CN111054283B - Phase change energy storage microcapsule with polyurethane modified organic silicon resin as shell material and preparation method thereof - Google Patents
Phase change energy storage microcapsule with polyurethane modified organic silicon resin as shell material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a phase change energy storage microcapsule taking polyurethane modified organic silicon resin as a shell material and a preparation method thereof, and particularly discloses a preparation method which comprises the following steps: (1) uniformly mixing the monomers for generating the organic silicon resin, adding a catalyst for prepolymerization to obtain a prepolymer of polysiloxane; (2) adding the polyurethane prepolymer into the step (1) to react to obtain a polyurethane modified organic silicon resin prepolymer; (3) uniformly mixing the core material and the shell material prepolymer to obtain a mixture of the core material and the shell material prepolymer; (4) preparing an aqueous solution of a surfactant; (5) mixing and emulsifying a core material and shell material prepolymer mixture and a surfactant aqueous solution to obtain an emulsion, adding a catalyst until the reaction is finished, and separating and drying to obtain the polyurethane modified organic silicon resin shell phase change energy storage microcapsule. The method is green and pollution-free, the operation is simple, the obtained microcapsule has smooth surface, good compactness, adjustable phase-change temperature, controllable particle size, good heat resistance and high phase-change enthalpy value.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage, and particularly relates to a phase change energy storage microcapsule taking polyurethane modified organic silicon resin as a shell material and a preparation method thereof.
Background
The phase-change energy storage technology is a technology for forming a composite phase-change energy storage material with a core-shell structure by coating a layer of film with stable performance on the surface of solid-liquid phase-change energy storage material particles by applying a microcapsule technology. The problems of leakage, volume change and easy corrosion of the phase-change energy storage material can occur in the application process, so that the phase-change energy storage material needs to be microencapsulated.
The shell materials of the phase-change energy-storage microcapsule can be generally divided into organic shell materials and inorganic shell materials, most of the inorganic shell materials coat the phase-change energy-storage material by performing hydrolysis-condensation on an inorganic precursor on the surface of the phase-change energy-storage material, but the inorganic shell materials have poor toughness, are easy to break in the using process and are difficult to industrialize. The organic shell material has excellent toughness, is easy to process and realize industrialization.
For example, patent document No. CN109054768A reports paraffin @ calcium carbonate phase change energy storage microcapsules, which use paraffin as a core material and calcium carbonate as a shell material. The phase change energy storage microcapsule takes inorganic material calcium carbonate as a shell material, has poor shell toughness, is easy to break in the processing process, is not acid-resistant, is easy to degrade in an acid environment, is easy to agglomerate in the drying process of the microcapsule, and can not form powder with uniform particle size in the drying process.
For example, the phase change energy storage microcapsule reported in the patent publication No. CN109868116A uses melamine-formaldehyde resin as a shell material, and SEM picture shows that the microcapsule has a large amount of shell breaking phenomenon, which indicates that the toughness of the shell material is not sufficient, and meanwhile, the presence of carcinogenic formaldehyde in the production and use process of the phase change energy storage microcapsule of the shell material easily causes environmental pollution and physical injury to operators and users.
Disclosure of Invention
Aiming at the defects of the existing phase change energy storage microcapsule, the invention aims to provide the polyurethane modified organic silicon resin shell phase change energy storage microcapsule with excellent shell material toughness, controllable particle size and excellent processing performance. The phase change energy storage microcapsule is directly synthesized in a water phase in the preparation process, so that the production cost can be effectively reduced, and the environmental pollution is reduced; the processing technology is simple, and the product does not cause physical damage to producers and users.
