CN101822962A - Preparation method of phase-change energy-storing capsule adopting non-isocyanate polyurethane as capsule walls - Google Patents
Preparation method of phase-change energy-storing capsule adopting non-isocyanate polyurethane as capsule walls Download PDFInfo
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Abstract
The invention relates to a preparation method of a phase-change energy-storing capsule adopting non-isocyanate polyurethane as capsule walls, comprising the following steps: (1) taking an organic phase-change material and adopting alginate and polyethylene and the like as base materials to prepare shape-stabilized phase-change material particles; (2) adding the prepared shape-stabilized phase-change material particles into organic polyamine monomer or low polymer for soaking, taking out the prepared shape-stabilized phase-change material particles and air-drying; and (3) putting 10 parts of the obtained shape-stabilized phase-change material particles by surface treatment into 12-25 parts of cyclocarbonate monomer diluted by ethyl acetate under stirring condition, reacting at the temperature of 30-70 DEG C, generating non-isocyanate polyurethane layers on the surfaces of the shape-stabilized phase-change material particles, filtering and washing and drying the product to obtain the phase-change energy-storing capsule. The preparation method adopts environment-friendly non-isocyanate polyurethane as the capsule walls, replaces the traditional isocyanate type polyurethane with larger toxicity, covers the shape-stabilized phase-change material capsule core again, avoids the leakage of phase-change materials, and the obtained energy-storing capsule is especially applicable to the use of solar heat storage systems and insulating wall bodies of energy-saving buildings.
Description
Technical field
The present invention relates to phase-changing energy storage material and preparation technology thereof, especially a kind of is the preparation method and products thereof of the phase-change accumulation energy capsule of clad material with the non-isocyanate polyurethane.
Background technology
The novel energy material is to support the mankind nowadays civilization and ensure the important material base of social development.Phase-changing energy storage material is when experience changes mutually in specific temperature range, can absorb, store or discharge a large amount of heat energy, and self-temperature to remain unchanged.In the current society that the energy and environmental problem highlight, phase-changing energy storage material can be alleviated the contradiction of energy supply and demand on time-space.Develop high performance phase-changing energy storage material and have important theory and using value promoting China's ecological energy-saving building materials.
Shaping phase-change material is a kind of novel energy-storing material, is made up of phase-change material and backing material, has realized the phase-change material solid state, has made things convenient for the application of phase-change material.Phase-change material in the shaping phase-change material generally adopts organic alkane of different phase transition temperatures, and backing material has polyethylene, polystyrene, styrene-butadiene-copolymer, expanded graphite, imvite etc.As calendar year 2001, it is the typing phase-change material of backing material with the expanded graphite that people such as Xavier have prepared, wherein the shared mass fraction of phase-change material can be greatly to 0.65～0.95, and the thermal conductivity factor of composite phase-change material improves a lot with respect to the thermal conductivity factor that pure phase becomes material.People such as calendar year 2001 Xiao Min have then made paraffin-styrene-butadiene-copolymer shaping phase-change material.2003, two kinds of phase-change materials of human A such as Fang Guiyin, B were compound, mixed 53% solid support material then, and having made phase transition temperature is 54.6 ℃, and the phase transformation enthalpy is the shaping phase-change material of 117.8KJ/kg.2004, people such as people such as Ye Hong and Ahmet Sari are is phase-change material with paraffin, be that backing material prepares shaping phase-change material with the high density polyethylene (HDPE), shaping phase-change material is used for energy saving building is expected partly or entirely to replace heating installation and air-conditioning, reach the purpose of energy-saving and emission-reduction.
Shaping phase-change material has advantages such as high efficiency, low cost, preparation technology are simple, has bright application prospect.But also there are some problems in practical application.At first have fast problem such as decline of organic phase change material leakage, frosting and hot property, this is because backing material only plays " supports " to phase-change material and acts on, and is that a kind of open to the outside world type wraps up, and causes the phase-change material sealing property is relatively poor.It is necessary that shaping phase-change material is carried out surface treatment.
