CN109679585B - Phase-change microcapsule synthesized by adopting photocuring method and preparation method thereof - Google Patents
Phase-change microcapsule synthesized by adopting photocuring method and preparation method thereof Download PDFInfo
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- CN109679585B CN109679585B CN201811550763.8A CN201811550763A CN109679585B CN 109679585 B CN109679585 B CN 109679585B CN 201811550763 A CN201811550763 A CN 201811550763A CN 109679585 B CN109679585 B CN 109679585B
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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
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
Abstract
The invention relates to a phase-change microcapsule synthesized by adopting a photocuring method and a preparation method thereof, wherein the method comprises the steps of dissolving metal oxide nanoparticles in deionized water, and performing dispersion treatment to form a suspension as a water phase; mixing paraffin, methyl methacrylate, a cross-linking agent pentaerythritol tetraacrylate and a light curing agent, and heating to form an oil phase; mixing the water phase and the oil phase, and emulsifying by using an emulsifying machine to obtain an emulsified suspension; irradiating the emulsified suspension with ultraviolet light to perform photocuring reaction, and filtering and drying the emulsified suspension after the reaction to form the phase-change microcapsule; the temperature of the drying treatment process is not higher than the paraffin solidification temperature. Compared with the prior art, the invention has the advantages of high reaction efficiency, environment-friendly additive, high hot melting, good heat conductivity, simple preparation process, low manufacturing cost and the like, and can be applied to the fields of energy storage, medical treatment, buildings and the like.
Description
Technical Field
The invention relates to a preparation method of a hot-melt phase-change microcapsule with high thermal conductivity, in particular to a phase-change microcapsule synthesized by adopting a photocuring method and a preparation method thereof, belonging to the field of organic phase-change materials.
Background
The phase change energy storage technology is a technology for realizing energy storage based on absorption or release of heat in a material phase change process, and is widely applied to the field of industrial and enterprise energy recovery. The phase change energy storage material is a substance with a specific function which can not only generate substance phase change at a specified temperature or temperature range (phase change temperature), but also can absorb or release a large amount of phase change latent heat, and can be used for storing heat and storing cold. Compared with sensible heat energy storage, the phase change energy storage has high energy storage density, and the energy storage and release are easily controlled and approach to isothermal process, so that the phase change energy storage is very suitable for solving the problems of energy supply and demand imbalance. Has great significance for improving the energy utilization rate and the energy structure. Therefore, the development of high-performance phase-change materials becomes a core technology of phase-change energy storage. The microcapsule technology is widely applied to the encapsulation of the phase-change material, solves the leakage problem of the phase-change material in the using process, and is particularly applied to the scene of building envelope structures. However, the hydrothermal polymerization reaction adopted in the traditional phase-change microcapsule preparation process has the defects of slow reaction speed and unfriendly additive environment. The photocuring is a new curing technology, adopts the photocuring agent to form curing under the irradiation of ultraviolet light, and has the advantages of simple process, high efficiency and lower cost.
Patent CN105498652A discloses a method for preparing phase-change microcapsules by photo-curing, in which formaldehyde is used as a solvent, which is relatively environmentally-friendly. Therefore, how to develop the phase change microcapsule which is green and environment-friendly, has low cost and simple preparation process, and has high hot melting and high thermal conductivity has important significance. The preparation process is developed and manufactured based on the concepts.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a phase-change microcapsule synthesized by adopting a photocuring method and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: a preparation method for synthesizing phase-change microcapsules by adopting a photocuring method comprises the following steps:
dissolving metal oxide nano particles in deionized water, and performing dispersion treatment to form a suspension as a water phase;
mixing paraffin, Methyl Methacrylate (MMA), pentaerythritol tetraacrylate (PETRA) and light curing agent Photonitiator, and heating to form oil phase; wherein the heating temperature is such that the paraffin is in a molten state.
Mixing the water phase and the oil phase, and emulsifying by using an emulsifying machine to obtain an emulsified suspension;
the emulsifier is preferably a high-speed emulsifier, the rotation speed of the emulsifier determines the size of the formed phase-change microcapsules, and the higher the rotation speed, the smaller the particle size of the formed microcapsules.
Irradiating the emulsified suspension with ultraviolet light to perform photocuring reaction, and filtering and drying the emulsified suspension after the reaction to form the phase-change microcapsule; the temperature of the drying treatment process is not higher than the paraffin solidification temperature.
