CN115322327A - Microcapsule phase change energy storage material based on silicon-containing waterborne polyurethane - Google Patents
Microcapsule phase change energy storage material based on silicon-containing waterborne polyurethane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
Abstract
The invention discloses a microcapsule phase change energy storage material based on silicon-containing waterborne polyurethane, and discloses anionic silicon-containing waterborne polyurethane, which comprises the following raw materials: diisocyanate, hydroxyl-terminated silicone oil, polyether polyol, a hydrophilic chain extender, a capping agent containing unsaturated double bonds and organic base, wherein the molar ratio of the hydroxyl-terminated silicone oil to the polyether polyol is 1-9:1. The invention also discloses a preparation method of the anionic silicon-containing waterborne polyurethane and application of the anionic silicon-containing waterborne polyurethane in a microcapsule phase change energy storage material. The invention also discloses a microcapsule phase change energy storage material, which comprises a core material and a wall material, wherein the wall material comprises the following raw materials: substance A and the anionic silicon-containing aqueous polyurethane. The invention also discloses a preparation method of the microcapsule phase change energy storage material. The microcapsule phase change energy storage material prepared by the invention has small particle size, uniform particle size distribution and high latent heat of phase change energy storage.
Description
Technical Field
The invention relates to the technical field of microcapsule phase change energy storage materials, in particular to a microcapsule phase change energy storage material based on silicon-containing waterborne polyurethane.
Background
In recent years, due to the frequent extreme abnormal weather around the world caused by global warming, the influence on the world energy industry is increasing, and the sustainable and stable energy resource supply faces a serious challenge. A key problem in a new low-carbon technology material is how to improve the energy utilization rate, reduce the loss in the energy transmission process and improve the transmission efficiency. The phase change energy storage microcapsule material is an important means for improving the energy utilization rate at present.
The phase change energy storage microcapsule material stores partial heat through the phase change process of the core material, and then releases energy under proper conditions, and the material has high energy storage density, small volume and easy design, thereby being widely applied to the fields of buildings, textiles and the like. However, the traditional phase change energy storage microcapsule material has low latent heat of energy storage, and the phase change energy storage microcapsule has large particle size and uneven particle size distribution; the further application of the phase change energy storage microcapsule material is limited.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a microcapsule phase change energy storage material based on silicon-containing waterborne polyurethane.
The invention provides anionic silicon-containing waterborne polyurethane which comprises the following raw materials: diisocyanate, hydroxyl-terminated silicone oil, polyether polyol, a hydrophilic chain extender, a capping agent containing unsaturated double bonds and organic base, wherein the molar ratio of the hydroxyl-terminated silicone oil to the polyether polyol is 1-9:1.
Preferably, the hydrophilic chain extender is at least one of dihydroxypropionic acid, ethylene glycol, propylene glycol, 1,4-butanediol, and diethanolamine.
Preferably, the end-capping agent containing unsaturated double bonds is at least one of hydroxyethyl acrylate, 2-propen-1-ol, 2-butenol and 4-penten-1-ol.
Preferably, the organic base is at least one of triethylamine and tripropylamine.
Preferably, the total number of moles of the hydroxyl terminated silicone oil and the polyether polyol is the same as the number of moles of the diisocyanate.
Preferably, the molar ratio of diisocyanate, hydrophilic chain extender and blocking agent containing unsaturated double bond is 1.
The invention also provides a preparation method of the anionic silicon-containing waterborne polyurethane, which comprises the following steps: in an inert gas atmosphere, carrying out copolymerization reaction on hydroxyl-terminated silicone oil, diisocyanate and polyether polyol under the action of a catalyst, adding a hydrophilic chain extender to carry out chain extension reaction, then adding a capping reagent containing unsaturated double bonds to carry out capping reaction, and adjusting the pH to be more than 7 by using organic alkali to obtain the silicon-containing waterborne polyurethane.
Preferably, the catalyst is an organometallic catalyst.