The invention adopts an interfacial polymerization method, takes polyurethane modified organic silicone grease prepolymer as an oil-soluble reaction monomer, takes water as a water-soluble reaction monomer, and has the following main reaction formula:
one aspect of the invention provides a preparation method of a phase change energy storage microcapsule taking polyurethane modified organic silicon resin as a shell material, which comprises the following steps:
(1) uniformly mixing the monomers for generating polysiloxane, adding a catalyst for prepolymerization to obtain a polysiloxane prepolymer;
(2) adding the polyurethane prepolymer into a polysiloxane prepolymer, and reacting to obtain a polyurethane modified organic silicon resin prepolymer;
(3) uniformly mixing the core material and the polyurethane modified organic silicon resin prepolymer to obtain a mixture of the core material and the polyurethane modified organic silicon resin prepolymer;
(4) preparing an aqueous solution of a surfactant;
(5) mixing and emulsifying a core material, a polyurethane modified organic silicon resin prepolymer mixture and a water solution of a surfactant to obtain an emulsion, adding a catalyst until the reaction is finished, and separating and drying to obtain a polyurethane modified organic silicon resin shell phase change energy storage microcapsule;
the core material is a phase change energy storage material; the surfactant is an oil-in-water emulsifier.
In the technical scheme of the invention, the monomers for generating polysiloxane are vinyl silicone oil and hydrogen-containing silicone oil with the hydrogen content of 0.1-2.0.
In the technical scheme of the invention, the vinyl silicone oil is selected from methyl vinyl silicone oil, styryl silicone oil, divinyl silicon oil, tetramethyl divinyl disiloxane or polyvinyl silicone oil, and preferably tetramethyl divinyl disiloxane.
In the technical scheme of the invention, the hydrogen-containing silicone oil with the hydrogen content of 0.1-2.0 is selected from polymethylhydrosiloxane.
In the technical scheme of the invention, the polyurethane prepolymer is a polyurethane prepolymer synthesized by taking a diisocyanate monomer and polyether diol as raw materials, wherein the diisocyanate monomer is selected from diphenylmethane diisocyanate (MDI), 2, 4-Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) and a dimer or polymer thereof, and the diphenylmethane diisocyanate monomer, the 2, 4-toluene diisocyanate monomer and the dimer or polymer thereof are preferred.
In the technical scheme of the invention, the adding amount of the polyurethane prepolymer is 4-20%, preferably 5-10% of that of the polysiloxane prepolymer.
In the technical scheme of the invention, the HLB value of the emulsifier is 8-15, more preferably, the emulsifier is styrene maleic anhydride copolymer sodium salt, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, OP-10, Tween 80, cocamidopropyl dimethyl aminolactone, polyoxyethylene (16) sorbitan mono-tall oil acid ester, polyoxyethylene (10) sorbitan monolaurate, polyoxyethylene (20) sorbitan dioleate, sodium abietate, C14-18 alkyl sodium sulfate, dialkyl sulfosuccinate or their compound, PVA.
In the technical scheme of the invention, the catalyst in the steps (1) and (5) is independently selected from a platinum catalyst and an organic tin catalyst, preferably, the organic tin catalyst is dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate, dibutyltin dichloride, methyltin trichloride, trimethyltin chloride, dibutyltin didecanoate, zinc isooctanoate and bismuth neodecanoate, and the platinum catalyst is platinum (0) -divinyl tetramethyl disiloxane complex (Karstedt catalyst).
In the technical scheme of the invention, the amount of the catalyst used in the step (1) is 0.025-0.1% of the amount of the reaction monomer.
In the technical scheme of the invention, the amount of the catalyst in the step (5) is 5-20 times that of the catalyst in the step (1).
In the technical scheme of the invention, the core material is selected from n-alkane or oil-soluble ester phase-change materials,
preferably, the oil-soluble ester phase-change material is selected from one or more of methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl behenate and ethyl behenate.
Preferably, the n-alkane is tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane or hexacosane.
In the technical scheme of the invention, the prepolymerization time in the step (1) is 30-60 min, and the prepolymerization temperature is 40-70 ℃.
In the technical scheme of the invention, the reaction time in the step (2) is 5-30 min, and the reaction temperature is 40-70 ℃.
In the technical scheme of the invention, the adding amount of the polyurethane prepolymer in the step (2) is 4-20%, preferably 5-10% of that of the polysiloxane prepolymer.