Under the drive of ultraviolet light, the hybrid shell of the microcapsule is cured, the drying treatment can be carried out in an oven, and the drying time is set to be 24h, thus forming the PMMA/metal oxide @ paraffin phase-change microcapsule
The metal oxide is selected from Al2O3、SiO2Or TiO2One or more of them.
The mass of the metal oxide is 1-20% of that of the paraffin.
Preferably, the metal oxide mass is 10% of the paraffin mass.
The light curing agent is a light curing agent 819.
The mass ratio of the paraffin, the methyl methacrylate, the cross-linking agent and the light curing agent is 1-4: 2-5: 0.4-1.0: 0.1-0.25.
The rotation speed of the emulsifying machine is 5000-20000 revolutions, and the emulsifying time is 3-15 minutes, preferably 5 minutes.
In the process of irradiating the emulsified suspension by the ultraviolet light, the power of the ultraviolet light is 5-100W, the wavelength is 254-420 nm, and the irradiation time is 5-30 minutes.
Preferably, during the process of irradiating the emulsified suspension by the ultraviolet light, the power of the ultraviolet light is 60W, the wavelength is 365nm, and the irradiation time is 10 minutes.
The phase-change microcapsule is prepared by the preparation method, the wall material of the phase-change microcapsule is a hybrid wall of polymethyl methacrylate and metal oxide, the core material is paraffin, and the average particle size is 3-16 mu m.
The invention adopts the hybrid mixed wall of polymethyl methacrylate and metal oxide as the shell of the phase-change microcapsule. The organic shell can enable the shell and the core (phase change material) to be well coated, so that the coating rate of the phase change material is improved, and the organic shell can reduce the heat conductivity coefficient of the phase change material. The inorganic shell can improve the heat-conducting property of the composite phase-change material, but the compatibility of the inorganic shell and the core is poor, and the coating rate of the phase-change microcapsule is reduced. By adopting an organic and inorganic hybridization mode, the compatibility of the shell and the core can be ensured, and the heat conduction of the phase change microcapsule can be enhanced. The capsule form can prevent the paraffin from leaking in the phase change process, improve the thermal conductivity and thermal stability of the phase change material and prolong the service life.
In the present invention, the size of the microcapsules is controlled by the rotation speed of the emulsifying machine. When the rotating speed of the emulsifying machine is lower than the lowest value of the invention, the formed microcapsules are difficult to form, and the formed particles are too large, which is not beneficial to the coating of the phase-change microcapsules. The rotating speed exceeding the rotating speed of the invention can cause the particle size of the phase-change microcapsule to be too small, and the coating rate can not be ensured.
The selection of the ultraviolet light wave band is directly connected with the selection of the light curing agent. The light curing agent can play the best curing role under the irradiation of ultraviolet light with specific wavelength. The light curing agent 819 used in the present invention achieves the best curing effect under the irradiation of ultraviolet light with the wavelength of 365 nm. The power of the ultraviolet lamp influences the light curing time. Too little power and longer curing time, but too much, can result in a less energy efficient manufacturing process.
Compared with the prior art, the invention provides the synthesis method of the phase-change microcapsule, which has the advantages of simple process, lower cost, short synthesis time and environment-friendly preparation process, the phase-change microcapsule prepared according to the invention is a phase-change microcapsule with the temperature of 0-60 ℃, has high heat value and large heat conductivity coefficient, and can be applied to the fields of energy storage, medical treatment, construction and the like.
Drawings
FIG. 1 is an SEM photograph of phase change microcapsules prepared according to the present invention;
FIG. 2 is a chart of DSC data of phase change microcapsules prepared in accordance with the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
(1) Commercial P25 (TiO)2)0.4g was dissolved in 50ml of deionized water, stirred and sonicated for 10 minutes to form a suspension, forming an aqueous phase.
(2) 3g of paraffin wax, 3g of Methyl Methacrylate (MMA), 0.6g of pentaerythritol tetraacrylate (PETRA) and 0.15g of Photonitiator 819 as a light curing agent were mixed, melted and stirred to form an oil phase, wherein the paraffin wax component was octadecane.
(3) And (3) mixing the oil phase in the step (2) with the water phase in the step (1), and emulsifying by using a high-speed emulsifying machine, wherein the rotating speed of the emulsifying machine is 17000 revolutions, and the emulsifying time is 5 minutes.
(4) And irradiating the emulsified suspension for 10 minutes under the irradiation of ultraviolet light (an ultraviolet lamp with the power of 60W and the wavelength of 365 nm).
