CN113926400A - Microcapsule preparation method and cold storage agent - Google Patents
Microcapsule preparation method and cold storage agent Download PDFInfo
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- CN113926400A CN113926400A CN202010601883.7A CN202010601883A CN113926400A CN 113926400 A CN113926400 A CN 113926400A CN 202010601883 A CN202010601883 A CN 202010601883A CN 113926400 A CN113926400 A CN 113926400A
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- 239000011232 storage material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 230000002378 acidificating effect Effects 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000012782 phase change material Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000012295 chemical reaction liquid Substances 0.000 claims description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 229920000877 Melamine resin Polymers 0.000 claims description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 239000008098 formaldehyde solution Substances 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000011162 core material Substances 0.000 abstract description 25
- 239000002826 coolant Substances 0.000 abstract description 13
- 238000004781 supercooling Methods 0.000 abstract description 9
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- 238000002474 experimental method Methods 0.000 abstract description 5
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- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
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- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
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- 230000002745 absorbent Effects 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 239000011343 solid material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The application discloses a microcapsule preparation method and a coolant, and the method comprises the following steps: preparing an acidic emulsifier solution; preparing a prepolymer solution; dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio, and reacting the prepolymer solution with the emulsifier solution for a preset time to obtain a first reaction solution; adjusting the pH value of the first reaction solution to be alkaline to obtain a microcapsule solution; and concentrating the microcapsule solution to obtain the microcapsule. According to the method, an acidic emulsifier solution is prepared, an emulsifier solution is dripped into the prepolymer solution, the reaction speed is controlled by controlling the dripping speed of the prepolymer solution when the prepolymer solution reacts with the emulsifier solution under an acidic condition, and the problems that the generated microcapsules are sticky and the wall materials are too thick to influence the release of core materials wrapped by the wall materials are avoided. Experiments prove that the supercooling degree of the cold storage agent can be effectively reduced, the freezing efficiency of the cold storage agent is improved, and energy is saved.
Description
Technical Field
The application relates to the field of phase-change materials, in particular to a microcapsule preparation method and a coolant.
Background
A Phase Change Material (PCM-Phase Change Material) is a Material that absorbs, stores, and releases heat energy using Phase Change latent heat, and absorbs and releases heat during a Phase Change process as Phase Change latent heat while maintaining its own temperature, and has been widely used in the field of energy storage and temperature control.
In fresh logistics packaging, phase change materials are usually used as main components to prepare cold storage agents such as ice bags, ice boxes and the like to control the ambient temperature in the packaging, so that the fresh products are guaranteed. However, the existing cold-storage agent often has a supercooling phenomenon in the using process. The supercooling of the coolant causes problems such as waste of energy and delay of the cold storage function.
Disclosure of Invention
The embodiment of the application provides a microcapsule preparation method and a cold storage agent, and aims to solve the problems that in the prior art, the microcapsule preparation process is sticky, the wall material of the microcapsule is too thick, and the release of a core material is influenced.
In a first aspect, embodiments herein provide a method for preparing microcapsules, the method comprising: preparing an acidic emulsifier solution;
preparing a prepolymer solution;
dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio to enable the prepolymer solution and the emulsifier solution to react for a preset time to obtain a first reaction solution;
adjusting the pH value of the first reaction solution to be alkaline to obtain a microcapsule solution;
and concentrating the microcapsule solution to obtain the microcapsule.
Further, the preparing the acidic emulsifier solution comprises:
mixing a preset emulsifier and deionized water according to a first preset proportion to obtain a second reaction solution;
adding a preset phase change material reaching nano dispersion into the second reaction liquid to obtain a third reaction liquid;
shearing and emulsifying the third reaction solution to obtain a fourth reaction solution;
and adjusting the fourth reaction solution to be acidic to obtain the acidic emulsifier solution.
Further, the preset emulsifier is a composite emulsifier, and the composite emulsifier comprises a plurality of different emulsifiers.