In the technical scheme of the invention, the mass ratio of the core material in the step (3) to the polyurethane modified organic silicon resin prepolymer is 1: 1-1: 6.
In the technical scheme of the invention, the concentration of the aqueous solution of the surfactant in the step (4) is 1-10%.
In the technical scheme of the invention, the emulsifying time in the step (5) is 15-60 min, the emulsifying rate is 1000-10000 rpm, and the emulsifying temperature is 50-70 ℃.
In the technical scheme of the invention, the catalyst is added in the step (5) and then the mixture is heated for reaction, wherein the reaction temperature is 80-95 ℃.
The invention also provides a phase change energy storage microcapsule taking polyurethane modified organic silicon resin prepared by the method as a shell material.
The invention further provides a phase change energy storage microcapsule taking polyurethane modified organic silicon resin as a shell material, which comprises an outer shell of the polyurethane modified organic silicon resin and an inner core of the phase change energy storage material.
In the technical scheme of the invention, the organic silicon resin is polysiloxane.
In the technical scheme of the invention, the particle size of the phase change energy storage microcapsule is 500nm-100 um.
In the technical scheme of the invention, the proportion of the core material to the shell material is as follows: 1:1 to 6: 1.
The phase change energy storage microcapsule directly disperses the core material and the shell material in water in the production process, and the microcapsule can be directly washed by water in the post-treatment, so that the production cost is greatly reduced, the production process is simple, the requirement on production equipment is low, and the industrialization is easy. Meanwhile, as the organic silicon resin is a non-flammable material, the flame retardant property of the phase change energy storage microcapsule is obviously improved.
Advantageous effects
The microcapsule prepared by the interfacial polymerization method can adopt hexadecane, octadecane, eicosane, docosane, methyl laurate or ethyl laurate, methyl stearate or ethyl stearate, methyl behenate or ethyl behenate and a compound of two or more of the hexadecane, the octadecane, the eicosane, the docosane, the methyl laurate or the ethyl laurate, the methyl stearate or the ethyl stearate and the compound of two or more of the methyl behenate or the ethyl behenate as core materials, polyurethane modified organic silicon resin is taken as a shell material, the phase change temperature can be regulated according to the actual use temperature of the phase change energy storage microcapsule, the phase change temperature of the phase change energy storage microcapsule can be regulated, and meanwhile, the phase change value of the phase change.
The phase change energy storage microcapsules with different particle sizes are prepared according to different emulsifiers, emulsification time and emulsification rate, and the particle size of the phase change energy storage microcapsules can be controlled between 500nm and 100 um.
The organic silicon resin has excellent performances of temperature resistance, flame retardance, high hardness and the like, but as a shell material of the microcapsule, the organic silicon resin has poor film forming property, and the shell material of the formed microcapsule is brittle, poor in flexibility and low in coating rate. The polyurethane has excellent flexibility, wear resistance, adhesion and solvent resistance. The polyurethane is introduced into the organic silicon resin, so that the good heat resistance of the organic silicon resin is kept, the defects of poor mechanical strength, solvent resistance, film forming property, poor adhesive force and low coating rate of the organic silicon resin are overcome, and the curing temperature of the organic silicon resin can be effectively reduced.
The polyurethane modified organic silicon resin is used as the shell of the phase change energy storage microcapsule, the crosslinking density is high, and polymer molecules present a spatial network structure, so that the obtained phase change energy storage microcapsule has a smooth surface, good shell compactness (as shown in figures 1,2 and 3), certain strength, excellent processability, heat resistance (the heat resistance can reach more than 200 ℃, as shown in figure 3), excellent thermal oxidation stability, electric insulation performance, weather resistance, water resistance, salt mist resistance, mold resistance, biocompatibility and the like.
