CN1958711A - Energy storage material of solid - solid phase change in opal / polyurethane type, and preparation method - Google Patents
Energy storage material of solid - solid phase change in opal / polyurethane type, and preparation method Download PDFInfo
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Abstract
This invention relates to a method for preparing opal/polyurethane solid-solid phase transition energy-storage material. The molecular structure of the material is shown in formula I, where, poly (ethylene glycol) is the soft segment, while aliphatic and aromatic isocyanate, and trihydroxyl substance are the hard segments. The method comprises: (1) preparing prepolymer of poly (ethylene glycol) with terminal groups activated by isocyanate groups; (2) preparing opal/polyurethane solid-solid phase transition energy-storage material. The method has such advantages as low raw material cost, no toxicity of the product, and simple process. The addition of natural nanomaterial (opal) can increase the phase transition enthalpy value and heat response rate of the material, and can reduce the cost. The opal/polyurethane solid-solid phase transition energy-storage material can effectively save energy, and has potential applications in such fields as agriculture, energy resources, textile, construction and electronics.
Description
Technical field
The invention belongs to solid-solid phase transition material that has energy-storage function and preparation method thereof.Be specifically related to opal/polyurethane-type solid-solid phase-change energy-storage material and preparation method thereof.
Background technology
In information, the energy, the material epoch as three big mainstay industries, energy storage material has been subjected to increasing attention.(phase change material is in recent years both at home and abroad at energy utilization and material one of focus of science aspect developing research PCM) for phase-change accumulation energy and phase change material.Should be solid-liquid phase change material and solid-solid phase transition material at present the most widely.
The solid-liquid phase change material liquid state can occur in phase transition process, so need container in use phase change material and thermal conductor are separated, by the heat exchange between interchanger realization heat-transfer fluid and the phase change material.This has not only increased the cost of system, has also limited its use range.
Solid-solid phase transition material keeps solid state always in the phase change process, need not the container splendid attire, so solid-solid phase-change has advantage than the solid-liquid phase change material on using.Common solid-solid phase transition material has polyalcohols and high score subclass, wherein the polyvalent alcohol energy storage material is being heated more than the solid-solid phase-change temperature, when becoming plastic crystals by the crystalline state solid, because of plastic crystal has very big vapour pressure, volatile loss, so that it still needs container sealing when using, and also is difficult to widespread use.At this class phase change material, the polymer solid-solid phase transition material is made various forms greatly, easily, can be directly become the most rising research field of phase-changing energy storage material as the characteristics such as structured material of system with its storage thermal capacity.It mainly is divided into two classes: the first kind is a cross-linking type crystalline polymer phase change material, and second class then is that some polymkeric substance are the composite phase-change material of matrix.
Cross-linking type crystalline polymer phase change material mainly contains polyolefins phase change material and polyethylene glycols phase change material.What use was maximum in the polyolefins phase change material is high density polyethylene(HDPE), and it is cheap, the latent heat of phase change height, and be processed into various forms easily.But very big shortcoming is also arranged, and as Chinese patent CN1482204A, energy storage material volume when undergoing phase transition changes, and expansion repeatedly can be shortened its work-ing life with contraction.Polyoxyethylene glycol phase change material chain structure is simple, easily crystallization, and can regulate transformation temperature by regulating relative molecular mass, play the effect that improves enthalpy, so have the range of application of broad.But polyoxyethylene glycol (PEG) itself is a kind of solid-liquid phase change materials, though after various processing, can change it into solid-solid phase transition material, but still have many weak points, Chinese patent CN1710012A, the blend of using polyoxyethylene glycol formation does not have thermoplasticity, the polyoxyethylene glycol amount that is adsorbed on fiber surface is less, influences heat accumulation, and constant temperature time is short.And its complicated process of preparation, the solvent system price height of use is difficult to reclaim, and causes the cost of this material to improve relatively.
Another kind of is to be the composite phase-change material of matrix with the polymkeric substance.When the solid-liquid in the matrix material was transformed into branch mutually and is attended by the transformation mutually of energy absorption or release, polymeric matrix played and coats and the effect of structural framework.Though have many good qualities, shortcoming is also comparatively remarkable.As being the phase-change accumulation energy cross-linked material,,, between the heat storage capacity of material and morphological stability, but there be the problem of control balance than difficulty as Chinese patent CN1754937A though advantages such as heat storage capacity is big, the source is abundant, cheap are arranged with paraffin.Polyvalent alcohol/polymkeric substance composite phase-change material latent heat of phase change is bigger, and can change transformation temperature and latent heat of phase change by polyvalent alcohol material more than 2 kinds is mixed in different ratios, to adapt to different Application Areass.But certain shortcoming is also arranged, and the performance of polyvalent alcohol is very unstable, volatile when elevated temperature, so will decompose gradually and lost efficacy through phase transformation system after the thermal cycling repeatedly, the life-span is shorter.