Further, the adding the preset phase change material reaching the nano dispersion into the second reaction liquid includes:
performing ultrasonic oscillation on the preset phase-change material to obtain the preset phase-change material reaching nano dispersion;
and dripping the preset phase change material reaching the nano dispersion into the second reaction liquid.
Further, the adjusting the fourth reaction solution to be acidic includes:
and adding an acetic acid solution into the fourth reaction liquid to adjust the pH value of the fourth reaction liquid to 3-5.
Further, the preparation of the prepolymer solution comprises the following steps:
mixing melamine, formaldehyde solution and deionized water according to a second preset proportion to obtain fifth reaction liquid;
adjusting the fifth reaction liquid to be alkaline, so that the melamine and the formaldehyde solution are subjected to prepolymer reaction in an alkaline environment to obtain a sixth reaction liquid;
and stirring the sixth reaction solution until the sixth reaction solution is transparent.
Further, the adjusting of the fifth reaction solution to be alkaline includes:
and adding a triethanolamine solution into the fifth reaction solution to ensure that the pH value of the sixth reaction solution is 7.5-9.
Further, the step of dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio to allow the prepolymer solution to react with the emulsifier solution for a preset time to obtain a first reaction solution includes:
and dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio at a preset speed, so that the prepolymer solution and the emulsifier react for a preset time, and stirring the emulsifier solution at a preset stirring speed in the dripping process to obtain a first reaction liquid.
Further, the concentrating the microcapsule solution to obtain the microcapsule comprises:
under the vacuum condition, washing the microcapsule solution for multiple times by using water and alcohol, and filtering to obtain a particle filtrate of the microcapsule;
drying the particle filtrate of the microcapsule for 11h-13h at the temperature of 40-50 ℃ to obtain the microcapsule.
In a second aspect, the present application further provides a coolant, wherein the coolant comprises microcapsules obtained by the microcapsule preparation method according to any one of the above.
According to the microcapsule preparation method and the cold storage agent provided by the embodiment of the application, the acidic emulsifier solution is prepared, and the prepolymer solution is dripped into the acidic emulsifier solution. The reaction speed is controlled by controlling the dripping speed of the prepolymer solution, and the phenomenon that the generated microcapsules are adhered and the wall materials are too thick to influence the release of the core materials wrapped by the wall materials can be avoided. After the cold storage agent is prepared according to the microcapsules, experiments prove that the supercooling degree of the cold storage agent can be effectively reduced, the freezing efficiency is improved, and energy is saved.
Drawings
The technical solution and other advantages of the present application will become apparent from the detailed description of the embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a schematic flow chart of an embodiment of a microcapsule preparation method provided in the embodiments of the present application;
FIG. 2 is a schematic flow chart illustrating one embodiment of a process for preparing an acidic emulsifier solution provided in embodiments herein;
FIG. 3 is a schematic flow chart of an embodiment of preparing a prepolymer solution according to the embodiments of the present disclosure;
fig. 4 is a schematic flow chart of an embodiment of the present application for concentrating microcapsules.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may comprise direct contact of the first and second features, or may comprise contact of the first and second features not directly but through another feature in between. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.
The process of transformation of materials in solid, liquid and gas states is called phase change; while the material absorbs or releases heat during the phase change process, the object made of the phase change material maintains a constant temperature. In the field of fresh logistics packaging, phase-change materials are generally used as main components of cold storage agents such as ice bags and ice boxes and are used for controlling the environment temperature in packaging so as to achieve the quality guarantee effect of fresh products.
When the phase change material is in the phase change process, the phenomenon that the actual crystallization temperature of the phase change material is lower than the theoretical crystallization temperature is called as a supercooling phenomenon; the temperature difference between the actual crystallization temperature and the theoretical crystallization temperature is called the supercooling degree, and the coolant which can be obtained after the phase change material is used has many problems in the actual use process. For example: in the freezing process of the cold storage agent, when the ambient temperature reaches the phase change point, the cold storage agent still can not be frozen, the temperature needs to be continuously reduced and kept for a period of time until the supercooled state is broken, and the phase change material begins to crystallize, so that energy waste is caused. For another example, when the ambient temperature reaches the phase transition point of the coolant, the phase transition of the coolant is delayed due to the supercooling degree, so that the anti-freezing effect is delayed and the anti-freezing failure is caused.