2003, Chinese patent CN1546596A has announced a patent of invention-" the shaping phase-change material surface being prevented blending the method for flame treatment " of people such as Yang Rui, in the patent grafting is carried out on the shaping phase-change material surface, by light-initiated polar monomer is received the shaping phase-change material surface, form one deck polar layer.Make the surface of paraffin ooze out phenomenon be improved significantly, this material has also possessed certain fire resistance simultaneously.But this preparation technology is loaded down with trivial details, and cost is higher, is unfavorable for large-scale production.
2005, Chinese patent CN1657587A has announced people's such as Wang Shujun patent of invention-" a kind of preparation method of phase transformation material for microcapsult packing and forming ", and they have carried out encapsulated encapsulation by situ aggregation method to the paraffin shaping phase-change material with cyanurotriamide modified urea resin.This preparation section is complicated, shaping phase-change material need be ground into encapsulation again behind the micron particles.It should be noted that residually in the wall material of this capsule has a free formaldehyde, is unfavorable for environmental protection and human health.
2008, Chinese patent CN101284986A has announced people's such as Zhang Xingxiang patent-" a kind of preparation method of macrocapsule of wax shaping phase-change material ", they repeat successively at fixed phase change particle surface spraying cyst wall liquid (sodium silicate aqueous solution that contains plasticizer), cover consolidation liquid (any one in sulfuric acid, nitric acid, hydrochloric acid, acetic acid and the phosphoric acid) behind the hot blast drying, hot blast drying.Obtain a kind of macrocapsule of wax shaping phase-change material at last.This preparation technology's more complicated, and encapsulating material poor-performing.
In addition, it is the phase-change accumulation energy capsule of cyst wall that some researchers have studied with the polyisocyanic acid ester polyurethane, and as " preparation method of energy-storing polyurethane microcapsule (CN101029215A) " of Hua Mingyang, the cyst wall of microcapsules is to adopt the polyisocyanates polyurethane material.Yet because the median surface polymerization of capsule preparation process is insufficient, the hypertoxic monomer-polyisocyanates that remains in the capsule has limited its application.
In applicant's range of search, adopting environmentally friendly non-isocyanate polyurethane is cyst wall, and the research that coats the shaping phase-change material aspect yet there are no report.
Summary of the invention
For the problems such as phase-change material leakage, poor fire and complicated process of preparation that the shaping phase-change material that solves prior art for preparing exists, the invention provides a kind of is the phase-change accumulation energy capsule preparation method thereof and products thereof of cyst wall with the non-isocyanate polyurethane.The phase-change accumulation energy capsule that this method makes is a kind of monokaryon shell structure, it is that cyst wall replaces conventional urethane with the non-isocyanate type polyurethane material, capsule-core comprises that for the typing phase-change material with high polymers such as alginate, silicate, polyethylene be the shaping phase-change material of base material.
The present invention is the phase-change accumulation energy capsule preparation method thereof of cyst wall with the non-isocyanate polyurethane, may further comprise the steps:
(1), get the organic phase change material that latent heat of phase change is 100～300J/g, be that base material is made the shaping phase-change material particle with alginate, silicate, polyethylene, polypropylene or polystyrene;
(2), shaping phase-change material particle that step (1) is made joins in organic multicomponent amine monomers or the oligomer and soaks 10～120min, takes out air-dry surface; Described organic multicomponent amine comprises diethylenetriamine or TEPA.
(3), surface treated shaping phase-change material particle 10 mass parts that step (2) is obtained, under 10～100rpm rotating speed stirs, put in the cyclic carbonate ester monomer or oligomer solution 12～25 mass parts with the ethyl acetate dilution, and at 30～70 ℃ of following reaction 1.5～6hr, surface at surface treated shaping phase-change material particle generates the non-isocyanate polyurethane layer, with product filter, washing, air-dryly promptly be able to the phase-change accumulation energy capsule that non-isocyanate polyurethane is a cyst wall; Wherein, the ethyl acetate consumption is 6～50% of cyclic carbonate ester monomer or an oligomer quality in cyclic carbonate ester monomer or the oligomer solution.
Wherein, one of preparation method of described shaping phase-change material particle is: the described organic phase change material of 30～80 mass parts and the base materials such as described polyethylene, polypropylene or polystyrene of 20～70 mass parts are mixed, through double screw extruder blend granulation.