In sum, how to select having high enthalpy of phase change, thermal response rates, high stability, suitable controlled transformation temperature, the solid-solid phase-change energy-storage material of long service life will become the focus of people's research efficiently.
Summary of the invention
The purpose of this invention is to provide a kind of opal/polyurethane-type solid-solid phase-change energy-storage material and preparation method thereof, this material is widely used, and technology is simple, and solvent can recycle and reuse.
Opal provided by the present invention/polyurethane-type solid-solid phase-change energy-storage material is to be soft section with polyethylene glycols, aliphatics and aromatic isocyanate, is with triatomic material to be hard section, and molecular structure is as follows:
Described R is a polyoxyethylene glycol, and molecular weight is 200～2,000,000, and optimum weight is 1,000～10, any one of 000;
Described M is the derivative of vulcabond, be selected from 4-tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI), poly methylene poly phenyl poly isocyanate (PAPI), 2,6-two isocyanato methyl caproates (LDI), mphenylenedimethylim-vulcabond (XDI), to any one of hexichol isocyanic ester, a hexichol isocyanic ester;
Described N is for being with triatomic material, is selected from any one of glycerine, TriMethylolPropane(TMP), hexanetriol, trolamine;
Described Q is a solvent, is selected from ketone, ether, cyclic ethers, aromatic hydrocarbons, ester or the acid any one.
Described L is a catalyzer, is selected from triethylenediamine, triethylamine, N, any one of N dimethylcyclohexylam,ne, stannous octoate, dibutyltin dilaurate.
Above-mentioned polyoxyethylene glycol R, it and two monomers carry out obtaining solid-solid phase transition material after the polymerization.Its transformation temperature of this material is between 20 ℃～70 ℃, and the phase transformation enthalpy is 60～160J/g, and its transformation temperature is reversible, is that a kind of phase transition process reversible consolidate-encloses phase change materials, and the variation of its phase transformation enthalpy and transformation temperature can be controlled and regulate.The enthalpy of phase change of this material promptly has better phase-change thermal storage performance apparently higher than like product.And, therefore have better chemical stability and mechanical property because it has block little crosslinked polyurethane structural of holding concurrently.
The preparation method of opal of the present invention/polyurethane-type solid-solid phase-change energy-storage material comprises the steps:
(1) polyoxyethylene glycol end group isocyano activated sample prepolymer preparation
The isocyanates that takes by weighing 0.005～0.05mol is dissolved in the solvent of 10～30ml, adds in the three-necked bottle, drip to add appropriate amount of catalysts, and, after stirring, add 0.1g inorganic nano opal (opal), at N
2Add 20～50ml under the situation of gas shiled and contain polyoxyethylene glycol (PEG) solution of the dissolution with solvents of 0.002～0.02mol certain molecular weight, stir after 5～30min, be heated to backflow, react after 2～3 hours, promptly obtain activated sample;
(2) preparation of opal/urethane solid-to-solid transition material
Take by weighing 0.005～0.05mol with triatomic substance dissolves in the solvent of 10～30ml, add in the three-necked bottle, drip and add appropriate amount of catalysts, after stirring, wait to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 2～3 hours, the product that obtains is put into vacuum drying oven the solvent oven dry is promptly obtained opal/urethane solid-solid phase change material.
Described opal/polyurethane-type solid-solid phase-change energy-storage material, be that polyethylene glycols with certain molecular weight is soft section, aliphatics and aromatic isocyanate, with triatomic material is little cross-linked block copolymer of hard section, what wherein play a major role in the solid-solid phase-change process is soft section of polyoxyethylene glycol, soft section of polyoxyethylene glycol when temperature is elevated to transformation temperature, segment begins deliquescing, but can not flow by macroscopic, because the existence of material hard segment domains, in material, play a part physical crosslinking point, thereby limited the free movement of PEG, polyoxyethylene glycol (PEG) two is terminated on the skeleton of hard segment domains, therefore even when solid-solid phase transition material is heated to above 30～40 ℃ of PEG fusing points, present solid-state so still can macro-flow not take place.
Simultaneously, after adding natural nano inorganic materials opal, because opal is rich in natural nanoporous, the effect of its nano-scale, make the specific surface area of inorganic materials bigger, not only improved the phase transformation enthalpy of material, and improved its crystal property, making polymkeric substance is rapidly that nucleus carries out crystallization at short notice with the opal, crystallization rate is accelerated, impel the thermal response rates of material to accelerate, the heat transfer efficiency height, and present very regular and complete spherocrystal state.And the opaline mineral reserve of natural nano inorganic materials are abundant in China's standing stock, and are cheap, can reduce the cost of solid-solid phase-change energy-storage material like this.
