CN112094626B - Double-shell gradient phase change microcapsule and preparation method thereof - Google Patents
Double-shell gradient phase change microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a double-shell gradient phase change microcapsule and a preparation method thereof. The double-shell gradient phase change microcapsule comprises: the outer-layer phase change microcapsule comprises an outer shell layer and an outer-layer phase change material arranged in the outer shell layer; the inner phase change microcapsule is arranged in the outer phase change material; the inner-layer phase-change microcapsule comprises an inner-layer and an inner-layer phase-change material arranged in the inner-layer; the phase change temperature of the outer layer phase change material is lower than that of the inner layer phase change material. This double-shell gradient phase change microcapsule through adopting the higher inlayer phase change material of phase transition temperature and the lower inlayer phase change material of phase transition temperature, has effectively improved the phase transition latent heat of microcapsule to enlarge the application temperature scope of microcapsule, effectively avoided the emergence of microcapsule thermal breakdown phenomenon.
Description
Technical Field
The invention relates to the technical field of phase change heat insulation materials, in particular to a double-shell gradient phase change microcapsule and a preparation method thereof.
Background
Thermal energy storage by means of phase change materials is an important research area. General phase change insulation material is solid-liquid phase transition type, and its low price is easily obtained, the phase transition enthalpy is high, phase transition in-process volume change is little, but if not directly using through the cladding, can take place to reveal at the in-process of heat absorption phase transition, and most organic phase change material heat conductivity is low, and easily fires, and most inorganic phase change material has stronger corrosivity, can destroy the storage container.
The above problems can be effectively solved by microencapsulation. Generally, various organic polymers are used as wall materials of the phase change microcapsule, the organic wall materials are rich in types and have good structural elasticity, and the volume change in the phase change process can be borne, but the organic wall materials are low in thermal conductivity and can possibly release harmful gases. The inorganic wall material has the advantages of high thermal conductivity, excellent thermal stability and chemical stability, non-inflammability and the like, but has larger brittleness and poor mechanical strength, and is easy to crack in the processing process of being mixed with other materials for use.
At present, research on single-shell phase change microcapsules is not in progress, but the phase change temperature of a single-layer microcapsule is a fixed value, and in practical use, once the use temperature exceeds the phase change temperature more and a heat source lasts, the single-layer microcapsule has the risk of losing the heat storage and temperature regulation capacity due to thermal breakdown.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a double-shell gradient phase change microcapsule and a preparation method thereof. According to the double-shell gradient phase change microcapsule, the inner phase change material with higher phase change temperature and the inner phase change material with lower phase change temperature are adopted, so that the phase change latent heat of the microcapsule is effectively improved, the service temperature range of the microcapsule is expanded, and the thermal breakdown phenomenon of the microcapsule is effectively avoided.
In one aspect of the invention, the invention provides a double-shell gradient phase change microcapsule. According to an embodiment of the present invention, the double-shell gradient phase change microcapsule comprises: the outer-layer phase change microcapsule comprises an outer shell layer and an outer-layer phase change material arranged in the outer shell layer; the inner phase change microcapsule is arranged in the outer phase change material; the inner-layer phase-change microcapsule comprises an inner-layer and an inner-layer phase-change material arranged in the inner-layer; the phase change temperature of the outer layer phase change material is lower than that of the inner layer phase change material.
According to the double-shell gradient phase change microcapsule disclosed by the embodiment of the invention, the inner-layer phase change material with higher phase change temperature and the inner-layer phase change material with lower phase change temperature are adopted, so that the phase change latent heat of the microcapsule is effectively improved, the service temperature range of the microcapsule is expanded, and the thermal breakdown phenomenon of the microcapsule is effectively avoided.
In addition, the double-shell gradient phase change microcapsule according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the outer shell layer is formed from a composite of an inorganic material and an emulsion polymerized high molecular polymer.
In some embodiments of the present invention, the high molecular weight polymer is a copolymer or homopolymer formed by emulsion polymerization of a monomer selected from styrene, methyl methacrylate, butyl acrylate, acrylonitrile, butadiene.
In some embodiments of the present invention, the high molecular weight polymer is a mixture of polyurethane and polyurea, or a mixture comprising a copolymer or homopolymer formed by polymerization of the monomers.
In some embodiments of the invention, the inner shell layer is formed of an inorganic material.
In some embodiments of the invention, the inorganic material is selected from at least one of silica, titania.