The microcapsule is a micro-container or a wrapper with a polymer or inorganic wall, and is used by making a phase change material into a microcapsule in the actual use process of the phase change material. The microcapsule made of the phase-change material can reduce the volatility of the phase-change material, improve the stability of the phase-change material and control the release speed of the phase-change material. The microcapsule structure generally comprises a core material and a wall material, wherein in the microcapsule made of the phase-change material, the core material is generally the phase-change material, the wall material wraps the core material and is formed on the outer side of the core material, and the core material can be released from the microcapsule. Therefore, the phase-change material can be selected to prepare the microcapsule, thereby achieving the effect of temperature control and fresh keeping. However, in the microcapsule prepared by the microcapsule preparation method in the prior art, the release of the core material wrapped by the wall material is influenced due to the thick wall material, so that the temperature-control fresh-keeping effect is influenced.
An embodiment of the present application provides a method for preparing a microcapsule, and as shown in fig. 1, is a schematic flow chart of an embodiment of the method for preparing a microcapsule provided in the embodiment of the present application, and the method for preparing a microcapsule includes:
11. an acidic emulsifier solution was prepared.
12. Preparing a prepolymer solution.
13. And (3) dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio, so that the prepolymer solution and the emulsifier solution react for a preset time to obtain a first reaction solution.
14. And adjusting the pH value of the first reaction solution to be alkaline to obtain a microcapsule solution.
15. And concentrating the microcapsule solution to obtain the microcapsule.
According to the microcapsule preparation method provided by the embodiment of the application, the acidic emulsifier solution is prepared, the prepolymer solution is dripped into the acidic emulsifier solution, and through the test of the inventor, the emulsifier solution is acidic, so that when the prepolymer solution is dripped into the acidic emulsifier solution, the prepolymer solution is fully contacted with the acidic emulsifier solution, the reaction rate is higher, and the reaction is more sufficient. The reaction speed is controlled by controlling the dripping speed of the prepolymer solution, and the phenomenon that the generated microcapsules are adhered and the wall materials are too thick to influence the release of the core materials wrapped by the wall materials can be avoided. After the cold storage agent is prepared according to the microcapsules, experiments prove that the supercooling degree of the cold storage agent can be effectively reduced, the freezing efficiency is improved, and energy is saved.
Among others, in the embodiments of the present application, the microcapsules may be prepared using an in-situ polymerization method. In the in-situ polymerization method, a reactive monomer (or a soluble prepolymer thereof) and a catalyst are all added into a dispersed phase (or a continuous phase), and a core material is the dispersed phase. Since the monomer (or prepolymer) is kosher in a single phase and its polymer is insoluble throughout the mixed system, all polymerization occurs on the dispersed phase core. And after the reaction is started, the monomers are prepolymerized, the prepolymer is polymerized, and after the polymerization size of the prepolymer is gradually increased, the prepolymer is deposited on the surface of the core material.
In the examples of the present application, it is necessary to prepare the core material and the wall material of the microcapsule separately, i.e., to prepare a solution including the core material and a solution including the wall material separately. In some embodiments of the present application, it is desirable to prepare an acidic emulsifier solution in which the core material is dissolved.
Specifically, as shown in fig. 2, for a schematic flow chart of an embodiment of preparing an acidic emulsifier solution provided in the embodiment of the present application, the preparing an acidic emulsifier solution including a core material may include:
21. and mixing a preset emulsifier and deionized water according to a first preset proportion to obtain a second reaction solution.
22. And adding the preset phase-change material reaching the nano dispersion into the second reaction liquid to obtain a third reaction liquid.
