CN113136173A - Bowl-shaped organic silicon thermal energy storage phase change microcapsule and preparation method thereof - Google Patents
Bowl-shaped organic silicon thermal energy storage phase change microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention provides a bowl-shaped organic silicon thermal energy storage phase change microcapsule and a preparation method thereof, relating to the technical field of nano material preparation. The invention discloses a preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules, which comprises the following steps: adding an organosilane coupling agent into an acidic solution with a preset pH value, and mixing and reacting to obtain a first reaction solution; adding the oil phase solution dissolved with the phase-change material into the first reaction solution, and mixing to obtain a second reaction solution; and adding an alkali catalyst into the second reaction solution to react to obtain the bowl-shaped organic silicon thermal energy storage phase change microcapsule. The preparation method is an organic whole, and has the advantages of simple process, mild reaction conditions (only stirring or ultrasound at 50-70 ℃ and the like), low cost of preparation raw materials and good repeatability.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a bowl-shaped organic silicon thermal energy storage phase change microcapsule and a preparation method thereof.
Background
In recent years, increasing the energy utilization rate has been receiving increasing attention. The heat energy storage technology can solve the contradiction that the heat energy utilization is not matched in time and space, and effectively improves the heat energy utilization rate. The phase-change energy storage has the advantages of stable temperature, large energy storage density and the like in the phase-change process, and is the main mode of heat energy storage at present.
Among various phase change types, solid-liquid phase change has received wide attention due to small volume change, large enthalpy value, good energy storage, and wide phase change temperature range. However, the problem of melt flow must be overcome by container packaging during use, so that the use of the container in narrow spaces such as surfaces of precision instruments, aerospace equipment, coatings and the like is greatly limited. In order to solve the problem, researchers microcapsule the phase-change material, and select a proper wall material to coat the phase-change material, during the phase-change process, the phase-change material in the microcapsule is subjected to solid-liquid phase transition, but the appearance of the microcapsule is always in a solid state. The application range of the phase-change material is greatly widened by the microcapsule technology.
In the currently mainstream paraffin phase change microcapsules, organic high molecular polymers such as melamine-urea-formaldehyde (MUF) resin, organic silicon, acrylic-based polymer, peach gum/chitosan, gelatin/acacia, polyethylene diamine, polyethylene glycol and the like are commonly used as wall material materials. The organosilicon material as a wall material has the advantages of good stability, low toxicity, good biocompatibility and the like, and is widely applied and researched in recent years. In addition, the microcapsule can be further subjected to surface modification, modification and other treatments, so that the microcapsule has more functions by being connected with functional groups. For example, the surface of the organic silicon wall material is subjected to hole expansion to form a mesoporous structure, so that internal and external mass and heat transfer are facilitated, and the mass and heat transfer efficiency is improved; the microcapsule has responsiveness to external stimuli such as light, magnetism, pH and the like by connecting a specific group.
At present, the heat energy storage phase change microcapsule mainly takes a spherical structure as a main part, and other nanostructure types are few. Among various nano-structure types, the bowl-shaped structure not only inherits the advantages of a typical hollow structure, such as high specific surface area, low density, adjustable particle size aperture, large central cavity, permeable shell layer and the like, but also has low symmetry, a windowing structure and higher packing density. Under the same specific gravity, the bowl-shaped structure has stronger binding capacity with other substances compared with other nano-structure types, can greatly improve the volume bulk density while keeping a high specific surface, has larger contact area among particles, and can obviously improve the mass transfer effect.
The bowl-shaped structure composite material is mainly synthesized by a sol-gel method, a chemical vapor deposition method, an electrochemical deposition method, a solvothermal method and the like, and can be applied to multiple fields of lithium ion batteries, microwave absorption, water decomposition reaction, photocatalysis and the like. At present, few reports about bowl-shaped structure composite materials exist, and in the prior art, microspheres, metal salt and organic resin are added into a solvent, stirred and ultrasonically treated, then the product is ultrasonically etched and dried, and finally the product and sublimed sulfur are subjected to a vulcanization reaction under an inert atmosphere to obtain the bowl-shaped structure metal sulfide/carbon composite electrode material. The method can obtain the energy storage electrode with the bowl-shaped structure with large specific surface area, but the preparation process is relatively complex and is difficult to prepare in large batch. At present, functional monomers and cross-linking agents are introduced into a microgel system through the traditional free radical emulsion polymerization, and then the microgel system is adsorbed to the surfaces of different matrixes, and Bi is added3+And soaking in the metal ion solution, washing with deionized water, and annealing to obtain the microgel particles with bowl-shaped structures. The two methods are used for preparing the bowl-shaped structure nano-microspheres with simple structures. So far, the structure integrating the bowl-shaped structure, the energy storage phase change function and the microcapsule structure has less materials, and the preparation process is more complex if any, and the repeatability of the obtained result is poor.