Preferably, the temperature of the copolymerization reaction, the chain extension reaction and the end capping reaction is 50-60 ℃.
Preferably, the time of the copolymerization reaction is 2 to 3 hours.
Preferably, the time of the chain extension reaction is 1.5 to 2.5h.
The molecular weight of the hydroxyl-terminated silicone oil can be 1000-3000.
The polyether polyol may be PPG2000, PPG1000, or the like.
The diisocyanate may be isophorone diisocyanate, diphenylmethane-4,4' -diisocyanate, toluene-2,3-diisocyanate, toluene-3,4-diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, or the like.
The dosage of the catalyst is not specified, and is determined according to specific operation; the time of the blocking reaction is not specified, and the reaction is carried out until no isocyanate group exists.
The invention also provides application of the anionic silicon-containing waterborne polyurethane in a microcapsule phase change energy storage material.
The invention also provides a microcapsule phase change energy storage material, which comprises a core material and a wall material, wherein the wall material comprises the following raw materials: a substance A and the anionic silicon-containing waterborne polyurethane, wherein the substance A is at least one of acrylate and styrene.
Preferably, the average particle size of the microcapsule phase change energy storage material is 180-355nm.
Preferably, the acrylate is at least one of tripropylene glycol diacrylate and methyl methacrylate.
Preferably, the weight ratio of the core material, the anionic silicon-containing aqueous polyurethane and the substance A is 2.8-3.2.
Preferably, the core material is at least one of paraffin and octadecane.
The invention also provides a preparation method of the microcapsule phase change energy storage material, which comprises the following steps: heating and uniformly mixing the anionic silicon-containing aqueous polyurethane emulsion, the core material and the substance A, and uniformly mixing and emulsifying the mixture, water and a defoaming agent to obtain emulsion; and adding a redox initiator in an inert gas atmosphere, and carrying out copolymerization reaction to obtain the microcapsule phase change energy storage material.
Taking Paraffin as a core material and tripropylene glycol diacrylate as a substance A as an example, the preparation mechanism of the microcapsule phase change energy storage material is shown in fig. 1, and fig. 1 is a preparation mechanism diagram of the microcapsule phase change energy storage material, wherein deionmized water is Deionized water, ASPU is anionic silicon-containing waterborne polyurethane, paraffin is a core material Paraffin, and TPGDA is tripropylene glycol diacrylate; the anionic silicon-containing waterborne polyurethane can be uniformly dispersed around paraffin droplets and copolymerized with the tripropylene glycol diacrylate to prepare a microcapsule phase change energy storage material; and the anionic silicon-containing waterborne polyurethane can ensure that the particle size of the paraffin droplets becomes smaller and uniform.
Preferably, the redox initiator is a mixture of ammonium persulfate and sodium bisulfite in equimolar ratio.
Preferably, the temperature of the copolymerization reaction is 55-65 ℃, and the time of the copolymerization reaction is 3.5-4.5h.
The dosage of the antifoaming agent and the redox initiator is not specified, and the dosage is determined according to specific operation; the defoaming agent is an aqueous defoaming agent.
The water is deionized water.
Advantageous effects
According to the invention, hydroxyl-terminated silane and polyether polyol are selected to be matched in a proper proportion to prepare anionic silicon-containing waterborne polyurethane, the anionic silicon-containing waterborne polyurethane is used for preparing a microcapsule phase change energy storage material, and a Si-O chain segment and a polyether chain segment are matched with each other, so that the anionic polyurethane can be uniformly dispersed around a core material liquid drop, the particle size of the core material liquid drop is smaller and uniform, the surface of the microcapsule is smooth and compact, and the microcapsule can be prevented from being adhered; polyurethane uniformly distributed around the core material liquid drop is blocked by unsaturated double bonds, and can be copolymerized with a proper amount of substance A to coat the core material, so that the density of the wall material is improved, the leakage of the core material is avoided, and the phase change energy storage latent heat of the microcapsule is improved; and the introduction of the Si-O chain segment can improve the high temperature resistance of the invention.