23. And shearing and emulsifying the third reaction liquid to obtain a fourth reaction liquid.
24. And (4) adjusting the fourth reaction solution to be acidic to obtain an acidic emulsifier solution.
In the examples of the present application, the emulsifier solution is prepared in order to dissolve the core material substance in the emulsifier, forming spherical and dispersed small particle substances. The prepared emulsifier solution is acidic, so that the problem that the release of the core material is influenced due to the fact that the wall material wrapped on the outer side of the core material is too thick is avoided.
Specifically, in some embodiments of the present disclosure, a predetermined emulsifier material may be mixed with deionized water according to a first predetermined ratio to obtain a second reaction solution. Wherein the emulsifier is a compound which forms an undefined emulsion from a mixture of two or more immiscible components. In the embodiment of the present application, the emulsifier can fuse the core material (i.e., the phase change material) with the deionized water to obtain a stable mixed solution.
Firstly, mixing a preset emulsifier with deionized water according to a first preset proportion to obtain a second reaction solution; and adding a preset phase-change material into the second reaction liquid to obtain a third reaction liquid.
In the embodiment of the present application, the predetermined emulsifier may be a complex emulsifier, that is, the emulsifier mixed with the deionized water is a mixture of a plurality of emulsifiers. Wherein the emulsifier can be a mixture of triton and alkylbenzene sulfonic acid. Alkyl benzene sulfonic acid is a molecule having a general formula of R-C6H 4 (benzene ring) -SO 3H, wherein R is generally a hydrocarbon of 10-20, and may be a straight chain or a branched chain. In the embodiment of the application, dodecylbenzene sulfonic acid can be selected as an emulsifier, namely a mixture of triton and dodecylbenzene sulfonic acid is selected as the emulsifier to be mixed with deionized water; and the volume ratio of the triton to the dodecylbenzene sulfonic acid can be 1:1.
in the embodiment of the present application, the first predetermined ratio may be 1:200, that is, the volume ratio of the mixed emulsifier and the deionized water is 1: 200.
After the mixed emulsifier and the deionized water are mixed, the reaction is carried out under certain conditions to obtain a second reaction solution. Specifically, after the mixed emulsifier and the deionized water are mixed, the mixed solution is stirred at the temperature of 45-55 ℃, so that the emulsifier is better dispersed in the deionized water. Specifically, the mixed solution may be stirred at a temperature of 50 ℃ for 15min to obtain a second reaction solution.
In the embodiment of the application, different emulsifiers can be dispersed in deionized water, and experiments prove that the dispersing effect of the composite emulsifier solution is better, so that the emulsifier obtained by mixing various emulsifiers can be selected in the embodiment of the application. Meanwhile, for different emulsifiers, the reaction temperature and the stirring time can be different after the emulsifiers are mixed with the deionized water, and the emulsifiers are uniformly dispersed in the deionized water.
After the second reaction solution is prepared, a preset phase-change material is required to be dispersed in the second reaction solution. In the embodiment of the application, the preset phase-change material can be subjected to ultrasonic oscillation to obtain nano-level dispersion of the preset phase-change material; and mixing the preset phase-change material reaching the nano dispersion with the second reaction liquid, so that the phase-change material can be more uniformly dispersed in the second reaction liquid, and the microcapsule can be conveniently prepared subsequently.
In the embodiment of the application, different phase-change materials can be selected according to different temperature control requirements. A common phase change material is water, which absorbs or releases heat during the transition between solid and liquid states and changes state for a period of time, rather than reaching the phase change point.
In the embodiment of the present application, water may be selected as the predetermined phase change material; meanwhile, the volume ratio of the deionized water to the water can reach 4: 1. And the preset phase-change material is subjected to ultrasonic vibration, namely the aqueous solution is subjected to ultrasonic vibration, so that the water molecules are dispersed in a nanometer mode. Meanwhile, after the preset phase change material, i.e., water, reaching the nano dispersion is added to the second reaction solution to obtain a third reaction solution, the third reaction solution needs to be sheared and emulsified to obtain a fourth reaction solution.