The preparation method of described another kind of shaping phase-change material particle is: with 10 mass parts of the organic phase change material after the fusion and concentration is the emulsifier aqueous solution 30-90 mass parts of 1～10wt%, add in the sodium alginate aqueous solution 10-100 mass parts of 2.0～5.0wt%, abundant stirring and emulsifying under 30～60 ℃, 1000～5000 rev/mins conditions, leave standstill, deaeration obtains thick emulsion; Under 10～500 rev/mins of rotating speeds stir, emulsion droplets is added to the CaCl of 1～4wt% by the orifice device then
2In the coagulating bath, coagulation forming promptly gets alginic acid alkali shaping phase-change material particle.Wherein, emulsifying agent is styrene maleic anhydride copolymer, polyvinyl alcohol or polyvinylpyrrolidone.
Described organic phase change material is selected aliphatic hydrocarbon, fatty alcohol, aliphatic acid or fatty acid ester etc. for use, and latent heat of phase change is 100～300J/g.Wherein, the preferred C of described aliphatic hydrocarbon
14～C
50Alkane in any or its any combination, especially be preferably the tetradecane, hexadecane, octadecane, eicosane, No. 25 phase transformation paraffin or No. 30 phase transformation paraffin.The preferred lauryl alcohol of described fatty alcohol, tetradecyl alchohol, hexadecanol, 18 alcohol, cyclohexanol, the tert-butyl alcohol, 2,2- dimethyl 1,3 propane diols or 2-amino-2 methyl isophthalic acid, 3 glycerine.The preferred capric acid of described aliphatic acid, laurate, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoid acid or their at least two kinds mixture, but be not limited thereto the material that list in the place.Described cyclic carbonate ester monomer or oligomer adopt propene carbonate-propane diols cyclic carbonate ester, propane diols cyclic carbonate ester or the like.
Adopting a kind of of method for preparing is the phase-change accumulation energy capsule of cyst wall with the non-isocyanate polyurethane, it is characterized in that: this phase-change accumulation energy capsule is a kind of monokaryon shell structure, cyst wall is the non-isocyanate type polyurethane material, this cyst wall coats typing phase-change material capsule-core densely, comprise in this typing phase-change material capsule-core that latent heat of phase change is the organic phase change material of 100～300J/g, the quality percentage composition of this organic phase change material in this phase-change accumulation energy capsule is 20～80%.
Described phase-change accumulation energy capsule is light brown, spherical shape, and average particle size distribution is at 100 μ m～5mm; The thickness of non-isocyanate type polyurethane material cyst wall is 200～400 μ m.
Wherein, described typing phase-change material capsule-core is for being the shaping phase-change material capsule-core of base material with alginate, silicate, polyethylene, polypropylene or polystyrene.
It is that cyst wall, shaping phase-change material are the capsule of capsule-core with the non-isocyanate type polyurethane that the present invention adopts the interfacial polymerization preparation.Compared with prior art, the present invention has the following advantages:
It is cyst wall that the present invention adopts the non-isocyanate polyurethane of environmental protection more, replace the bigger isocyanates type polyurethane of traditional toxicity, the shaping phase-change material capsule-core is coated once more, avoided the seepage of phase-change material, improved the interface affinity energy of shaping phase-change material simultaneously.
It is capsule-core that the present invention adopts shaping phase-change material, has strengthened the mechanical performance of capsule greatly, enables to be widely used in building field, and field such as military, civilian, household electrical appliances.
The present invention adopts interfacial polymerization to prepare the shaping phase-change material capsule, and technology is simple, and environmentally safe is easy to suitability for industrialized production, reduces cost.The present invention obtains is that the phase-change accumulation energy capsule of cyst wall is particularly useful for uses such as solar heat-preservation system, ecological energy conservation building heat-preserving wall with the non-isocyanate polyurethane, has the energy-saving and emission-reduction meaning.
