7, and it can be seen from fig. 7 that the average diameter of the water-separated phase droplets of the emulsion obtained in this example is 30 μm.
The morphology of the porous material is observed by using a scanning electron microscope (SEM, S-3400N, JEOL), the scanning electron microscope image of the porous material obtained in the embodiment is shown in FIG. 8, and can be calculated according to FIG. 8, and the pore diameter of the obtained porous material is 32 microns.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the porosity was calculated, and the porosity of the porous material obtained in this example was 81%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. A process for preparing a water-in-oil high internal phase emulsion by continuous extrusion, comprising the steps of:
taking a solution obtained by dissolving an emulsifier in a hydrophobic monomer as an oil phase;
taking an aqueous solution containing electrolyte as an aqueous phase;
continuously adding the oil phase and the water phase into a double-screw extruder respectively, and fully emulsifying the oil phase and the water phase to form emulsion through the shearing action of the double screws;
the mass fraction of the emulsifier in the oil phase is 5-30%, the mass fraction of the electrolyte in the water phase is 0.5-3%, and the volume ratio of the oil phase to the water phase is 1: 40-1: 3 are respectively and continuously added into a double-screw extruder;
the screw rotating speed of the double-screw extruder is 50-350 revolutions per minute, and the temperature of the oil phase and the water phase in the double-screw extruder is controlled to be 20-50 ℃.
2. The continuous extrusion process for preparing a water-in-oil high internal phase emulsion according to claim 1, wherein the emulsifier is selected from one or more of the following: span80, Span60, polyglycerol alkenyl succinate or hypermer t 96;
the hydrophobic monomer is selected from one or more of the following substances: styrene, divinylbenzene, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, tetradecyl acrylate, lauryl methacrylate, butyl acrylate, tetradecyl methacrylate, glycidyl methacrylate or ethylene glycol dimethacrylate.
3. A method for preparing a polymer porous material is characterized in that,
taking a solution obtained by dissolving an emulsifier in a hydrophobic monomer as an oil phase;
taking an aqueous solution containing electrolyte and an initiator as a water phase;
continuously adding the oil phase and the water phase into a double-screw extruder respectively, and fully emulsifying the oil phase and the water phase to form emulsion through the shearing action of the double screws;
after the oil phase and the water phase are fully emulsified to form emulsion, initiating a hydrophobic monomer in the emulsion by an initiator to obtain a porous polymer material with a pore structure and an adjustable pore structure;
the mass fraction of the emulsifier in the oil phase is 5-30%, the mass fraction of the electrolyte in the water phase is 0.5-3%, and the volume ratio of the oil phase to the water phase is 1: 40-1: 3, continuously adding the initiator into a double-screw extruder respectively, wherein the using amount of the initiator is 1-3% of the mass of the hydrophobic monomer;
the screw rotating speed of the double-screw extruder is 50-350 revolutions per minute, and the temperature of the oil phase and the water phase in the double-screw extruder is controlled to be 20-50 ℃.
4. The method for preparing a polymer porous material according to claim 3, wherein the initiator is one or two selected from potassium persulfate and ammonium persulfate;
the electrolyte is selected from one or two of sodium chloride or calcium chloride;
the emulsifier is selected from one or more of the following substances: span80, Span60, polyglycerol alkenyl succinate or hypermer t 96;
the hydrophobic monomer is selected from one or more of the following substances: styrene, divinylbenzene, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, tetradecyl acrylate, lauryl methacrylate, butyl acrylate, tetradecyl methacrylate, glycidyl methacrylate or ethylene glycol dimethacrylate.
5. The method for preparing a polymer porous material according to claim 3, wherein the conditions for the initiator to initiate the hydrophobic monomer in the emulsion to obtain the polymer porous material are as follows: heating the obtained emulsion to 60-90 ℃.
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