In some embodiments of the invention, the phase change temperature of the outer phase change material is 25-45 ℃.
In some embodiments of the present invention, the phase transition temperature of the inner phase change material is 35-75 ℃.
In some embodiments of the present invention, the outer phase change material and the inner phase change material are each independently selected from at least one of an alkyl-based phase change material, a paraffin-based phase change material, and a fatty acid-based phase change material.
In some embodiments of the present invention, the outer phase change material and the inner phase change material further comprise an inorganic salt.
In some embodiments of the present invention, the diameter of the inner phase-change microcapsule is 1 to 30 μm.
In some embodiments of the present invention, the diameter of the outer phase-change microcapsule is 100 to 500 μm.
In another aspect of the present invention, the present invention proposes a method for preparing the double-shell gradient phase change microcapsules of the above embodiments. According to an embodiment of the invention, the method comprises: (1) carrying out first mixing on the inner phase-change material, the inorganic material precursor, the emulsifier and the solvent to obtain a first mixed solution; adding a hydrolytic agent into the first emulsion and carrying out a first reaction to obtain an inner-layer phase-change microcapsule; (2) carrying out second mixing on the outer-layer phase-change material, the inorganic material precursor and the inner-layer phase-change microcapsule to obtain a second mixed solution; adding a polymer monomer and a coupling agent into the second mixed solution, and carrying out third mixing to obtain a third mixed solution; adding a surfactant, an initiator, an emulsifier and a solvent into the third mixed solution, and carrying out fourth mixing to obtain a fourth mixed solution; and adding a hydrolytic agent into the fourth mixed solution and carrying out a second reaction to obtain the double-shell gradient phase change microcapsule. Therefore, the method can be used for simply, conveniently and efficiently preparing the double-shell gradient phase change microcapsule of the embodiment, and the prepared microcapsule has excellent phase change latent heat and thermal shock resistance.
In addition, the method for preparing the double-shell gradient phase-change microcapsule according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the inorganic material precursor is selected from at least one of ethyl orthosilicate and tetrabutyl titanate.
In some embodiments of the invention, the emulsifier is cetyltrimethylammonium bromide.
In some embodiments of the invention, the coupling agent is methacryloxypropyl trimethoxysilane.
In some embodiments of the invention, the hydrolysis agent is aqueous ammonia.
In some embodiments of the invention, in the step (1), the mass ratio of the inner phase-change material, the inorganic material precursor, the emulsifier and the hydrolytic agent is (15-20): 25-35): 2-5): 3-8.
In some embodiments of the invention, in the step (2), the mass ratio of the outer-layer phase-change material, the inorganic material precursor and the inner-layer phase-change microcapsule is (7-15): (10-20): 2-8).
In some embodiments of the invention, in the step (2), the mass ratio of the polymer monomer, the initiator, the coupling agent, the emulsifier and the hydrolytic agent is (2-8): 1-20): 0.5-1.5): 1-5): 2-4.
In some embodiments of the present invention, the first mixing is performed at 25 to 65 ℃ for 5 to 45 min.
In some embodiments of the present invention, the first reaction is performed at 35 to 85 ℃ for 10 to 28 hours, and the first reaction is performed at a stirring speed of 1000 to 2500rpm or under ultrasonic vibration.
In some embodiments of the invention, the second mixing is performed at 30 to 60 ℃.
In some embodiments of the invention, the third mixing is performed at 30 to 60 ℃.
In some embodiments of the present invention, the fourth mixing is performed at 30 to 80 ℃ for 15 to 80min, and the fourth mixing is performed at a stirring speed of 300 to 1000 rpm.
In some embodiments of the present invention, the second reaction is performed at 35 to 95 ℃ for 2 to 10 hours, and the second reaction is performed at a stirring speed of 200 to 600 rpm.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural diagram of a double-shell gradient phase change microcapsule according to one embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for preparing a double-shell gradient phase-change microcapsule according to an embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first," "second," "third," "fourth," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicit to a number of indicated technical features. Thus, features defined as "first," "second," "third," "fourth," etc. may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, the invention provides a double-shell gradient phase change microcapsule. Referring to fig. 1, according to an embodiment of the present invention, the double-shell gradient phase change microcapsule includes: outer phase change microcapsules 100 and inner phase change microcapsules 200. Wherein, the outer-layer phase-change microcapsule 100 comprises an outer-shell layer 101 and an outer-layer phase-change material 102 arranged in the outer-shell layer 101; the inner phase-change microcapsule 200 is arranged in the outer phase-change material 102; the inner phase change microcapsule 200 includes an inner shell layer 201 and an inner phase change material 202 disposed in the inner shell layer 201.