Description of drawings
What Fig. 1 made for the present invention is the phase-change accumulation energy capsule enlarged photograph of cyst wall with the non-isocyanate polyurethane;
Fig. 2 is the enlarged photograph after the grain phase-change accumulation energy capsule partly cut-away one of among Fig. 1;
Fig. 3 is the DSC curve of phase-change accumulation energy capsule of the present invention.
The specific embodiment
Below in conjunction with embodiment the present invention is described in detail.
1, preparation alginic acid alkali shaping phase-change material
Make emulsifier aqueous solution A with mixing in the 2.0g maleic anhydride of styrene emulsifying salt agent adding 100.0g water, to add after the fusion of 20.0g n-octadecane among the emulsifier aqueous solution A then, and under 5000rpm emulsify at a high speed 3min, system temperature remains on 40 ℃, make stable emulsion B, outward appearance is the milky opaque liquid.Sodium alginate aqueous solution 120g is added among the above-mentioned emulsion B, fully stir, and leave standstill the 30min deaeration and obtain thick emulsion C.Sodium alginate aqueous solution is pressed sodium alginate: the weight ratio preparation of water=2: 98.
Adopt the orifice device with emulsion C then, under 10～500rpm stirs, drop to CaCl
2In the coagulating bath, take out alginic acid alkali shaping phase-change material particle behind the coagulation forming.CaCl
2CaCl is pressed in coagulating bath
2: H
2O=4: 96 weight ratio preparation.
2, alginic acid alkali shaping phase-change material particle is carried out surface treatment
The shaping phase-change material particle that makes joined soak 60min in the diethylenetriamine, it is standby to take out air-dry surface.
3, with surface treated alginic acid alkali shaping phase-change material particle 20g, under the 50rpm stirring action, put into in the 40g cyclic carbonate ester monomer solution, and under 60 ℃, react the 2hr time, after surface treated shaping phase-change material particle surface generates one deck non-isocyanate polyurethane, product is filtered, and washing air-dryly promptly is able to the phase-change accumulation energy capsule that non-isocyanate polyurethane is a cyst wall.Wherein, the cyclic carbonate ester monomer solution is preparation in 4: 1 by the mass ratio of cyclic carbonate ester and ethyl acetate.
Adopt the hot property of fixed this phase-change accumulation energy capsule of differential scanning calorimeter test, phase transition temperature is 28 ℃, and the average phase change enthalpy is about 129J/g.
Take by weighing the n-octadecane of 50 mass parts, add the high density polyethylene (HDPE) of 50 mass parts, mix,, obtain cylinder bodily form n-octadecane/polyethylene composite shape-setting phase-change material particle through double screw extruder blend granulation.
The gained particle joined soak 100min in the diethylenetriamine, it is standby to take out air-dry surface.
With surface treated shaping phase-change material particle 100g, under 60rpm stirs, put in the 150g cyclic carbonate ester monomer solution, and under 40 ℃, react the 5hr time, after surface treated shaping phase-change material particle surface generates one deck non-isocyanate polyurethane, with the product filtration washing, air-dryly promptly be able to the phase-change accumulation energy capsule that non-isocyanate polyurethane is a cyst wall.Wherein, the cyclic carbonate ester monomer solution is preparation in 7: 1 by the mass ratio of cyclic carbonate ester and ethyl acetate.
Adopt the hot property of differential scanning calorimeter test shaping phase-change material capsule, phase transition temperature is 28 ℃, and the average phase change enthalpy is 96J/g.
Take by weighing No. 30 paraffin of 60 mass parts, add the polystyrene of 40 mass parts, mix,, obtain cylinder bodily form n-octadecane/polyethylene composite shape-setting phase-change material particle through double screw extruder blend granulation.
The gained particle joined soak 60min in the TEPA, it is standby to take out air-dry surface.
With surface treated shaping phase-change material particle 500g, under the 60rpm stirring action, in the 750g cyclic carbonate ester monomer solution, and under 60 ℃, react the 5hr time, after surface treated shaping phase-change material particle surface generates one deck non-isocyanate polyurethane, product is filtered, and washing air-dryly promptly is able to the phase-change accumulation energy capsule that non-isocyanate polyurethane is a cyst wall.Wherein, the cyclic carbonate ester monomer solution is preparation in 6: 1 by the mass ratio of cyclic carbonate ester and ethyl acetate.