Drawings
FIG. 1 is a preparation mechanism diagram of a microcapsule phase change energy storage material, wherein Deionized water is deionzed water, ASPU is anionic silicon-containing waterborne polyurethane, paraffin is core material Paraffin, and TPGDA is tripropylene glycol diacrylate.
FIG. 2 is an infrared spectrum of anionic silicon-containing waterborne polyurethane, a microcapsule phase change energy storage material and paraffin, wherein a is the paraffin, b is the anionic silicon-containing waterborne polyurethane, and c is the microcapsule phase change energy storage material.
FIG. 3 is a particle size distribution diagram of a microcapsule phase change energy storage material, wherein a is comparative example 1, b is comparative example 2, c is example 1, and d is example 2,e is example 3.
FIG. 4 is an electron micrograph of a microencapsulated phase change energy storage material, wherein a is comparative example 1, b is comparative example 2, c is example 1, and d is example 2,e is example 3.
Fig. 5 is a TGA curve of a microcapsule phase change energy storage material.
Fig. 6 is a DTG curve of a microcapsule phase change energy storage material.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of anionic silicon-containing waterborne polyurethane comprises the following steps:
adding 5mmol of hydroxyl-terminated silicone oil (molecular weight is 1000), 10mmol of isophorone diisocyanate and 5mmol of polypropylene glycol PPG2000 into a four-neck flask with a stirring device and a reflux condenser tube, adding 0.5mmol of dibutyltin dilaurate, heating to 55 ℃ under the protection of nitrogen, stirring for copolymerization reaction for 2.5h, adding 5mmol of dimethylolpropionic acid, continuing to perform heat preservation and stirring for chain extension reaction for 2h, adding acetone for uniform mixing, then adding 2.5mmol of hydroxyethyl acrylate, continuing to perform heat preservation and stirring for end-capping reaction, taking reaction liquid for infrared spectrum detection, stopping reaction until no characteristic peak of isocyanate groups exists, and cooling to 30 ℃; adding triethylamine to adjust the pH value to be more than 7, and removing the solvent to obtain the anionic silicon-containing waterborne polyurethane.
A preparation method of a microcapsule phase change energy storage material comprises the following steps:
adding 2g of the anionic silicon-containing waterborne polyurethane into water, uniformly mixing to obtain a water emulsion, adding 3g of paraffin and 1g of tripropylene glycol diacrylate into an emulsification container, heating to 75 ℃, and uniformly stirring; then transferring the mixture into a high shear emulsifying machine, slowly increasing the rotating speed to 8000rpm, adding deionized water and 0.2g of aqueous defoaming agent, and stirring for 5min to obtain emulsion (the solid content of the anionic silicon-containing aqueous polyurethane in the emulsion is 10 wt%); pouring the emulsion into a three-neck flask, continuously stirring at 200rpm under the protection of nitrogen, adding 0.2g of redox initiator (namely a mixture consisting of ammonium persulfate and sodium bisulfite with equal molar ratio), heating to 60 ℃, reacting for 4h, and then cooling to 30 ℃ to obtain the microcapsule phase change energy storage material.
Infrared spectrum detection is carried out on the anionic silicon-containing waterborne polyurethane, the microcapsule phase change energy storage material and the paraffin wax prepared in the embodiment 3, and the result is shown in fig. 2, wherein fig. 2 is an infrared spectrum of the anionic silicon-containing waterborne polyurethane, the microcapsule phase change energy storage material and the paraffin wax, wherein a is the paraffin wax, b is the anionic silicon-containing waterborne polyurethane, and c is the microcapsule phase change energy storage material.
FIG. 2 shows that the hydroxyl-terminated silicone oil has been successfully grafted into the polyurethane backbone; in the microcapsule phase change energy storage material, a wall material is successfully coated with a paraffin core material.
Example 2
The same procedure as in example 3 was repeated, except that 7mmol of the hydroxyl terminated silicone oil and 3mmol of the polypropylene glycol PPG2000 were used.