The double-shell gradient phase change microcapsules according to embodiments of the present invention are further described in detail below.
In the double-shell gradient phase change microcapsule, the outer-layer phase change material and the inner-layer phase change material are respectively encapsulated in the outer shell and the inner shell, and the phase change temperature of the outer-layer phase change material is lower than that of the inner-layer phase change material, so that an energy storage gradient is formed. When the external temperature reaches the phase change temperature of the outer phase change material, the outer phase change material changes phase and absorbs heat; when the external temperature continuously rises, the temperature of the outer phase-change material is continuously increased, and when the phase-change point of the inner phase-change material is reached, the inner phase-change material changes phase and absorbs heat. Therefore, the damage of the shell layer caused by the volume increase of the phase change material with the overhigh temperature of the outer phase change material can be effectively avoided, and the thermal breakdown of the phase change microcapsule is also avoided. The composite use of the gradient phase-change material not only effectively improves the phase-change latent heat of the microcapsule, but also expands the phase-change temperature of the microcapsule from a fixed temperature point to a temperature range, and improves the thermal shock resistance of the microcapsule.
According to some embodiments of the invention, the outer shell layer is formed from a composite of an inorganic material and an emulsion polymerized high molecular polymer. The organic-inorganic hybrid wall formed by the inorganic material and the high molecular polymer has higher thermal conductivity relative to a single organic wall material, and can accelerate the conduction from the environment temperature to the phase change material. Meanwhile, the strength of the hybrid wall material is further improved by adding the inorganic component. On the other hand, the organic-inorganic hybrid wall has higher toughness and elasticity relative to a single inorganic wall material, so that the wall material can bear pressure on the wall material due to the increase of the volume of the phase change material with certain strength. In summary, the organic-inorganic hybrid wall combines the advantages of the traditional inorganic wall material and the organic wall material, simultaneously makes up the respective determinations of the two, has better strength and toughness compared with the single organic/inorganic wall material, can ensure the integrity of the organic-inorganic hybrid wall material in use or in the mixing process with other materials, and avoids the damage of the wall material and the leakage of the phase change material.
According to some embodiments of the present invention, the polymer may be a copolymer or homopolymer formed by emulsion polymerization of a monomer selected from styrene, methyl methacrylate, butyl acrylate, acrylonitrile, butadiene; alternatively, the high molecular weight polymer may be a mixture of polyurethane and polyurea, or a mixture containing a copolymer or homopolymer obtained by polymerizing the above-mentioned monomer. Therefore, the organic-inorganic hybrid wall material formed by the high molecular polymer and the inorganic material has better performance.
According to some embodiments of the invention, the inner shell layer is formed of an inorganic material. The inorganic material has better heat-conducting property, and the inner shell layer is made of the inorganic material, so that the conduction of temperature from the outer-layer phase-change material to the inner-layer phase-change material is further facilitated.
According to some embodiments of the present invention, the inorganic material may be at least one selected from silica and titania.
According to some embodiments of the present invention, the phase transition temperature of the outer phase change material may be 25 to 45 ℃, such as 25 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 35 ℃, 40 ℃, 42 ℃, 45 ℃ and the like. The phase transition temperature of the inner phase change material may be 35 to 75 ℃, for example, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and the like. The phase change temperature of the outer phase change material and the phase change temperature of the inner phase change material are set to be in the range, and the phase change temperature of the outer phase change material is lower than that of the inner phase change material, so that the temperature application range of the phase change microcapsule can be further expanded.
According to some embodiments of the present invention, the outer phase-change material and the inner phase-change material are respectively and independently selected from at least one of alkyl phase-change material, paraffin phase-change material and fatty acid phase-change material. In some embodiments of the present invention, the outer phase change material and the inner phase change material further comprise an inorganic salt (e.g., water glass, etc.).