Adopt the hot property of differential scanning calorimeter test shaping phase-change material capsule, phase transition temperature is 30 ℃, and the average phase change heat content is 82J/g.
Adopting said method can prepare with the non-isocyanate polyurethane is the phase-change accumulation energy capsule of cyst wall, this phase-change accumulation energy capsule is a kind of monokaryon shell structure, cyst wall is the non-isocyanate type polyurethane material, this cyst wall coats typing phase-change material capsule-core densely, comprise in this typing phase-change material capsule-core that latent heat of phase change is the organic phase change material of 100～300J/g, the quality percentage composition of this organic phase change material in this phase-change accumulation energy capsule is 20～80%.Wherein, described typing phase-change material capsule-core is for being the shaping phase-change material capsule-core of base material with alginate, silicate, polyethylene, polypropylene or polystyrene.
What Fig. 1 made for the embodiment of the invention 1 is the phase-change accumulation energy capsule enlarged photograph in kind of cyst wall with the non-isocyanate polyurethane.Cyst wall is the non-isocyanate polyurethane material, and capsule-core is a sodium alginate base shaping phase-change material, and this as can be seen capsule is light brown, regular spherical shape, and particle diameter is evenly distributed, and average grain diameter is about 2.5mm.In this phase-change accumulation energy capsule, the quality percentage composition of n-octadecane is 55%.
Fig. 2 is the enlarged photograph after Fig. 1 phase-change accumulation energy capsule partly cut-away.As can be seen, this capsule has tangible monokaryon shell structure from section portion, and beige non-isocyanate polyurethane is coated on the shaping phase-change material surface evenly, densely, and thickness is about 200～400 μ m.Fig. 3 is the DSC curve of phase-change accumulation energy capsule of the present invention.As can be seen, the heat content that the fusion of capsule absorbs is 124.39J/g, and melt temperature is 29.26 ℃, and the enthalpy that crystallization discharges is 132.90J/g, and crystallization temperature is 16.51 ℃, has energy storage effect preferably.
Claims (9)
1. one kind is the phase-change accumulation energy capsule preparation method thereof of cyst wall with the non-isocyanate polyurethane, it is characterized in that may further comprise the steps:
(1), get the organic phase change material that latent heat of phase change is 100～300J/g, be that base material is made the shaping phase-change material particle with alginate, silicate, polyethylene, polypropylene or polystyrene;
(2), shaping phase-change material particle that step (1) is made joins in organic multicomponent amine monomers or the oligomer and soaks 10～120min, takes out air-dry surface; Described organic multicomponent amine comprises diethylenetriamine or TEPA.
(3), surface treated shaping phase-change material particle 10 mass parts that step (2) is obtained, under 10～100rpm rotating speed stirs, put in the cyclic carbonate ester monomer or oligomer solution 12～25 mass parts with the ethyl acetate dilution, and at 30～70 ℃ of following reaction 1.5～6hr, surface at surface treated shaping phase-change material particle generates the non-isocyanate polyurethane layer, with product filter, washing, air-dryly promptly be able to the phase-change accumulation energy capsule that non-isocyanate polyurethane is a cyst wall; Wherein, the ethyl acetate consumption is 6～50% of cyclic carbonate ester monomer or an oligomer quality in cyclic carbonate ester monomer or the oligomer solution.
2. preparation method as claimed in claim 1, the preparation method who it is characterized in that described shaping phase-change material particle is: the described organic phase change material of 30～80 mass parts and described polyethylene, polypropylene or the polystyrene base material of 20～70 mass parts are mixed, through double screw extruder blend granulation.
3. preparation method as claimed in claim 1, the preparation method who it is characterized in that described shaping phase-change material particle is: with 10 mass parts of the organic phase change material after the fusion and concentration is emulsifier aqueous solution 30～90 mass parts of 1～10wt%, add in sodium alginate aqueous solution 10～100 mass parts of 2.0～5.0wt%, abundant stirring and emulsifying under 30～60 ℃, 1000～5000rpm condition, leave standstill, deaeration obtains thick emulsion; Wherein, emulsifying agent is styrene maleic anhydride copolymer, polyvinyl alcohol or polyvinylpyrrolidone;
Under 10～500rpm rotating speed stirs, emulsion droplets is added to the CaCl of 1～4wt% by the orifice device then
2In the coagulating bath, coagulation forming promptly gets alginic acid alkali shaping phase-change material particle.