(5) Filtering the particles in the suspension, and drying in an oven below the paraffin solidification temperature for 24 hours to form PMMA/TiO2@ n-octadecane phase change microcapsules.
The structure of the phase-change microcapsule prepared in this example is shown in fig. 1, and it can be seen that the phase-change microcapsule prepared in this example has a uniform individual and a uniform surface to which TiO is attached2。
Further, performance tests are performed on the phase-change microcapsule of the present embodiment, and a DSC curve of the phase-change microcapsule prepared in the present embodiment is shown in fig. 2, which shows that the enthalpy value of the phase-change microcapsule prepared in the present embodiment can reach 180J/g, the enthalpy value of pure paraffin is 267J/g, and the coating rate can reach 68%.
This example uses a photo-curing method to prepare phase-change microcapsules with mixed organic and inorganic shells. The microcapsule wall material of the invention is polymethyl methacrylate (PMMA) and TiO2The core material of the hybrid wall is composed of paraffin, and the particle size of the microcapsule is 3-16 mu m. By introducing the light curing agent, the polymerization reaction can be completed in a short time under the irradiation of ultraviolet light. The method solves the problems of low efficiency and unfriendly additive environment of the common hydrothermal polymerization reaction. The prepared organic and inorganic hybrid shell phase-change microcapsule has high hot melting and good heat conducting property, and can be applied to the fields of energy storage, medical treatment, construction and the like. In addition, the preparation process is simple and the manufacturing cost is low.
Example 2
(1) Commercial Al2O30.1g was dissolved in 50ml of deionized water, stirred and sonicated for 10 minutes to form a suspension, forming an aqueous phase.
(2) 1g of paraffin wax, 2g of Methyl Methacrylate (MMA), 0.4g of pentaerythritol tetraacrylate (PETRA) and 0.1g of Photonitiator 819 as a light curing agent were mixed, melted and stirred to form an oil phase.
(3) And (3) mixing the oil phase in the step (2) with the water phase in the step (1), and emulsifying by using a high-speed emulsifying machine, wherein the rotating speed of the emulsifying machine is 5000 revolutions, and the emulsifying time is 5 minutes.
(4) And irradiating the emulsified suspension for 5 minutes under the irradiation of ultraviolet light (an ultraviolet lamp with the power of 60W and the wavelength of 365 nm).
(5) Filtering the particles in the suspension, drying in an oven below the paraffin solidification temperature for 24 hours to form PMMA/Al2O3@ paraffin phase change microcapsules.
Example 3
(1) Will commercial SiO20.4g was dissolved in 50ml of deionized water, stirred and sonicated for 10 minutes to form a suspension, forming an aqueous phase.
(2) 4g of paraffin wax, 5g of Methyl Methacrylate (MMA), 1g of pentaerythritol tetraacrylate (PETRA) and 0.25g of Photonitiator 819 as a light curing agent were mixed, melted and stirred to form an oil phase, in which the paraffin wax component was octadecane.
(3) Mixing the oil phase in the step (2) and the water phase in the step (2), and emulsifying by using a high-speed emulsifying machine, wherein the rotating speed of the emulsifying machine is 20000 revolutions, and the emulsifying time is 5 minutes.
(4) And irradiating the emulsified suspension for 30 minutes under the irradiation of ultraviolet light (an ultraviolet lamp with the power of 60W and the wavelength of 365 nm).
(5) Filtering the particles in the suspension, and drying in an oven below the paraffin solidification temperature for 24 hours to form PMMA/SiO2@ paraffin phase change microcapsules.
Example 4
(1) Commercial P25 (TiO)2)0.03g was dissolved in 50ml of deionized water, stirred and sonicated for 10 minutes to form a suspension, forming an aqueous phase.
(2) 3g of paraffin wax, 3g of Methyl Methacrylate (MMA), 0.6g of pentaerythritol tetraacrylate (PETRA) and 0.15g of Photonitiator 819 as a light curing agent were mixed, melted and stirred to form an oil phase, wherein the paraffin wax component was octadecane.
(3) And (3) mixing the oil phase in the step (2) with the water phase in the step (1), and emulsifying by using a high-speed emulsifying machine, wherein the rotating speed of the emulsifying machine is 17000 revolutions, and the emulsifying time is 5 minutes.
(4) And irradiating the emulsified suspension for 10 minutes under the irradiation of ultraviolet light (an ultraviolet lamp with the power of 5W and the wavelength of 254 nm).