According to some embodiments of the present invention, the diameter of the inner-layer phase-change microcapsule may be 1 to 30 μm, such as 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, etc.; the diameter of the outer-layer phase-change microcapsule may be 100 to 500 μm, for example, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, etc. The diameters of the outer-layer phase-change microcapsule and the inner-layer phase-change microcapsule can be adjusted by controlling parameters such as critical micelle concentration, initiator dosage, stirring speed and the like in the preparation process. The inventors found that by controlling the diameters of the outer phase-change microcapsules and the inner phase-change microcapsules to be within the above ranges, the performance of the outer phase-change microcapsules and the inner phase-change microcapsules can be further facilitated. If the diameter of the inner-layer phase-change microcapsule is too large, the inner-layer phase-change microcapsule is difficult to wrap in the outer-layer microcapsule, and if the diameter of the outer-layer phase-change microcapsule is too small, the inner-layer phase-change microcapsule is difficult to wrap, so that the thermal performance of the microcapsule is adversely affected.
In another aspect of the present invention, the present invention proposes a method for preparing the double-shell gradient phase change microcapsules of the above embodiments. Referring to fig. 2, according to an embodiment of the invention, the method comprises:
s100: preparing inner-layer phase-change microcapsules
In the step, the inner phase-change material, the inorganic material precursor, the emulsifier and the solvent are subjected to first mixing to obtain a first mixed solution; and adding a hydrolyzing agent into the first emulsion and carrying out a first reaction to obtain the inner-layer phase-change microcapsule.
According to some embodiments of the present invention, the inorganic material precursor may be tetraethyl orthosilicate. The tetraethoxysilane can be hydrolyzed into silicon dioxide under the action of a hydrolyzing agent so as to obtain an inner shell layer.
According to some embodiments of the invention, the emulsifier may be cetyltrimethylammonium bromide.
According to some embodiments of the invention, the coupling agent may be methacryloxypropyltrimethoxysilane.
According to some embodiments of the invention, the above-mentioned hydrolyzing agent may be ammonia water.
In S100, the dosage ratio of each material can be adjusted according to the specific types of the precursor and the hydrolytic agent, for example, according to some embodiments of the present invention, the mass ratio of the inner phase-change material, the inorganic material precursor, the emulsifier, and the hydrolytic agent can be (15-20): (25-35): (2-5): (3-8). Specifically, the mass fraction of the inner phase change material may be 15, 17, 18, 20, etc., the mass fraction of the inorganic material precursor may be 25, 28, 30, 32, 35, etc., the mass fraction of the emulsifier may be 2, 3, 4, 5, etc., and the mass fraction of the hydrolytic agent may be 3, 5, 6, 7, 8, etc. By controlling the proportion of the components within the range, the preparation of the inner phase-change microcapsule can be further facilitated, and the diameter of the inner phase-change microcapsule is controllable, so that the performance is better.
According to some embodiments of the invention, the first mixing is performed at 25 to 65 ℃ for 5 to 45 min. Specifically, the mixing temperature can be 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, etc., and the mixing time can be 5min, 8min, 10min, 12min, 15min, 20min, 30min, 40min, 45min, etc.
According to some embodiments of the present invention, the first reaction is performed at 35-85 ℃ for 10-28 h, and the first reaction is performed at a stirring speed of 1000-2500 rpm or under ultrasonic vibration. Specifically, the reaction temperature may be 30 ℃, 35 ℃, 40 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃, 85 ℃ and the like, the reaction time may be 10h, 15h, 20h, 22h, 24h, 26h, 28h and the like, and the stirring rotation speed may be 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 2000rpm, 2500rpm and the like. Therefore, the preparation of the inner phase-change microcapsule can be further facilitated, the diameter of the inner phase-change microcapsule is controllable, and the performance is better.
S200: preparing outer-layer phase-change microcapsules
In the step, the outer-layer phase-change material, the inorganic material precursor and the inner-layer phase-change microcapsule are subjected to second mixing to obtain a second mixed solution; adding a polymer monomer and a coupling agent into the second mixed solution, and carrying out third mixing to obtain a third mixed solution; adding a surfactant, an initiator, an emulsifier and a solvent into the third mixed solution, and carrying out fourth mixing to obtain a fourth mixed solution; and adding a hydrolytic agent into the fourth mixed solution and carrying out a second reaction to obtain the double-shell gradient phase change microcapsule.
According to some embodiments of the present invention, the inorganic material precursor may be at least one selected from the group consisting of ethyl orthosilicate and tetrabutyl titanate. The tetraethoxysilane can be hydrolyzed into silicon dioxide under the action of a hydrolyzing agent, and the tetrabutyl titanate can be hydrolyzed into titanium dioxide under the action of the hydrolyzing agent, and further compounded with the high molecular polymer to form a shell layer.