Disclosure of Invention
An object of the first aspect of the present invention is to provide a method for preparing a bowl-shaped silicone thermal energy storage phase change microcapsule, which exploits a path for preparing a bowl-shaped silicone thermal energy storage phase change microcapsule in the prior art, and solves the problems in the prior art that the preparation process of the bowl-shaped silicone thermal energy storage phase change microcapsule is complicated, and the degree of depression of the prepared bowl-shaped silicone thermal energy storage phase change microcapsule is not adjustable.
The second aspect of the invention aims to provide a bowl-shaped organic silicon thermal energy storage phase change microcapsule.
Particularly, the invention provides a preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules, which comprises the following steps:
adding an organosilane coupling agent into an acidic solution with a preset pH value, and mixing and reacting to obtain a first reaction solution;
adding the oil phase solution dissolved with the phase-change material into the first reaction solution, and mixing to obtain a second reaction solution;
and adding an alkali catalyst into the second reaction solution to react to obtain the bowl-shaped organic silicon thermal energy storage phase change microcapsule.
Optionally, the organosilane coupling agent is selected from any one of Vinyltriethoxysilane (VTES), Phenyltriethoxysilane (PTES), Methacryloxypropyltrimethoxysilane (MPS).
Optionally, the process of adding the organosilane coupling agent into the acidic solution with the preset pH value for mixing reaction comprises:
adding an organosilane coupling agent into an acidic solution with a preset pH value, and stirring at the rotating speed of 200-1200 rpm for 0.5-24 h at the temperature of 50-70 ℃; the acid solution is an aqueous solution of glacial acetic acid, and the preset pH value is 3.0-6.0.
Optionally, the phase change material is selected from C18～C30Any of straight-chain alkanes (paraffins).
Optionally, the oil phase is selected from any one or more of styrene, toluene, trimethylbenzene and cyclohexane.
Optionally, the volume ratio of the phase change material, the organosilane coupling agent, the base catalyst, the oil phase, and the acidic solution is 1: 4-5: 4-5: 6-15: 200 to 300.
Optionally, the reaction process after the alkali catalyst is added into the second reaction solution includes stirring and reacting for 0.5-24 h at 50-70 ℃, wherein the pH value of the solution after the alkali catalyst is added into the second reaction solution is 9.0-11.0.
Optionally, the base catalyst is selected from at least one of ammonia, triethylamine, sodium hydroxide or triethanolamine.
Optionally, before obtaining the organic silicon thermal energy storage phase change microcapsule with a bowl-shaped structure, the method further comprises:
and carrying out centrifugal washing on the solution after the alkali catalyst and the second reaction solution react.
In particular, the invention also provides a bowl-shaped organic silicon thermal energy storage phase change microcapsule which is optionally prepared by the preparation method of the bowl-shaped organic silicon thermal energy storage phase change microcapsule.
According to the invention, the bowl-shaped organic silicon heat energy storage phase change microcapsule with the heat energy storage phase change material, the bowl-shaped structure and the microcapsule structure integrated is obtained through the preparation method, the organic silicon nano material and the heat energy storage phase change material are innovatively synthesized into the novel nano phase change material with the bowl-shaped structure through a sol-gel method, and a new thought is provided for the appearance synthesis direction of the organic silicon nano material and the compounding field of the heat energy storage phase change material.
The preparation method of the invention is an organic whole, and the preparation method has simple process, mild reaction conditions (only stirring or ultrasound and the like at 50-70 ℃), low cost of preparation raw materials and good repeatability.