The phase change energy storage microcapsule is directly synthesized in water, and the post-treatment is directly carried out by washing with water, so that the use of a large amount of organic solvents is avoided, the environment is protected, the toxicity is avoided, and the production cost is reduced. The production process is simple, the requirement on production equipment is low, and the scale-up experiment is easy to realize for industrialization. Meanwhile, as the organic silicon resin is a non-flammable material, the flame retardant property of the phase change energy storage microcapsule is obviously improved. Therefore, the phase change energy storage microcapsule has wide application prospect in thermal interface materials.
Drawings
FIG. 1 is a photograph taken by a conventional optical microscope of example 1 of the present invention;
FIG. 2 is a photograph taken by a polarization microscope of example 1 of the present invention;
FIG. 3 is a photograph of a scanning electron microscope showing examples 1 of the present invention;
FIG. 4 is a differential scanning calorimetry curve for n-docosane of example 1 of this invention;
FIG. 5 is a differential scanning calorimetry curve of example 1 of the invention;
FIG. 6 is a thermogravimetric analysis curve of example 2 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with figures are described in detail below, but the present invention is not to be construed as limiting the implementable range thereof.
It is prepared by the following steps:
example 1 preparation of phase change energy storage microcapsules with polyurethane modified silicone resin as shell material
(1) The preparation of polysiloxane prepolymer, namely, uniformly mixing reaction monomers of tetramethyl divinyl disiloxane and polymethylhydrosiloxane, adding a catalyst of platinum (0) -divinyl tetramethyl disiloxane compound accounting for 0.025 percent of the mass of the monomers, and carrying out prepolymerization in a water bath at the temperature of 60 ℃ for 45min to prepare 20 g of polysiloxane prepolymer.
(2) And (3) preparing a shell material prepolymer, namely adding 1 g of polyurethane prepolymer into the mixture (1), and stirring for 15 minutes at a constant temperature of 60 ℃ to obtain the polyurethane modified organic silicon resin prepolymer.
(3) Weighing core material ethyl laurate with the mass fraction of 4:1, and uniformly mixing the core material ethyl laurate with the shell material prepolymer for later use.
(4) 200mL of an aqueous solution containing 2% of SDS as a surfactant was weighed.
(5) And (4) adding the (3) into the (4) for emulsification, wherein the stirring speed is 6000rpm, the emulsification temperature is 60 ℃, and the emulsification time is 35 min.
(6) And after emulsification, reducing the rotating speed, adding a catalyst dibutyltin dilaurate with the mass being 0.5% of that of the monomer, heating to 80 ℃, continuing to react for 4 hours to finish the reaction, washing with deionized water, carrying out reduced pressure filtration to obtain a filter cake, and drying in an oven at 70 ℃ for 5-8 hours to obtain the polyurethane modified organic silicon resin shell phase-change energy-storage microcapsule powder.
Example 2 preparation of phase change energy storage microcapsule with polyurethane modified silicone resin as shell material
(1) The preparation of polysiloxane prepolymer, namely, uniformly mixing reaction monomers of tetramethyl divinyl disiloxane and polymethylhydrosiloxane, adding a catalyst of platinum (0) -divinyl tetramethyl disiloxane compound accounting for 0.03 percent of the mass of the monomers, and carrying out prepolymerization in a water bath at the temperature of 55 ℃ for 40min to prepare 16 g of polysiloxane prepolymer.
(2) And (3) preparing a shell material prepolymer, namely adding 0.8 g of polyurethane prepolymer into the mixture (1), uniformly stirring, and stirring for 15 minutes at a constant temperature of 60 ℃ to obtain the polyurethane modified organic silicon resin prepolymer.
(3) Weighing core material methyl behenate with the mass fraction of 4.5:1, and uniformly mixing the core material methyl behenate with the shell material prepolymer for later use.
(4) 200mL of an aqueous solution containing 2% of SDS as a surfactant was weighed.
(5) And (4) adding the (3) into the (4) for emulsification, wherein the stirring speed is 1500rpm, the emulsification temperature is 65 ℃, and the emulsification is carried out for 45 min.