(5) Filtering the particles in the suspension, and drying in an oven below the paraffin solidification temperature for 24 hours to form PMMA/TiO2@ n-octadecane phase change microcapsules.
Example 5
(1) Commercial P25 (TiO)2)0.6g was dissolved in 50ml of deionized water, stirred and sonicated for 10 minutes to form a suspension, forming an aqueous phase.
(2) 3g of paraffin wax, 3g of Methyl Methacrylate (MMA), 0.6g of pentaerythritol tetraacrylate (PETRA) and 0.15g of Photonitiator 819 as a light curing agent were mixed, melted and stirred to form an oil phase, wherein the paraffin wax component was octadecane.
(3) And (3) mixing the oil phase in the step (2) with the water phase in the step (1), and emulsifying by using a high-speed emulsifying machine, wherein the rotating speed of the emulsifying machine is 17000 revolutions, and the emulsifying time is 30 minutes.
(4) And irradiating the emulsified suspension for 10 minutes under the irradiation of ultraviolet light (an ultraviolet lamp with the power of 100W and the wavelength of 420 nm).
(5) Filtering the particles in the suspension, and drying in an oven below the paraffin solidification temperature for 24 hours to form PMMA/TiO2@ n-octadecane phase change microcapsules.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. A preparation method for synthesizing phase-change microcapsules by adopting a photocuring method is characterized by comprising the following steps:
dissolving metal oxide nano particles in deionized water, and performing dispersion treatment to form a suspension as a water phase;
mixing paraffin, methyl methacrylate, a cross-linking agent pentaerythritol tetraacrylate and a light curing agent, and heating to form an oil phase;
mixing the water phase and the oil phase, and emulsifying by using an emulsifying machine to obtain an emulsified suspension;
irradiating the emulsified suspension with ultraviolet light to perform photocuring reaction, and filtering and drying the emulsified suspension after the reaction to form the phase-change microcapsule; the temperature in the drying treatment process is not higher than the paraffin solidification temperature;
the light curing agent is a light curing agent 819;
in the process of irradiating the emulsified suspension by the ultraviolet light, the power of the ultraviolet light is 5-100W, the wavelength is 254-420 nm, and the irradiation time is 5-30 minutes;
the mass of the metal oxide is 1-20% of that of the paraffin;
the mass ratio of the paraffin, the methyl methacrylate, the cross-linking agent and the light curing agent is 1-4: 2-5: 0.4-1.0: 0.1-0.25;
the rotating speed of the emulsifying machine is 5000-20000 revolutions; the emulsifying time is 3-15 minutes.
2. The method for preparing phase-change microcapsule by photocuring method according to claim 1, wherein the metal oxide is selected from Al2O3、SiO2Or TiO2One or more of them.
3. The method for preparing phase-change microcapsules by photocuring according to claim 1, wherein the metal oxide is 10% by mass.
4. The method of claim 1, wherein the emulsification time is 5 minutes.
5. The preparation method of the phase-change microcapsule by adopting the photocuring method as claimed in claim 1, wherein the dispersion treatment is ultrasonic treatment, and the ultrasonic treatment time is 5-30 minutes.
6. The method for preparing phase-change microcapsules by photocuring according to claim 5, wherein the ultrasonic treatment time is 10 minutes.
7. The method for preparing phase-change microcapsules by photocuring as claimed in claim 1, wherein the power of the ultraviolet light is 60W, the wavelength is 365nm, and the irradiation time is 10 minutes in the process of irradiating the emulsified suspension with the ultraviolet light.
8. The phase-change microcapsule prepared by the preparation method of claim 1, wherein the wall material of the phase-change microcapsule is a polymethyl methacrylate and metal oxide hybrid wall, the core material is paraffin, and the average particle size is 3-16 μm.
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| CN114746277B (en) * | 2019-10-11 | 2024-04-09 | 多哈科技大学 | Rapid mercury-free photochemical micro/nano encapsulation under ambient conditions |
| CN114797699B (en) * | 2022-04-22 | 2023-05-26 | 广东工业大学 | Method for eliminating supercooling degree of paraffin phase-change microcapsule and loss-free phase-change enthalpy, prepared phase-change microcapsule and application thereof |
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| CN102516951B (en) * | 2011-11-01 | 2014-02-19 | 河北工业大学 | Photopolymerization solid-solid energy storage phase-change material and preparation method thereof |
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