Example 3
The same procedure as in example 3 was repeated, except that 9mmol of the hydroxyl terminated silicone oil and 1mmol of the polypropylene glycol PPG2000 were used.
Comparative example 1
The same procedure as in example 3 was repeated, except that 1mmol of the hydroxyl terminated silicone oil and 9mmol of the polypropylene glycol PPG2000 were used.
Comparative example 2
The same procedure as in example 3 was repeated, except that 3mmol of the hydroxyl terminated silicone oil and 7mmol of the polypropylene glycol PPG2000 were used.
The microcapsule phase change energy storage materials prepared in examples 1-3 and comparative examples 1-2 were used to detect the average particle size and particle size distribution of the microcapsule phase change energy storage materials. The results are shown in Table 1.
TABLE 1 average particle size of microencapsulated phase change energy storage materials
| Example 1 | 200.99 |
| Example 2 | 181.45 |
| Example 3 | 352.48 |
| Comparative example 1 | 440.89 |
| Comparative example 2 | 384.79 |
Typical particle size distribution diagrams and typical electron micrographs of the microcapsule phase change energy storage material are shown in fig. 3-4, and fig. 3 is the particle size distribution diagram of the microcapsule phase change energy storage material, wherein a is comparative example 1, b is comparative example 2, c is example 1, and d is example 2,e is example 3; FIG. 4 is an electron micrograph of a microencapsulated phase change energy storage material, wherein a is comparative example 1, b is comparative example 2, c is example 1, and d is example 2,e is example 3.
As can be seen from table 1 and fig. 3-4: when the hydroxyl-terminated silane and the polyether polyol are matched according to the molar ratio of 1-9:1, the average particle size of the microcapsule phase change energy storage material is small, the minimum average particle size is 181.45nm, the particle size distribution is uniform, the particle size surface is smooth, and adhesion is not easy to generate; for the microcapsule phase change energy storage material, the problem of core material leakage due to rupture is easily caused by larger particle size, the phase change latent heat of the microcapsule can be greatly reduced, and the microcapsule phase change energy storage material with small particle size is ideal in the practical engineering application process.
The microcapsule phase change energy storage materials prepared in examples 1-3 and comparative examples 1-2 were taken to detect the paraffin content of the microcapsule phase change energy storage materials. The results are shown in Table 2.
Paraffin content = (Δ Hm, microcapsule + Δ Hc, microcapsule)/(Δ Hm, P + Δ Hc, P);
wherein, the Delta Hm, the microcapsule and the Delta Hc, the microcapsule is respectively the melting heat and the crystallization heat (J/g) of paraffin in the microcapsule phase change energy storage material; Δ Hm, P and Δ Hc, P are the heat of fusion and crystallization (J/g) of the pure paraffin wax, respectively.
TABLE 2 Paraffin content test results
Remarking: t is a unit of om The initial temperature of the endothermic peak of the heating curve is shown; t is pm The peak temperature of the heating curve is shown; Δ H m Is the enthalpy value of the heating curve; t is oc The initial temperature of the endothermic peak of the cooling curve; t is pc The peak temperature of the cooling curve; Δ H c Is the enthalpy value of the cooling curve.
As can be seen from table 2: when the hydroxyl-terminated silane and the polyether polyol are matched according to the molar ratio of 1-9:1, the paraffin content is far higher than that of the comparative examples 1-2, and the latent heat of phase change energy storage is high.
TGA and DTG detection is carried out on the microcapsule phase change energy storage materials prepared in examples 1-3 and comparative examples 1-2, and the results are shown in figures 5-6, and figure 5 is a TGA curve of the microcapsule phase change energy storage material; fig. 6 is a DTG curve of a microcapsule phase change energy storage material.