(6) And after emulsification, reducing the rotating speed, adding a catalyst platinum (0) -divinyl tetramethyl disiloxane compound accounting for 0.4% of the mass of the monomer again, heating to 85 ℃, continuing to react for 5 hours to finish the reaction, washing with deionized water, carrying out reduced pressure filtration to obtain a filter cake, and drying in an oven at 70 ℃ for 5-8 hours to obtain polyurethane modified organic silicon resin shell phase change energy storage microcapsule powder with the particle size of 10-40 microns (the average particle size is 30 microns).
Example 3 preparation of phase change energy storage microcapsule with polyurethane modified silicone resin as shell material
(1) The preparation of polysiloxane prepolymer, namely, uniformly mixing reaction monomers of tetramethyl divinyl disiloxane and polymethylhydrosiloxane according to a certain proportion, adding dibutyltin dilaurate accounting for 0.05 percent of the mass of the monomers, and carrying out prepolymerization in a water bath at the temperature of 70 ℃ for 35min to prepare 30 g of polysiloxane prepolymer.
(2) And (3) preparing a shell material prepolymer, namely adding 2 g of polyurethane prepolymer into the mixture (1), uniformly stirring, and stirring for 15 minutes at a constant temperature of 60 ℃ to obtain the polyurethane modified organic silicon resin prepolymer.
(3) Weighing core material n-octadecane with the mass fraction of 5:1, and uniformly mixing the core material n-octadecane with the shell material prepolymer for later use.
(4) 200mL of an aqueous solution containing 7% of a surfactant PVA was weighed.
(5) And (4) adding the (3) into the (4) for emulsification, wherein the stirring speed is 8000rpm, the emulsification temperature is 70 ℃, and the emulsification is carried out for 25 min.
(6) And after emulsification, reducing the rotating speed, adding a catalyst dibutyltin dilaurate with the mass being 0.5% of that of the monomer, heating to 90 ℃, continuing to react for 3 hours to finish the reaction, washing with deionized water, carrying out reduced pressure filtration to obtain a filter cake, and drying in an oven at 70 ℃ for 5-8 hours to obtain the polyurethane modified organic silicon resin shell phase-change energy storage microcapsule powder with the particle size of 300-1.0 mu m (the average particle size is 800 nm).
Example 4 preparation of phase change energy storage microcapsule with polyurethane modified silicone resin as shell material
(1) The preparation of polysiloxane prepolymer, namely, mixing reaction monomers of tetramethyl divinyl disiloxane and polymethylhydrosiloxane according to the proportion of 1:1, adding a catalyst of platinum (0) -divinyl tetramethyl disiloxane compound accounting for 0.03 percent of the mass of the monomers, and carrying out prepolymerization in a water bath at the temperature of 45 ℃ for 15min to prepare 16 g of polysiloxane prepolymer.
(2) And (3) preparing a shell material prepolymer, namely adding 4 g of polyurethane prepolymer into the mixture obtained in the step (1), and stirring for 15 minutes at a constant temperature of 60 ℃ to obtain the polyurethane modified organic silicon resin prepolymer.
(3) Weighing a mixture of core material methyl stearate and n-eicosane with the mass fraction of 6:1, and uniformly mixing the mixture with the shell material prepolymer for later use.
(4) 300mL (pH value: 4.0-5.0) of aqueous solution containing 10% of SMA as a surfactant is weighed.
(5) And (4) adding the (3) into the (4) for emulsification, wherein the stirring speed is 3000rpm, the emulsification temperature is 70 ℃, and the emulsification is carried out for 25 min.
(6) And after emulsification, reducing the rotating speed, adding a catalyst platinum (0) -divinyl tetramethyl disiloxane compound accounting for 0.3% of the mass of the monomer, heating to 95 ℃, continuing to react for 5 hours to finish the reaction, washing with deionized water, carrying out reduced pressure filtration to obtain a filter cake, and drying in an oven at 70 ℃ for 5-8 hours to obtain the polyurethane modified organic silicon resin shell phase-change energy storage microcapsule powder with the particle size of 5-22 microns (the average particle size is 18 microns).