Specifically, after the third reaction solution is obtained, the third reaction solution is subjected to shearing emulsification under certain reaction conditions, so that the phase-change material and the emulsifier can better form a uniform solution. The shearing emulsification is kinetic energy brought by high-shearing linear velocity and high-frequency mechanical effect generated under high-speed rotation, so that various materials are subjected to comprehensive actions of strong mechanical and hydraulic shearing, centrifugal extrusion, liquid layer friction, impact tearing, turbulent flow and the like in narrow gaps of a stator and a rotor, so that immiscible solid phase, liquid phase and gas phase are instantly, uniformly and finely dispersed and emulsified under the combined action of a corresponding mature process and a proper amount of additives, and finally a stably dispersed product is obtained through high-frequency cyclic reciprocation.
In the embodiment of the application, since the molecules in the solution are more active and easier to separate due to the high temperature, the third reaction solution can be subjected to high-speed shear emulsification at 60-75 ℃, and the rotation speed can be 5000-. Specifically, the third reaction solution may be sheared and emulsified at a speed of 6000rpm/min at 70 ℃ to obtain a fourth reaction solution.
Similarly, the temperature can be selected to be 60, 65 ℃, 75 ℃ and the like, and the rotating speed can be selected to be 5500rpm/min, 7000rpm/min, 8000rpm/min and the like. The selection of the temperature and the rotation speed can be changed according to the actual requirement and the selection of the raw material, and is not limited in any way.
And (3) adjusting the fourth reaction solution to be acidic after preparing the fourth reaction solution to obtain an acidic emulsifier solution. In the embodiment of the present application, an acetic acid solution may be added to the fourth reaction solution to adjust the PH of the fourth reaction solution to 3 to 5. In the above embodiment, the concentration of the acetic acid solution may be 10%.
In other embodiments of the present application, other different acidic solutions with different concentrations may be selected to adjust the PH of the fourth reaction solution, and no matter what solution is selected, the adjusted emulsifier solution is acidic. Meanwhile, the added acidic solution cannot react with the fourth reaction solution, which affects the components in the fourth reaction solution.
In the examples of the present application, since the acidic solution volatilizes, it is necessary to first shear and emulsify the third reaction solution to obtain the fourth reaction solution, and then adjust the fourth reaction solution to be acidic.
After the emulsifier solution containing the phase-change material is prepared, a prepolymer solution needs to be prepared, and the prepolymer solution can be solidified under certain conditions to form a wall material of the microcapsule. As shown in fig. 3, a schematic flow chart of an embodiment of the preparation of a prepolymer solution provided in the embodiments of the present application, the preparation of the prepolymer solution may include:
31. and mixing the melamine, the formaldehyde solution and the deionized water according to a second preset proportion to obtain a fifth reaction solution.
32. And adjusting the fifth reaction liquid to be alkaline, so that the melamine and the formaldehyde solution are subjected to prepolymer reaction in an alkaline environment to obtain a sixth reaction liquid.
33. Stirring the sixth reaction solution until the sixth reaction solution is transparent.
In the examples of the present application, melamine, formaldehyde solution and deionized water were selected to prepare the fifth reaction liquid. Specifically, melamine, formaldehyde solution and deionized water are mixed according to a second preset proportion to obtain a fifth reaction solution. Since melamine is solid at normal temperature, in the examples of the present application, melamine needs to be dissolved, and after obtaining a melamine solution, mixing is performed.
The volume ratio of the melamine solution, the formaldehyde solution and the deionized water which are mixed can be 1:1.5-2.5: 2-3; the proportion of the third reaction solution, the fourth reaction solution and the fourth reaction solution can be selected manually, and different proportions can affect the stability of the fifth reaction solution and the stability of the wall material formed by the prepolymer solution in a forming way. In one embodiment of the present application, the ratio of the melamine solution, the formaldehyde solution and the deionized water solution may be 7:13: 14. Meanwhile, in the embodiment of the present application, the concentration of the formaldehyde solution may be 35% to 45%. Specifically, the concentration of the formaldehyde solution may be 37%.