As can be seen in fig. 5-6: with the increase of the molar ratio of the hydroxyl-terminated silane to the polyether polyol, the decrease range of the first-stage decomposition weight loss rate of the microcapsule phase change energy storage material is increased, which indicates that the paraffin coating rate is also increased, wherein the first-stage weight loss rate of the microcapsule phase change energy storage material of the embodiment 3 reaches 73.40%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. An anionic silicon-containing waterborne polyurethane is characterized by comprising the following raw materials: diisocyanate, hydroxyl-terminated silicone oil, polyether polyol, a hydrophilic chain extender, a capping agent containing unsaturated double bonds and organic base, wherein the molar ratio of the hydroxyl-terminated silicone oil to the polyether polyol is 1-9:1.
2. The anionic silicon-containing aqueous polyurethane of claim 1, wherein the hydrophilic chain extender is at least one of dihydroxypropionic acid, ethylene glycol, propylene glycol, 1,4-butanediol, and diethanolamine; preferably, the end-capping reagent containing unsaturated double bonds is at least one of hydroxyethyl acrylate, 2-propylene-1-alcohol, 2-butenol and 4-pentene-1-alcohol; preferably, the organic base is at least one of triethylamine and tripropylamine.
3. The anionic silicon-containing aqueous polyurethane according to claim 1 or 2, wherein the total number of moles of the hydroxyl-terminated silicone oil and the polyether polyol is the same as the number of moles of the diisocyanate; preferably, the molar ratio of diisocyanate, hydrophilic chain extender and blocking agent containing unsaturated double bond is 1.
4. A process for the preparation of the anionic silicon-containing aqueous polyurethane according to any of claims 1 to 3, comprising the steps of: in an inert gas atmosphere, carrying out copolymerization reaction on hydroxyl-terminated silicone oil, diisocyanate and polyether polyol under the action of a catalyst, adding a hydrophilic chain extender to carry out chain extension reaction, then adding a capping reagent containing unsaturated double bonds to carry out capping reaction, and adjusting the pH to be more than 7 by using organic alkali to obtain the silicon-containing waterborne polyurethane.
5. The method for producing the anionic silicon-containing aqueous polyurethane according to claim 4, wherein the catalyst is an organometallic catalyst; preferably, the temperature of the copolymerization reaction, the chain extension reaction and the end capping reaction is 50-60 ℃; preferably, the time of the copolymerization reaction is 2 to 3 hours; preferably, the time of the chain extension reaction is 1.5 to 2.5h.
6. Use of the anionic silicon-containing aqueous polyurethane according to any one of claims 1 to 3 in a microencapsulated phase change energy storage material.
7. The microcapsule phase change energy storage material is characterized by comprising a core material and a wall material, wherein the wall material comprises the following raw materials: the anionic silicon-containing aqueous polyurethane according to any one of claims 1 to 3, wherein the substance A is at least one of acrylate and styrene.
8. The microencapsulated phase change energy storage material of claim 7 wherein the microencapsulated phase change energy storage material has an average particle size of 180 to 355nm; preferably, the acrylate is at least one of tripropylene glycol diacrylate and methyl methacrylate; preferably, the weight ratio of the core material, the anionic silicon-containing aqueous polyurethane and the substance A is 2.8-3.2; preferably, the core material is at least one of paraffin and octadecane.
9. A method for preparing the microcapsule phase change energy storage material according to claim 7 or 8, which comprises the following steps: heating and uniformly mixing the anionic silicon-containing waterborne polyurethane aqueous emulsion, the core material and the substance A, uniformly mixing the anionic silicon-containing waterborne polyurethane aqueous emulsion, the core material and the substance A with water and a defoaming agent, and emulsifying to obtain an emulsion; and adding a redox initiator in an inert gas atmosphere, and carrying out copolymerization reaction to obtain the microcapsule phase change energy storage material.
10. The preparation method of the microcapsule phase change energy storage material according to claim 9, wherein the redox initiator is a mixture of ammonium persulfate and sodium bisulfite in equimolar ratio; preferably, the temperature of the copolymerization reaction is 55-65 ℃, and the time of the copolymerization reaction is 3.5-4.5h.
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