The organic silicon thermal energy storage phase change microcapsule prepared by the preparation method has a bowl-shaped structure, and compared with other nano-structure phase change microcapsules, the bowl-shaped structure prepared by the method has larger contact area with the surface of a substrate material, so that the combination between the microcapsule and the substrate is tighter. Meanwhile, the bowl-shaped structure can adsorb and store smaller particles in the bowl-shaped cavity, has higher bonding and adsorption capacity with a substrate material, can be added into different coating substrate materials, and is applied to more fields.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
FIG. 1 is a schematic flow chart of a preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to one embodiment of the invention;
FIG. 2 is a transmission electron microscope image of a bowl-shaped silicone thermal energy storage phase change microcapsule prepared in example 1;
FIG. 3 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 1;
FIG. 4 is an infrared spectrum of a bowl-shaped silicone thermal energy storage phase change microcapsule prepared in example 1;
FIG. 5 is a DSC image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 1;
FIG. 6 is a transmission electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 2;
FIG. 7 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 2;
FIG. 8 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 3;
FIG. 9 is a scanning electron micrograph of the results obtained in example 4;
FIG. 10 is a scanning electron micrograph of the results obtained in example 5;
FIG. 11 is a transmission electron micrograph of the result obtained in example 6;
FIG. 12 is a scanning electron micrograph of the results obtained in example 6;
FIG. 13 is a transmission electron micrograph of the result obtained in example 7;
FIG. 14 is a scanning electron micrograph of the results obtained in example 7.
Detailed Description
FIG. 1 is a schematic flow chart of a preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to one embodiment of the invention. The preparation method of the bowl-shaped organic silicon thermal energy storage phase change microcapsule of the embodiment may include the following steps:
step S100, adding an organosilane coupling agent into an acidic solution with a preset pH value, and mixing and reacting to obtain a first reaction solution;
step S200, adding the oil phase solution dissolved with the phase-change material into the first reaction solution, and mixing to obtain a second reaction solution;
and step S300, adding an alkali catalyst into the second reaction liquid to react to obtain the organic silicon thermal energy storage phase change microcapsule with the bowl-shaped structure.
According to the embodiment, the bowl-shaped organic silicon heat energy storage phase change microcapsule with the heat energy storage phase change material, the bowl-shaped structure and the microcapsule structure integrated is obtained through the preparation method, the organic silicon nano material and the heat energy storage phase change material are innovatively synthesized into the novel nano phase change material with the bowl-shaped structure through a sol-gel method, and a new thought is provided for the organic silicon nano material morphology synthesis direction and the heat energy storage phase change material composite field.
In this embodiment, the organosilane coupling agent in step S100 is selected from any one of Vinyltriethoxysilane (VTES), Phenyltriethoxysilane (PTES), and Methacryloxypropyltrimethoxysilane (MPS).
In step S100, the process of adding the organosilane coupling agent into the acidic solution having the preset pH value for mixing reaction may include:
adding an organosilane coupling agent into an acidic solution with a preset pH value, and stirring at the rotating speed of 200-1200 rpm for 0.5-24 h at the temperature of 50-70 ℃. For example, the reaction temperature may be 50 ℃, 60 ℃ or 70 ℃. The stirring speed may be 200rpm, 600rpm or 1200 rpm. The reaction time may be 0.5h, 12h or 24 h. In this embodiment, the reaction temperature is preferably 65 ℃, the stirring time is preferably 12 hours, and the stirring speed is preferably 600 rpm. Since hydrolysis of the organosilane coupling agent is a relatively mild process, wherein the temperature is too low, the rate of hydrolysis of the organosilane coupling agent is too slow. The temperature is too high, and the hydrolysis rate of the organosilane coupling agent is too high. Similarly, the stirring time is similar to the influence of pH on the hydrolysis of the organosilane coupling agent, and the stirring time is too short, and the hydrolysis degree of the organosilane coupling agent is not enough, so that the number of silicon hydroxyl Si-OH groups is too small, and the stable O/W microemulsion is difficult to form. And the stirring time is too long, the number of Si-OH groups is too much, and the stable O/W microemulsion is difficult to form. The stirring speed mainly influences the stability of the O/W microemulsion and the grain size of bowl-shaped organic silicon, and the O/W microemulsion system is unstable due to overlarge rotating speed.
The acidic solution in this embodiment is an aqueous solution of glacial acetic acid, but as other embodiments, aqueous solutions of other acids may be used, and the conditions can be satisfied only by adjusting the preset pH value of the acidic solution to 3.0-6.0. In this embodiment, the predetermined pH may be 3, 4, 5, or 6. The preset pH value of this embodiment is preferably 4. In this embodiment, the acidic solution is used to provide an acidic environment for the hydrolysis of the organosilane coupling agent. Therefore, the acidic environment must be within a certain range. The acidity is too strong, the hydrolysis speed of the organosilane coupling agent is increased, excessive silicon hydroxyl Si-OH groups are generated, and molecules have strong hydrogen bond effect to form gel; the acidity is too weak, the prehydrolysis degree of the organosilane coupling agent is not enough, the number of silicon hydroxyl Si-OH groups is too small, and the stable O/W microemulsion is difficult to form. As an organic weak acid, acetic acid is used, compared with inorganic acid, the acetic acid does not bring impurity elements while providing acidic reaction conditions, and the purity of the product is ensured. In addition, acetic acid is used as weak acid, and the pH is regulated and controlled to be more stable.