After the fifth reaction solution is obtained, the fifth reaction solution needs to be adjusted to be alkaline, so that the melamine solution and the formaldehyde solution are subjected to prepolymer reaction in an alkaline environment to obtain a sixth reaction solution. In an embodiment of the present application, adjusting the fifth reaction solution to be alkaline so that the melamine solution and the formaldehyde solution perform a prepolymer reaction in an alkaline environment may include: and adding a triethanolamine solution into the fifth reaction liquid to change the fifth reaction liquid into an alkaline solution, wherein the melamine and the formaldehyde in the fifth reaction liquid are subjected to prepolymer reaction in an alkaline environment. The prepolymer is a high molecular polymer, and the triethanolamine solution is added to improve the reaction environment of melamine and formaldehyde; meanwhile, the prepolymer obtained after the reaction of the triethanolamine and the water-soluble organic solvent can only exist stably in an alkaline environment, the triethanolamine is an organic alkali, and the fifth reaction liquid can be maintained in the alkaline environment when the triethanolamine is added into a reaction system, so that the stability of the generated prepolymer is ensured.
After the sixth reaction solution is obtained, because the prepolymer obtained by the reaction of melamine and formaldehyde is a soluble substance, the sixth reaction solution needs to be stirred and statically precipitated until the sixth reaction solution is transparent.
After the emulsifier solution and the prepolymer solution are prepared respectively, the microcapsule solution can be prepared by using the emulsifier solution and the prepolymer solution. In an embodiment of the present application, preparing the microcapsule solution may include: and (3) dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio, so that the prepolymer solution and the emulsifier solution react for a preset time to obtain a first reaction solution. In the first reaction solution, microcapsules are already formed, but the first reaction solution needs to be adjusted to be alkaline so as to terminate the reaction of the prepolymer solution and the emulsifier solution, and finally, a microcapsule solution is obtained.
Specifically, in the examples of the present application, when preparing the microcapsule, it is necessary to drop the prepolymer solution into the emulsifier solution. Since the emulsifier solution is acidic and the prepolymer solution is basic, both need to react under acidic conditions, it is necessary to add the basic prepolymer solution to the acidic emulsifier solution rather than to add the emulsifier solution to the prepolymer solution or simply to mix the two. Meanwhile, in the process of dripping the emulsifier solution into the prepolymer solution, the added prepolymer solution can continuously react with the emulsifier solution to obtain the microcapsule because the emulsifier solution is acidic.
In the embodiment of the application, not only the alkaline prepolymer solution needs to be dropped into the acidic emulsifier solution, but also the emulsifier solution needs to be continuously stirred in the dropping process, so that the alkaline prepolymer solution and the emulsifier solution are fully contacted and react. In embodiments of the present application, the emulsifier solution may be stirred at a speed of 500rpm/min to 750 rpm/min. The stirring speed has a great influence on the forming of the microcapsule product, the stirring speed is also related to the equipment, and in the actual production process, the stirring speed can be adjusted according to the actual situation.
Since the reaction between the emulsifier solution and the prepolymer solution is carried out under acidic conditions, after the emulsifier solution and the prepolymer solution react for a preset time, an alkaline solution needs to be added into the reacted mixed solution to adjust the pH value of the mixed solution to be alkaline, so as to finish the whole reaction.
Specifically, in some embodiments of the present disclosure, after the reaction lasts for 70 to 100 minutes, a triethanolamine solution may be added to the mixed solution after the reaction of the emulsifier solution and the prepolymer solution, and the PH of the mixed solution after the reaction of the emulsifier solution and the prepolymer solution may be adjusted to 8.5 to 9.5, so that the reaction is terminated.