According to some embodiments of the invention, the emulsifier may be cetyltrimethylammonium bromide.
According to some embodiments of the invention, the coupling agent may be methacryloxypropyltrimethoxysilane.
According to some embodiments of the invention, the above-mentioned hydrolyzing agent may be ammonia water.
In S200, the dosage ratio of various materials can be adjusted according to the specific types of the precursor and the hydrolytic agent, for example, according to some embodiments of the invention, the mass ratio of the outer-layer phase-change material, the inorganic material precursor and the inner-layer phase-change microcapsule is (7-15): 10-20): 2-8. Specifically, the mass fraction of the phase-change material of the outer layer may be 7, 8, 10, 12, 15, etc., the mass fraction of the inorganic material precursor may be 10, 12, 15, 18, 20, etc., and the mass fraction of the phase-change microcapsule of the inner layer may be 2, 4, 5, 6, 8, etc. The mass ratio of the polymer monomer, the initiator, the coupling agent, the emulsifier and the hydrolytic agent is (2-8): 1-20): 0.5-1.5): 1-5): 2-4. Specifically, the mass fraction of the polymer monomer may be 2, 4, 5, 6, 8, etc., the mass fraction of the initiator may be 1, 5, 8, 10, 12, 15, 18, 20, etc., the mass fraction of the coupling agent may be 0.5, 0.8, 1.0, 1.2, 1.5, etc., the mass fraction of the emulsifier may be 1, 2, 3, 4, 5, etc., and the mass fraction of the hydrolyzing agent may be 2, 2.5, 3, 3.5, 4, etc. By controlling the proportion of the components within the range, the preparation of the outer-layer phase-change microcapsule can be further facilitated, and the diameter of the outer-layer phase-change microcapsule is controllable and the performance is better.
The specific type of the initiator is not particularly limited, and may be selected according to the specific type of the polymer monomer, and for example, azo type initiators, peroxy type initiators, oxidation-reduction type initiators, and the like, which are generally used in the art, may be used.
According to some embodiments of the present invention, the second mixing is performed at 30 to 60 ℃, and specifically, the mixing temperature may be 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 45 ℃, 50 ℃, 65 ℃, and the like.
According to some embodiments of the invention, the third mixing is performed at 30 to 60 ℃. Specifically, the mixing temperature may be 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 45 ℃, 50 ℃, 65 ℃ or the like.
According to some embodiments of the present invention, the fourth mixing is performed at 30 to 80 ℃ for 15 to 80min, and the fourth mixing is performed at a stirring speed of 300 to 1000 rpm. Specifically, the mixing temperature may be 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like, the mixing time may be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 70min, 80min and the like, and the stirring rotation speed may be 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm and the like. Therefore, the preparation of the outer-layer phase-change microcapsule can be further facilitated, the diameter of the outer-layer phase-change microcapsule is controllable, and the performance is better.
According to some embodiments of the present invention, the second reaction is performed at 35 to 95 ℃ for 2 to 10 hours, and the second reaction is performed at a stirring speed of 200 to 600 rpm. Specifically, the reaction temperature may be 35 ℃, 40 ℃, 50 ℃, 60 ℃, 65 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or the like, the reaction time may be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or the like, and the stirring rotation speed may be 200rpm, 300rpm, 400rpm, 500rpm, 600rpm or the like. Therefore, the preparation of the outer-layer phase-change microcapsule can be further facilitated, the diameter of the outer-layer phase-change microcapsule is controllable, and the performance is better.
In addition, it should be noted that all the features and advantages described above for the double-shell gradient phase change microcapsule are also applicable to the method for preparing the double-shell gradient phase change microcapsule, and are not described in detail herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
20g of paraffin with the phase transition temperature of 45 ℃ and 30mL of tetraethoxysilane are mixed at 50 ℃ to form transparent mixed liquid, then 5g of hexadecyl trimethyl ammonium bromide, 250mL of deionized water and 177mL of absolute ethyl alcohol are added, the mixed liquid is emulsified for 10min at 50 ℃ by an ultrasonic processor, then the obtained mixed liquid is transferred to a reaction kettle with mechanical stirring, then 5.2mL of ammonia water is added, and the stirring reaction is continued at the rotation speed of 1200rpm at 50 ℃ for 24 h. After the reaction is finished, filtering, washing with absolute ethyl alcohol, and drying to obtain the microcapsule A with the average grain diameter of 20 mu m, wherein the content of the core material is 50%, and the phase transition temperature is 45 ℃.