Examples of effects
Observing the appearance of the microcapsule as a spherical shape with smooth and compact surface by an optical microscope and a scanning electron microscope; the melting peak temperature of the microcapsule of the embodiment 1 of the invention is 45.96 ℃, the melting endothermic enthalpy is 183.4J/g, the crystallization exothermic enthalpy is 183.8J/g by differential scanning calorimetry, which shows that the microcapsule has higher heat storage capacity; the microcapsules of the embodiment 2 of the invention have good stability at the temperature of below 227.52 ℃ by thermogravimetric analysis.
Claims (22)
1. A preparation method of a phase change energy storage microcapsule taking polyurethane modified organic silicon resin as a shell material comprises the following steps:
(1) uniformly mixing the monomers for generating polysiloxane, adding a catalyst for prepolymerization to obtain a polysiloxane prepolymer;
(2) adding a polyurethane prepolymer into a polysiloxane prepolymer, and reacting to obtain a polyurethane modified organic silicon resin prepolymer;
(3) uniformly mixing the core material and the polyurethane modified organic silicon resin prepolymer to obtain a mixture of the core material and the polyurethane modified organic silicon resin prepolymer;
(4) preparing an aqueous solution of a surfactant;
(5) mixing and emulsifying a core material, a polyurethane modified organic silicon resin prepolymer mixture and a water solution of a surfactant to obtain an emulsion, adding a catalyst until the reaction is finished, and separating and drying to obtain a polyurethane modified organic silicon resin shell phase change energy storage microcapsule;
the core material is a phase change energy storage material; the surfactant is an oil-in-water emulsifier.
2. The method according to claim 1, wherein the polysiloxane-forming monomer is a vinyl silicone oil and a hydrogen-containing silicone oil having a hydrogen content of 0.1 to 2.0.
3. The production method according to claim 2, wherein the vinyl silicone oil is selected from methyl vinyl silicone oil, styrene based silicone oil, divinyl silicone oil, tetramethyl divinyl disiloxane, or polyvinyl silicone oil.
4. The method of claim 3, wherein the vinyl silicone oil is selected from tetramethyldivinyldisiloxane.
5. The preparation method according to claim 2, wherein the hydrogen-containing silicone oil having a hydrogen content of 0.1 to 2.0 is polymethylhydrosiloxane.
6. The method of claim 1, wherein the polyurethane prepolymer is a polyurethane prepolymer synthesized from a diisocyanate monomer and a polyether diol, and the diisocyanate monomer is selected from the group consisting of diphenylmethane diisocyanate (MDI), 2, 4-Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), and dimers or multimers thereof.
7. The method according to claim 6, wherein the diisocyanate monomer is selected from the group consisting of diphenylmethane diisocyanate monomer, 2, 4-toluene diisocyanate monomer, and a dimer or a multimer thereof.
8. The method of claim 6, wherein the polyurethane prepolymer is added in an amount of 4-20% based on the polysiloxane prepolymer.
9. The method according to claim 1, wherein the emulsifier has an HLB value of 8 to 15.
10. The method according to claim 9, wherein the emulsifier is a sodium salt of a styrene maleic anhydride copolymer, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, sodium lauryl sulfate, OP-10, tween 80, cocamidopropyl dimethyl amine ethyl lactone, polyoxyethylene (16) sorbitan monolaurate, polyoxyethylene (10) sorbitan monolaurate, polyoxyethylene (20) sorbitan dioleate, sodium abietate, sodium C14-18 alkyl sulfate, dialkyl sulfosuccinate, or a combination thereof, PVA.
11. The production method according to claim 1, wherein the catalysts in the steps (1) and (5) are independently selected from a platinum catalyst, an organotin catalyst.
12. The method according to claim 11, wherein the amount of the catalyst used in step (1) is 0.025 to 0.1% by mass based on the mass of the reaction monomer.