In step S200, the phase change material is selected from C18～C30Any of straight-chain alkanes (paraffins). C of the number of carbon atoms18～C30The straight-chain alkane (paraffin) has the advantages of large phase change potential, almost no supercooling phenomenon, low steam pressure during melting, good chemical stability, small change of phase change temperature and phase change potential after repeated heat absorption and release, no phase separation, no corrosivity and the like, and can select the alkanes with different chain lengths (the phase change temperature is along with the alkane chain) according to application requirementsIncreasing with increasing length).
The oil phase in this embodiment is selected from any one or more of styrene, toluene, trimethylbenzene, and cyclohexane. The oil phase is used as a solvent for dissolving the phase-change material, and needs to have extremely strong volatility at normal temperature, and the oil phase coated in the oil phase can volatilize by itself in the post-treatment process of preparing the microcapsule, so that the heat energy storage phase-change material is left.
In step S200, the step of mixing may select ultrasonic mixing. Specifically, the ultrasonic temperature is about 50 ℃ to 70 ℃, and the ultrasonic time is about 1min to 5 min. When the ultrasonic temperature is too low or the ultrasonic time is too long, the temperature of the second reaction liquid is reduced too much, so that the phase-change material in the second reaction liquid is solidified, and the second reaction liquid is changed from a liquid phase to a solid phase. The ultrasonic time is too short, the second reaction liquid may not be sufficiently emulsified, and O/W microemulsion with uniform size is difficult to form.
In step S300, the reaction process after adding the alkali catalyst into the second reaction solution comprises stirring and reacting for 0.5-24 h at 50-70 ℃, wherein the pH value of the solution after adding the alkali catalyst into the second reaction solution is 9.0-11.0. The reaction temperature in this example may be 50 ℃, 60 ℃ or 70 ℃. The stirring time may be 0.5h, 10h, 12h or 24 h. The pH of the solution after the addition of the base catalyst to the second reaction solution may be 9, 10 or 11. It is preferable that the pH of the solution after the addition of the base catalyst to the second reaction liquid is about 10. Under the alkaline condition, condensation reaction occurs between the organic silicon source precursor molecules attached to the surface of the oil phase droplet, and the organic silicon source precursor molecules are mutually crosslinked to form a shell layer, so that the stable form of the organic silicon nano microsphere is facilitated. The alkalinity is too weak, the condensation rate of the organic silicon source precursor molecules is slow, and a stable and uniform shell layer is not easy to form. The alkalinity is too strong, the condensation rate of the organic silicon source precursor molecules on the shell layer is too high, and the nano microspheres are easily linked together, so that the product dispersibility is reduced.
In the whole reaction, the volume ratio of the phase-change material, the organosilane coupling agent, the alkali catalyst, the oil phase and the acidic liquid is 1: 4-5: 4-5: 6-15: 200 to 300. Preferably, the volume ratio of the phase-change material, the organosilane coupling agent, the base catalyst, the oil phase and the acidic liquid can be 1: 4.5: 4.5: 12: 240. the addition of the organosilane coupling agent is too little or the addition of the oil phase is too much, the amphiphilic organosilane coupling agent oligomer generated by hydrolysis is not enough to stabilize an O/W microemulsion system on an oil-water interface, and a condensed shell layer is too thin to crack; if too little organosilane coupling agent or too much oil phase is added, the shell layer of the microcapsule is too thick, and meanwhile, the redundant organic silicon source molecules form solid microspheres, so that the yield of the phase-change microcapsule is reduced.
The alkali catalyst in this embodiment is at least one selected from ammonia, triethylamine, sodium hydroxide, and triethanolamine.
In step S300, before obtaining the bowl-shaped silicone thermal energy storage phase change microcapsule, the method further includes:
and (4) centrifugally washing the solution after the alkali catalyst and the second reaction solution react.
Specifically, the process of the centrifugal washing in the present embodiment includes a plurality of repetitions of the centrifugal washing. More specifically, the centrifugal washing process can also comprise centrifugation, ethanol washing, centrifugation, deionized water washing, centrifugation, ethanol washing and centrifugation, so as to obtain the bowl-shaped organic silicon heat energy storage phase change microcapsule.