In the above embodiment, after the triethanolamine solution is added, the emulsifier solution and the prepolymer solution need to be reacted for a certain time, so that the emulsifier solution and the prepolymer solution can be reacted fully and completely to obtain the final microcapsule solution.
In one embodiment of the present application, the prepolymer solution and the acidic emulsifier solution may be set to a volume ratio of 1:1, the prepolymer solution is slowly dropped into the emulsifier solution at a rate of 0.3-0.6ml/min, and the emulsifier solution is stirred at a rate of 600rpm/min during the dropping of the prepolymer solution. And when the reaction is carried out for 90min, adding a triethanolamine solution into the mixed solution after the reaction, adjusting the pH of the mixed solution to 9.5, and continuing the reaction for 30min to ensure that the prepolymer solution and the emulsifier solution are fully and completely reacted. If the mixed solution is always an acidic solution, the prepolymer solution and the emulsifier solution can keep reacting all the time, so that the generated microcapsules are sticky, and the wall materials of the microcapsules are too thick.
In the embodiment of the present application, since the alkaline prepolymer solution is dropped into the acidic emulsifier solution, the prepolymer solution and the emulsifier solution need to react under an acidic condition, and thus the reaction speed can be controlled by controlling the dropping speed of the prepolymer solution. Meanwhile, the prepolymer solution and the emulsifier solution react, namely, the prepolymer in the prepolymer solution is deposited on the surface of the phase-change material to form a wall material of the microcapsule, and the phase-change material is a core material of the microcapsule; therefore, after the reaction speed is controlled, the thickness of the prepolymer deposited on the surface of the phase-change material can be controlled; the dripping speed of the prepolymer solution can be controlled, so that the thickness of the wall material of the microcapsule is controlled, the release of the core material of the microcapsule in use is further influenced, and the influence of the over-thick wall material on the release of the core material is avoided.
It should be noted that, when preparing the prepolymer solution and the microcapsule solution, the triethanolamine solution is added to adjust the ph value of the solutions, and the concentrations of the triethanolamine solutions added twice may be the same or different, and only the ph value of the mixed solution needs to be adjusted to meet the required requirements. In practice, triethanolamine solutions of the same concentration are usually used.
After the microcapsule solution is obtained, the microcapsule solution is further subjected to concentration treatment to obtain the microcapsule. Specifically, as shown in fig. 4, a schematic flow chart of an embodiment of the present application for concentrating microcapsules is provided; in some embodiments of the present application, concentrating the microcapsules to obtain microcapsules may include:
41. washing the microcapsule solution with water and alcohol under vacuum for several times to obtain microcapsule granule filtrate.
42. Drying the microcapsule particle filtrate for 11-13 h at 40-50 deg.C to obtain microcapsule.
In one embodiment of the present application, the concentrating of the microcapsule solution to obtain microcapsules may include: washing the microcapsule solution for many times by using water and alcohol in a vacuum device to obtain a particle filtrate of the microcapsule; the particulate filter of the microcapsules was placed in an oven at 45 ℃ for 12h to obtain the microcapsules of the examples of the present application.
Unless otherwise specified, the states of the various substances described in the examples of the present application are all states at normal temperature. For example, the mixed emulsifier is liquid at normal temperature, and the ratio of the plurality of emulsifiers in the mixed emulsifier is volume ratio. For solid materials at normal temperature such as melamine, a melamine solution is obtained and then the mixture ratio by volume is carried out.
The application also provides a cold-storage agent, which comprises the microcapsule prepared by the microcapsule preparation method.
In some embodiments of the present application, after the microcapsules are prepared by the foregoing microcapsule preparation method, the microcapsules are further used to prepare a coolant. Specifically, different phase-change materials can be selected according to different temperature control requirements, meanwhile, the phase-change materials, water-absorbent resin and other materials are mixed according to a proportion, and meanwhile, the phase-change microcapsules prepared according to the microcapsule preparation method are added to obtain the cold storage agent.
In the embodiments of the present application, the proportions of the phase change material, water absorbent resin, and the like in the coolant may be changed according to actual use conditions, and are not limited herein.