Opal/polyurethane-type solid-solid phase-change energy-storage material has controlled high phase transformation enthalpy and suitable transformation temperature, thermal response rates is fast, stability is strong, long service life, be widely used in multiple occasions such as civil and military field, as agricultural booth film, sun power utilization, waste heat recovery, intelligent automatic air-conditioning and construction thing, glasshouse, phase change energy-storage type air-conditioning, electrical equipment constant temperature, insulation clothes etc.Again because it is nontoxic, cost is low, but has the application prospect that large-scale industrialization is produced.Have also that preparation method's technology is simple, solvent can recycle and reuse, advantage such as cheap.
Embodiment
Embodiment 1
(1) preparation of polyoxyethylene glycol (M=2000)/TDI prepolymer
The TDI that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 2000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=2000)/TDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 2:
(1) preparation of polyoxyethylene glycol (M=5000)/TDI prepolymer
The TDI that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 5000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=5000)/TDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 3:
(1) preparation of polyoxyethylene glycol (M=10000)/TDI prepolymer
The TDI that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 10000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=10000)/TDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 4:
(1) preparation of polyoxyethylene glycol (M=2000)/MDI prepolymer
Take by weighing 4 of 0.01mol, 4-hexichol level methane diisocyanate (MDI) base is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 2000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=2000)/MDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 5:
(1) preparation of polyoxyethylene glycol (M=5000)/MDI prepolymer
Take by weighing 4 of 0.01mol, 4-hexichol level methane diisocyanate (MDI) base is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 5000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=5000)/MDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 6:
(1) preparation of polyoxyethylene glycol (M=10000)/MDI prepolymer
Take by weighing 4 of 0.01mol, 4-hexichol level methane diisocyanate (MDI) base is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 10000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=10000)/MDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 7:
(1) preparation of polyoxyethylene glycol (M=2000)/HDI prepolymer
The hexamethylene diisocyanate (HDI) that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 20ml contains 0.005mol molecular weight 2000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=2000)/HDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 8:
(1) preparation of polyoxyethylene glycol (M=5000)/HDI prepolymer
The hexamethylene diisocyanate (HDI) that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 5000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=5000)/HDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Embodiment 9:
(1) preparation of polyoxyethylene glycol (M=10000)/HDI prepolymer
The hexamethylene diisocyanate (HDI) that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, adds the micro mist of the opal of 0.1g, at N
2Add the PEG acetone soln that 30ml contains 0.005mol molecular weight 10000 under the situation of gas shiled, stir after the 10min, be heated to backflow, react after 3 hours, promptly obtain activated sample.
(2) preparation of polyoxyethylene glycol (M=10000)/HDI/ glycerol/opal solid-solid phase transition material
The glycerol that takes by weighing 0.01mol is dissolved in the acetone solvent of 10ml, adds in the three-necked bottle, drips to add appropriate amount of catalysts, after stirring, waits to dropwise, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours,, put into vacuum drying oven the solvent oven dry is promptly obtained solid-solid phase change material the product that obtains.
Claims (8)
1. opal/polyurethane-type solid-solid phase-change energy-storage material is characterized in that polymkeric substance is soft section with polyethylene glycols, aliphatics and aromatic isocyanate, is with triatomic material to be hard section, and molecular structure is as follows:
R is a polyoxyethylene glycol, and molecular weight is 200～2,000,000,
M is the derivative of vulcabond, and N is for being with triatomic material, and Q is a solvent.
2. a kind of opal according to claim 1/polyurethane-type solid-solid phase-change energy-storage material is characterized in that: polyoxyethylene glycol R, molecular weight are 1000～10000.
3. a kind of opal according to claim 1/polyurethane-type solid-solid phase-change energy-storage material, it is characterized in that: the derivative M of vulcabond is selected from 4-tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI), poly methylene poly phenyl poly isocyanate (PAPI), 2,6-two isocyanato methyl caproates (LDI), mphenylenedimethylim-vulcabond (XDI), to the hexichol isocyanic ester, between in the hexichol isocyanic ester any one.
4. a kind of opal according to claim 1/polyurethane-type solid-solid phase change energy storage material is characterized in that: triatomic material N is glycerine, TriMethylolPropane(TMP), hexanetriol or trolamine.
5. a kind of opal according to claim 1/polyurethane-type solid-solid phase change energy storage material is characterized in that: solvent Q is ketone, ether, cyclic ethers, aromatic hydrocarbons, ester or acid.