The present application will be specifically described below with reference to specific examples.
Example 1
240 parts by volume of the prepared dilute acetic acid solution (pH. apprxeq.4) are weighed out in a measuring cylinder into a clean round-bottomed flask, warmed to 65 ℃ and stirred at 600 rpm. Keeping the temperature for 10min, using a liquid transfer gun to transfer 4.5 volume parts of Vinyltriethoxysilane (VTES) to be rapidly added into a dilute acetic acid solution, and stirring for reaction for 12h to obtain a first reaction liquid;
weighing 1 part by volume of docosane by using an electronic balance, then transferring 12 parts by volume of styrene and docosane by using a liquid transfer gun, blending, adding into the first reaction liquid obtained in the step (1), and performing ultrasonic treatment at 65 ℃ for 2min to uniformly mix the mixture to obtain a second reaction liquid;
adding 4.5 parts by volume of 28% ammonia water into the second reaction solution, and then stirring for 12 hours by using a magnetic stirrer, keeping the temperature at 65 ℃, and finishing the reaction. And (3) treating the product according to the sequence of centrifugation, ethanol washing, centrifugation, deionized water washing, centrifugation, ethanol washing and centrifugation to obtain the bowl-shaped organic silicon thermal energy storage phase change microcapsule.
FIG. 2 is a transmission electron microscope image of a bowl-shaped silicone thermal energy storage phase change microcapsule prepared in example 1;
FIG. 3 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 1. As is clear from fig. 2 and 3, the preparation method of this example yielded a bowl-shaped microcapsule.
FIG. 4 is an infrared spectrum of a bowl-shaped silicone thermal energy storage phase change microcapsule prepared in example 1. As can be seen from the infrared spectrogram, the infrared spectrogram of docosane is 2900cm-1The wave number positions on the left and the right have a characteristic absorption peak. The bowl-shaped organic silicon thermal energy storage phase change microcapsule particle is positioned at 2900cm-1Still, there are relatively small peaks at the wave number positions around, indicating the presence of docosane in the synthesized particles.
FIG. 5 is a DSC image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 1. Thermogravimetric analysis is carried out on the synthesized bowl-shaped organic silicon heat energy storage phase change microcapsule particles, a lower side curve of a DSC image is a temperature rise process, and a downward peak appears due to environmental heat loss caused by heat absorption of the phase change material. The presence of docosane is further illustrated by the fact that the peak occurs at a position around 40 ℃ and is just close to the melting temperature of docosane. The upper side curve is the cooling process, because phase change material is exothermic, leads to the environmental heat to increase, upward peak appears, to sum up can show that the material possesses the energy storage effect.
Example 2
Compared with the example 1, only the added oil phase is changed from styrene to toluene, and the bowl-shaped organic silicon thermal energy storage phase change microcapsule is also obtained.
FIG. 6 is a transmission electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 2; FIG. 7 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 2. As can be seen from fig. 6 and 7, appropriate modification of the oil phase does not change the formation of the silicone thermal energy storage phase change microcapsules into a bowl-like structure.
Example 3:
compared with the example 1, the type of the added oil phase is changed from styrene to toluene, and the proportion of the oil phase is increased to 15 parts by volume, so that the bowl-shaped structural organic silicon thermal energy storage phase change microcapsule with deeper invagination is obtained.
FIG. 8 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 3. As can be seen in fig. 8, the bowl-like structure prepared in example 3 is largely recessed. Namely, the dosage of the oil phase is increased, and finally the obtained pits become deep.
Example 4:
compared with the example 1, the type of the added oil phase is changed from styrene to toluene, and the proportion of the oil phase is reduced to 8 parts by volume, so that the bowl-shaped structural organic silicon thermal energy storage phase change microcapsule with relatively shallow invagination is obtained.
FIG. 9 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 4. As can be seen from fig. 9, the pits of the bowl-like structure prepared in example 4 become shallower pits. That is, the amount of the oil phase is reduced, and the finally obtained pits become shallow and the number of the pits becomes small.
Example 5:
compared with the example 1, the type of the added oil phase is changed from styrene to toluene, and the proportion of the oil phase is reduced to 6 parts by volume, so that the bowl-shaped structural silicone thermal energy storage phase change microcapsule with the shallowest invagination is obtained.