10g of paraffin with the phase transition temperature of 28 ℃ and 15mL of tetraethoxysilane are mixed at 35 ℃ to form transparent mixed liquid, then 5g of the microcapsule A is added to form suspension, 1mL of methacryloxypropyl trimethoxysilane and 5mL of styrene monomer are added, and the mixture is continuously and uniformly mixed at 35 ℃. And then adding 1.23g of hexadecyl trimethyl ammonium bromide, 15mL of 0.01mol/L ammonium persulfate solution, 250mL of deionized water and 175mL of absolute ethyl alcohol into the mixed solution, stirring and dispersing at the rotating speed of 500rpm at 35 ℃ for 45min to form emulsion, introducing nitrogen into the reactor, adding 2.6mL of ammonia water, heating the reactor to 80 ℃, and continuing stirring and reacting at the rotating speed of 300rpm for 6 h. And after the reaction is finished, cooling to room temperature, filtering, washing with absolute ethyl alcohol, and drying to obtain the double-shell gradient phase change microcapsule with the average particle size of 300 mu m, wherein the phase change interval is 28-45 ℃.
Example 2
20g of paraffin with the phase transition temperature of 65 ℃ and 30mL of tetraethoxysilane are mixed at 70 ℃ to form transparent mixed liquid, then 5g of hexadecyl trimethyl ammonium bromide, 250mL of deionized water and 177mL of absolute ethyl alcohol are added, the mixed liquid is emulsified for 15min at 70 ℃ by an ultrasonic processor, then the obtained mixed liquid is transferred to a reaction kettle with mechanical stirring, then 5.2mL of ammonia water is added, and the stirring reaction is continued at 70 ℃ and the rotation speed of 1500rpm for 24 h. After the reaction is finished, filtering, washing with absolute ethyl alcohol, and drying to obtain microcapsule A with the average grain diameter of 10 microns, wherein the content of the core material is 45%, and the phase transition temperature is 65 ℃.
10g of paraffin with the phase transition temperature of 35 ℃ and 15mL of tetraethoxysilane are mixed at 40 ℃ to form transparent mixed liquid, then 6g of the microcapsule A is added to form suspension, 1mL of methacryloxypropyl trimethoxysilane and 5mL of acrylonitrile monomer are added, and the mixture is continuously and uniformly mixed at 40 ℃. Then adding 2.46g of hexadecyl trimethyl ammonium bromide, 2mL of 0.015mol/L ferrous ammonium sulfate, 0.4mL of 0.1mol/L sulfuric acid, 250mL of deionized water and 200mL of absolute ethyl alcohol into the mixed solution, stirring and dispersing for 60min at the rotating speed of 700rpm at 50 ℃ to form emulsion, then introducing nitrogen into the reactor, adding 2.6mL of ammonia water, continuing stirring and reacting for 4h at the rotating speed of 300rpm, and then adding 1% sodium carbonate solution to stop the reaction. And after the reaction is finished, cooling to room temperature, filtering, washing with absolute ethyl alcohol, and drying to obtain the double-shell gradient phase change microcapsule with the average particle size of 200 mu m, wherein the phase change interval is 35-65 ℃.
Comparative example
20g of paraffin with the phase transition temperature of 35 ℃ and 30mL of tetraethoxysilane are mixed at 40 ℃ to form transparent mixed liquid, then 5g of hexadecyl trimethyl ammonium bromide, 250mL of deionized water and 177mL of absolute ethyl alcohol are added, the mixed liquid is emulsified for 15min at 40 ℃ by an ultrasonic processor, then the obtained mixed liquid is transferred to a reaction kettle with mechanical stirring, then 5.2mL of ammonia water is added, and the stirring reaction is continued at 40 ℃ for 24h at the rotating speed of 800 rpm. After the reaction is finished, filtering, washing with absolute ethyl alcohol, and drying to obtain the microcapsule with the average grain diameter of 150 mu m, wherein the content of the core material is 70%, and the phase transition temperature is 35 ℃.
Test example
The microcapsules prepared in the embodiments 1, 2 and comparative examples are used for performance test by using a Differential Scanning Calorimeter (DSC), the test temperature range is-10 ℃ to 20 ℃ above the phase change temperature of the phase change material, and the temperature rise and fall rate is 5 ℃/min. The test results are shown in table 1.