13. The method according to claim 11, wherein the amount of the catalyst used in the step (5) is 5 to 20 times the amount of the catalyst used in the step (1).
14. The preparation method according to claim 1, wherein the phase change energy storage material is selected from one or more of n-alkane and oily ester phase change materials.
15. The preparation method of claim 14, wherein the oily ester phase-change material is selected from methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl behenate or ethyl behenate,
the n-alkane is selected from tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane or hexacosane.
16. The preparation method according to claim 1, wherein the reaction temperature of the prepolymerization in the step (1) is 40-70 ℃; the reaction time of the step (2) is 5-30 min, and the reaction temperature is 40-70 ℃; and (5) adding a catalyst, and heating for reaction at the reaction temperature of 80-95 ℃.
17. The preparation method according to claim 1, wherein the mass ratio of the core material in the step (3) to the polyurethane modified silicone resin prepolymer is 1: 1-1: 6.
18. The phase change energy storage microcapsule taking the polyurethane modified organic silicon resin obtained by the preparation method according to any one of claims 1 to 17 as a shell material.
19. The phase change energy storage microcapsule in which the polyurethane-modified silicone resin is a shell material of claim 18, comprising an outer shell of the polyurethane-modified silicone resin and an inner core of the phase change energy storage material.
20. The phase change energy storage microcapsule according to claim 19, wherein said silicone resin is a polysiloxane.
21. The phase change energy storage microcapsule according to claim 19, having a particle size of 500nm to 100 μ ι η.
22. The phase change energy storage microcapsule of claim 19, the ratio of core material to shell material being: 1:1 to 6: 1.
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| PCT/CN2020/130865 WO2021109891A1 (en) | 2019-12-06 | 2020-11-23 | Phase change energy storage microcapsule using polyurethane modified organic silicone resin as shell material, and preparation method therefor |
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| CN111054283B (en) * | 2019-12-06 | 2021-03-12 | 深圳先进电子材料国际创新研究院 | Phase change energy storage microcapsule with polyurethane modified organic silicon resin as shell material and preparation method thereof |
| CN111607300A (en) * | 2020-06-21 | 2020-09-01 | 武汉露能科技有限公司 | Durable anti-icing low-surface-energy material for wind power blade and preparation method thereof |
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| US20030138632A1 (en) * | 2002-01-22 | 2003-07-24 | Kun-Hsiang Huang | Heat-absorbing particle |
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| CN101717618A (en) * | 2009-11-10 | 2010-06-02 | 天津工业大学 | Preparation method of phase-change material microcapsule |
| CN105381767B (en) * | 2015-11-11 | 2018-12-18 | 上海伊纯实业有限公司 | A kind of polyurethane microcapsule encapsulating phase-change material and preparation method thereof |
| JP2017114965A (en) * | 2015-12-22 | 2017-06-29 | 理想科学工業株式会社 | Capsule type heat storage material and method for producing the same |
| CN106479445A (en) * | 2016-09-30 | 2017-03-08 | 华南理工大学 | A kind of bivalve layer microcapsules of storing energy through phase change and preparation method thereof |
| EP3574061B1 (en) * | 2017-01-27 | 2021-11-10 | Encapsys, LLC | Encapsulates |
| CN108084970A (en) * | 2017-12-20 | 2018-05-29 | 上海叹止新材料科技有限公司 | A kind of phase-change thermal storage padded coaming and preparation method and application |
| CN109126653A (en) * | 2018-08-29 | 2019-01-04 | 常州大学 | It is a kind of using polyurethane as the preparation method of the phase-change microcapsule of wall material |
| CN110144193B (en) * | 2019-06-03 | 2021-05-25 | 宁波特粒科技有限公司 | Silicon dioxide phase change energy storage microcapsule and preparation method thereof |
| CN111054283B (en) * | 2019-12-06 | 2021-03-12 | 深圳先进电子材料国际创新研究院 | Phase change energy storage microcapsule with polyurethane modified organic silicon resin as shell material and preparation method thereof |
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