FIG. 10 is a scanning electron microscope image of bowl-shaped silicone thermal energy storage phase change microcapsules prepared in example 5. As can be seen from fig. 10, the pits of the bowl-shaped structure prepared in example 5 become shallow pits. I.e. the amount of oil phase is greatly reduced and the resulting pits are shallowest.
From examples 3 to 5, it is understood that the depth of the pits can be adjusted by adjusting the amount of the oil phase according to the production method of the present application.
Example 6:
compared with the example 1, only the organic silicon thermal energy storage phase change microcapsule is obtained without adding the oil phase and under the same other conditions.
FIGS. 11 and 12 are transmission electron micrographs and scanning electron micrographs of the results obtained in example 6. As is clear from fig. 11 and 12, the bowl-shaped structure cannot be formed without the presence of the oil phase.
Example 7:
compared with the embodiment 1, the oil phase and the phase change material are not added, other conditions are the same, and only the solid organosilicon microspheres are obtained.
FIGS. 11 and 12 are transmission electron micrographs and scanning electron micrographs of the results obtained in example 6. As can be seen from fig. 11 and 12, the bowl-shaped structure cannot be formed and the thermal energy storage phase change microcapsule cannot be formed without the presence of the oil phase and the phase change material.
Therefore, the preparation method of the embodiment is an organic whole, the process of the preparation method is simple, the reaction conditions are mild (only conventional treatments such as stirring, ultrasound and the like at 50-70 ℃) are needed, and the cost of the preparation raw materials is low. The preparation method has good repeatability, and the obtained product has large quantity.
The organic silicon thermal energy storage phase change microcapsule prepared by the preparation method has a bowl-shaped structure, and the bowl-shaped structure has a high specific surface and a high bulk density, so that compared with other nano-structure phase change microcapsules, the recessed bowl-shaped structure prepared by the embodiment has a larger contact area with the surface of a substrate material, so that the combination between the microcapsule and the substrate is tighter. Meanwhile, the bowl-shaped structure can adsorb and store smaller particles in the bowl-shaped cavity, has higher bonding and adsorption capacity with a substrate material, can be added into different coating substrate materials, and is applied to more fields.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (10)
1. A preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules is characterized by comprising the following steps:
adding an organosilane coupling agent into an acidic solution with a preset pH value, and mixing and reacting to obtain a first reaction solution;
adding the oil phase solution dissolved with the phase-change material into the first reaction solution, and mixing to obtain a second reaction solution;
and adding an alkali catalyst into the second reaction solution to react to obtain the bowl-shaped organic silicon thermal energy storage phase change microcapsule.
2. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
the organosilane coupling agent is any one of vinyl triethoxysilane, phenyl triethoxysilane and methacryloxypropyl trimethoxysilane.
3. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
the process of adding organosilane coupling agent into the acid solution with the preset pH value for mixing reaction comprises the following steps:
adding an organosilane coupling agent into an acidic solution with a preset pH value, and stirring at the rotating speed of 200-1200 rpm for 0.5-24 h at the temperature of 50-70 ℃; the acid solution is an aqueous solution of glacial acetic acid, and the preset pH value is 3.0-6.0.
4. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
the phase change material is selected from C18～C30Any one of linear alkanes.
5. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
the oil phase is selected from any one or more of styrene, toluene, trimethylbenzene and cyclohexane.
6. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
the volume ratio of the phase-change material, the organosilane coupling agent, the base catalyst, the oil phase to the acidic liquid is 1: 4-5: 4-5: 6-15: 200 to 300.
7. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
and the reaction process after the alkali catalyst is added into the second reaction liquid comprises stirring and reacting for 0.5-24 h at the temperature of 50-70 ℃, wherein the pH value of the solution after the alkali catalyst is added into the second reaction liquid is 9.0-11.0.
8. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
the alkali catalyst is at least one of ammonia water, triethylamine, sodium hydroxide or triethanolamine.
9. The preparation method of bowl-shaped organic silicon thermal energy storage phase change microcapsules according to claim 1,
before the organic silicon thermal energy storage phase change microcapsule with a bowl-shaped structure is obtained, the method also comprises the following steps:
and carrying out centrifugal washing on the solution after the alkali catalyst and the second reaction solution react.
10. A bowl-shaped organic silicon thermal energy storage phase change microcapsule is characterized by being prepared by the preparation method of the bowl-shaped organic silicon thermal energy storage phase change microcapsule according to any one of claims 1-9.
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| CN116581093A (en) * | 2023-05-08 | 2023-08-11 | 东南大学 | Cooling device for heat storage type high-power device |
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