TABLE 1 test results
The test result shows that the double-shell gradient phase change microcapsule of the embodiment of the invention has higher latent heat of phase change and obviously improved thermal shock resistance compared with the traditional microcapsule.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (2)
1. A preparation method of a double-shell gradient phase change microcapsule is characterized by comprising the following steps:
mixing 20g of paraffin with the phase transition temperature of 45 ℃ and 30mL of tetraethoxysilane at 50 ℃ to form transparent mixed liquid, then adding 5g of hexadecyl trimethyl ammonium bromide, 250mL of deionized water and 177mL of absolute ethyl alcohol, emulsifying the mixed liquid for 10min at 50 ℃ by using an ultrasonic processor, then transferring the obtained mixed liquid into a reaction kettle with mechanical stirring, adding 5.2mL of ammonia water into the reaction kettle, and continuously stirring and reacting at the rotation speed of 1200rpm at 50 ℃ for 24 h; after the reaction is finished, filtering, washing with absolute ethyl alcohol, and drying to obtain a microcapsule A with the average particle size of 20 microns, wherein the content of the core material is 50%, and the phase transition temperature is 45 ℃;
mixing 10g of paraffin with the phase transition temperature of 28 ℃ and 15mL of tetraethoxysilane at 35 ℃ to form transparent mixed liquid, then adding 5g of the microcapsule A to form suspension, then adding 1mL of methacryloxypropyltrimethoxysilane and 5mL of styrene monomer, and continuously and uniformly mixing at 35 ℃; adding 1.23g of hexadecyl trimethyl ammonium bromide, 15mL of 0.01mol/L ammonium persulfate solution, 250mL of deionized water and 175mL of absolute ethyl alcohol into the mixed solution, stirring and dispersing at the rotating speed of 500rpm at 35 ℃ for 45min to form emulsion, introducing nitrogen into a reactor, adding 2.6mL of ammonia water, heating the reactor to 80 ℃, and continuously stirring and reacting at the rotating speed of 300rpm for 6 h; and after the reaction is finished, cooling to room temperature, filtering, washing with absolute ethyl alcohol, and drying to obtain the double-shell gradient phase change microcapsule with the average particle size of 300 mu m, wherein the phase change interval is 28-45 ℃.
2. A preparation method of a double-shell gradient phase change microcapsule is characterized by comprising the following steps:
mixing 20g of paraffin with the phase transition temperature of 65 ℃ and 30mL of tetraethoxysilane at 70 ℃ to form transparent mixed liquid, then adding 5g of hexadecyl trimethyl ammonium bromide, 250mL of deionized water and 177mL of absolute ethyl alcohol, emulsifying the mixed liquid for 15min at 70 ℃ by using an ultrasonic processor, then transferring the obtained mixed liquid into a reaction kettle with mechanical stirring, adding 5.2mL of ammonia water into the reaction kettle, and continuously stirring and reacting at 70 ℃ at the rotating speed of 1500rpm for 24 h; after the reaction is finished, filtering, washing with absolute ethyl alcohol, and drying to obtain a microcapsule A with the average particle size of 10 microns, wherein the content of the core material is 45%, and the phase transition temperature is 65 ℃;
mixing 10g of paraffin with the phase transition temperature of 35 ℃ and 15mL of tetraethoxysilane at 40 ℃ to form transparent mixed liquid, then adding 6g of the microcapsule A to form suspension, then adding 1mL of methacryloxypropyl trimethoxysilane and 5mL of acrylonitrile monomer, and continuously and uniformly mixing at 40 ℃; then adding 2.46g of hexadecyl trimethyl ammonium bromide, 2mL of 0.015mol/L ferrous ammonium sulfate, 0.4mL of 0.1mol/L sulfuric acid, 250mL of deionized water and 200mL of absolute ethyl alcohol into the mixed solution, stirring and dispersing for 60min at the rotating speed of 700rpm at 50 ℃ to form emulsion, then introducing nitrogen into the reactor, adding 2.6mL of ammonia water, continuing stirring and reacting for 4h at the rotating speed of 300rpm, and then adding 1% sodium carbonate solution to stop the reaction; and after the reaction is finished, cooling to room temperature, filtering, washing with absolute ethyl alcohol, and drying to obtain the double-shell gradient phase change microcapsule with the average particle size of 200 mu m, wherein the phase change interval is 35-65 ℃.
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