Experiments of inventors can find that the cooling rate is accelerated by adding the phase change microcapsule prepared by the microcapsule preparation method. In the actual use process, the time of cooling crystallization of the coolant is shortened, the freezing efficiency is improved, energy can be effectively saved, and the supercooling phenomenon of the coolant is slowed down.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The above detailed description is made on a method for preparing a microcapsule and a microcapsule provided in the embodiments of the present application, and a coolant prepared by using the microcapsule, and a specific example is applied in the detailed description to explain the principle and the implementation manner of the present application, and the description of the above embodiments is only used to help understanding the technical scheme and the core idea of the present application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (10)
1. A method of making microcapsules, the method comprising:
preparing an acidic emulsifier solution;
preparing a prepolymer solution;
dripping the prepolymer solution into the emulsifier solution according to a preset volume ratio to enable the prepolymer solution and the emulsifier solution to react for a preset time to obtain a first reaction solution;
adjusting the pH value of the first reaction solution to be alkaline to obtain a microcapsule solution;
and concentrating the microcapsule solution to obtain the microcapsule.
2. The method of claim 1, wherein the preparing an acidic emulsifier solution comprises:
mixing a preset emulsifier and deionized water according to a first preset proportion to obtain a second reaction solution;
adding a preset phase change material reaching nano dispersion into the second reaction liquid to obtain a third reaction liquid;
shearing and emulsifying the third reaction solution to obtain a fourth reaction solution;
and adjusting the fourth reaction solution to be acidic to obtain the acidic emulsifier solution.
3. The method for preparing a microcapsule according to claim 2, wherein the predetermined emulsifier is a complex emulsifier, and the complex emulsifier comprises a plurality of different emulsifiers.
4. The method for preparing microcapsules according to claim 2, wherein the adding the predetermined phase-change material to be nano-dispersed into the second reaction liquid comprises:
performing ultrasonic oscillation on the preset phase-change material to obtain the preset phase-change material reaching nano dispersion;
and dripping the preset phase change material reaching the nano dispersion into the second reaction liquid.
5. The method of claim 2, wherein said adjusting said fourth reaction solution to be acidic comprises:
and adding an acetic acid solution into the fourth reaction liquid to adjust the pH value of the fourth reaction liquid to 3-5.
6. The method of claim 1, wherein the preparing a prepolymer solution comprises:
mixing melamine, formaldehyde solution and deionized water according to a second preset proportion to obtain fifth reaction liquid;
adjusting the fifth reaction liquid to be alkaline, so that the melamine and the formaldehyde solution are subjected to prepolymer reaction in an alkaline environment to obtain a sixth reaction liquid;
and stirring the sixth reaction solution until the sixth reaction solution is transparent.
7. The method of claim 6, wherein the adjusting the fifth reaction solution to be basic comprises:
and adding a triethanolamine solution into the fifth reaction solution to ensure that the pH value of the sixth reaction solution is 7.5-9.
8. The method for preparing microcapsules of claim 1, wherein the dropping the prepolymer solution into the emulsifier solution according to a predetermined volume ratio to allow the prepolymer solution to react with the emulsifier solution for a predetermined time period to obtain a first reaction solution comprises:
and (3) dripping the prepolymer solution into the emulsifier solution at a preset speed according to a preset volume ratio, and stirring the emulsifier solution at a preset stirring speed in the dripping process to obtain a first reaction solution.
9. The method for preparing microcapsules according to claim 1, wherein the concentrating of the microcapsule solution to obtain the microcapsules comprises:
under the vacuum condition, washing the microcapsule solution for multiple times by using water and alcohol, and filtering to obtain a particle filtrate of the microcapsule;
drying the particle filtrate of the microcapsule for 11h-13h at the temperature of 40-50 ℃ to obtain the microcapsule.
10. A cold-storage agent comprising microcapsules prepared by the method of preparing microcapsules according to any one of claims 1 to 9.
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