6. the preparation method of opal/polyurethane-type solid-solid phase-change energy-storage material is characterized in that comprising that step is as follows:
(1) preparation of polyoxyethylene glycol end group isocyano activated sample prepolymer
The isocyanates of getting 0.005～0.05mol is dissolved in the solvent of 10～30ml, drips catalyzer, stirs, and adds 0.1g inorganic nano opal, at N
2Add 20～50ml under the situation of gas shiled and contain the polyglycol solution of 0.002～0.02mol, stir 5～30min, reflux was reacted 2～3 hours;
(2) preparation of opal/urethane solid-to-solid transition material
Get 0.005～0.05mol with triatomic substance dissolves in the solvent of 10～30ml, drip catalyzer, stir, at N
2Be heated to backflow under the gas shiled, reacted 2～3 hours, with the solvent oven dry of product.
7. the preparation method of a kind of opal according to claim 6/polyurethane-type solid-solid phase-change energy-storage material is characterized in that:
(1) preparation of polyoxyethylene glycol (M=2000)/4-toluene diisocyanate prepolymer
The 4-tolylene diisocyanate of getting 0.01mol is dissolved in the acetone solvent of 10ml, drips catalyzer, stirs, and adds the opaline micro mist of inorganic nano of 0.1g, at N
2Gas shiled adds the polyoxyethylene glycol acetone soln that 30ml contains 0.005mol molecular weight 2000 down, stirs after the 10min, is heated to backflow, reacts 3 hours.
(2) preparation of polyoxyethylene glycol (M=2000)/4-tolylene diisocyanate/glycerol/inorganic nano opal solid-solid phase transition material
The glycerol of getting 0.01mol is dissolved in the acetone solvent of 10ml, drips catalyzer, stirs, at N
2Be heated to backflow under the situation of gas shiled, react after 3 hours, solvent is dried.
8. the preparation method of a kind of opal according to claim 6/polyurethane-type solid-solid phase-change energy-storage material is characterized in that:
(1) preparation of polyoxyethylene glycol (M=10000)/4-toluene diisocyanate prepolymer
The 4-tolylene diisocyanate of getting 0.01mol is dissolved in the acetone solvent of 10ml, drips catalyzer, stirs, and adds the inorganic nano opal micro mist of 0.1g, at N
2Gas shiled adds the polyoxyethylene glycol acetone soln that 30ml contains 0.005mol molecular weight 10000 down, stirs after the 10min, is heated to backflow, reacts after 3 hours.
(2) preparation of polyoxyethylene glycol (M=10000)/4-tolylene diisocyanate/glycerol/inorganic nano opal solid-solid phase transition material
The glycerol of getting 0.01mol is dissolved in the acetone solvent of 10ml, drips catalyzer, stirs, at N
2Be heated to backflow under the gas shiled, reacted 3 hours, with the solvent oven dry of product.
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| FR3051479A1 (en) * | 2016-05-18 | 2017-11-24 | Univ Cergy-Pontoise | PHASE CHANGE MATERIAL FOR THERMAL ENERGY STORAGE, METHOD OF MANUFACTURE AND APPLICATIONS OF SUCH MATERIAL |
| WO2017198933A1 (en) | 2016-05-18 | 2017-11-23 | Universite Cergy-Pontoise | Phase-change material for storing thermal energy, manufacturing method and uses of such a material |
| CN107163547A (en) * | 2017-05-17 | 2017-09-15 | 北京大学 | A kind of solid-solid phase change thermal interfacial material and preparation method thereof |
| CN107602795A (en) * | 2017-09-18 | 2018-01-19 | 武汉纺织大学 | The method that graft copolymerization prepares solid-solid phase change material |
| CN108383968A (en) * | 2018-02-08 | 2018-08-10 | 中国工程物理研究院化工材料研究所 | High heat conduction polyurethane solid-solid phase transition material and preparation method thereof |
| CN108383968B (en) * | 2018-02-08 | 2021-01-26 | 中国工程物理研究院化工材料研究所 | High-thermal-conductivity polyurethane solid-solid phase change material and preparation method thereof |
| CN113319956A (en) * | 2021-05-31 | 2021-08-31 | 浙江农林大学 | Preparation method of heat-induced flexible phase change energy storage wood |
| CN113319956B (en) * | 2021-05-31 | 2022-05-20 | 浙江农林大学 | Preparation method of heat-induced flexible phase change energy storage wood |
| CN114621668A (en) * | 2022-03-25 | 2022-06-14 | 陕西科技大学 | Heat-insulation and heat-preservation polyethylene glycol-based polyurethane/tungsten-doped vanadium dioxide composite phase change coating and preparation method and application thereof |
| CN115010873A (en) * | 2022-06-21 | 2022-09-06 | 深圳大学 | Solid-solid phase change polymer material, preparation method thereof and glass window |
| CN115010873B (en) * | 2022-06-21 | 2023-12-01 | 深圳大学 | Solid-solid phase change polymer material, preparation method thereof and glass window |
| CN115028988A (en) * | 2022-06-30 | 2022-09-09 | 重庆理工大学 | Organic montmorillonite polyurethane solid-solid phase change material and preparation method and application thereof |
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