4. as claim 1 or 2 or 3 described preparation methods, it is characterized in that: described organic phase change material is selected aliphatic hydrocarbon, fatty alcohol, aliphatic acid or fatty acid ester for use.
5. preparation method as claimed in claim 4 is characterized in that: the preferred tetradecane of described aliphatic hydrocarbon, hexadecane, octadecane, eicosane, No. 25 phase transformation paraffin or No. 30 phase transformation paraffin;
The preferred lauryl alcohol of described fatty alcohol, tetradecyl alchohol, hexadecanol, 18 alcohol, cyclohexanol, the tert-butyl alcohol, 2,2-dimethyl 1,3 propane diols or 2-amino-2 methyl isophthalic acid, 3 glycerine;
Described aliphatic acid is preferably capric acid, laurate, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoid acid or their at least two kinds mixture.
6. preparation method as claimed in claim 1 is characterized in that: described cyclic carbonate ester monomer adopts propene carbonate-propane diols cyclic carbonate ester or propane diols cyclic carbonate ester.
7. one kind is the phase-change accumulation energy capsule of cyst wall with the non-isocyanate polyurethane, it is characterized in that: this phase-change accumulation energy capsule is a kind of monokaryon shell structure, cyst wall is the non-isocyanate type polyurethane material, this cyst wall coats typing phase-change material capsule-core densely, comprise in this typing phase-change material capsule-core that latent heat of phase change is the organic phase change material of 100～300J/g, the quality percentage composition of this organic phase change material in this phase-change accumulation energy capsule is 20～80%.
8. phase-change accumulation energy capsule as claimed in claim 8 is characterized in that: described phase-change accumulation energy capsule is light brown, spherical shape, and average particle size distribution is at 100 μ m～5mm; The thickness of non-isocyanate type polyurethane material cyst wall is 200～400 μ m.
9. phase-change accumulation energy capsule as claimed in claim 8 is characterized in that: wherein, described typing phase-change material capsule-core is for being the shaping phase-change material capsule-core of base material with alginate, silicate, polyethylene, polypropylene or polystyrene.
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| CN103468223A (en) * | 2013-09-30 | 2013-12-25 | 天津工业大学 | Phase change energy storage material macro-capsule and method for preparing same |
| CN103537238A (en) * | 2013-09-26 | 2014-01-29 | 航天海鹰(镇江)特种材料有限公司 | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule |
| CN103769021A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of organic-inorganic composite capsule wall energy-storage microcapsule |
| CN104559935A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Composite-wall phase-change energy storing microcapsule and preparation method thereof |
| CN105969316A (en) * | 2016-06-03 | 2016-09-28 | 宁海德宝立新材料有限公司 | Phase-change heat-storage composite material for hot compress |
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| CN103769021A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of organic-inorganic composite capsule wall energy-storage microcapsule |
| CN103769021B (en) * | 2012-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of preparation method of Organic-inorganic composite cyst wall accumulation energy microcapsule |
| CN103537238A (en) * | 2013-09-26 | 2014-01-29 | 航天海鹰(镇江)特种材料有限公司 | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule |
| CN103537238B (en) * | 2013-09-26 | 2015-06-10 | 航天海鹰(镇江)特种材料有限公司 | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule |
| CN103468223A (en) * | 2013-09-30 | 2013-12-25 | 天津工业大学 | Phase change energy storage material macro-capsule and method for preparing same |
| CN104559935B (en) * | 2013-10-24 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of compound cyst wall microcapsules of storing energy through phase change and preparation method thereof |
| CN104559935A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Composite-wall phase-change energy storing microcapsule and preparation method thereof |
| CN105969316A (en) * | 2016-06-03 | 2016-09-28 | 宁海德宝立新材料有限公司 | Phase-change heat-storage composite material for hot compress |
| CN105969316B (en) * | 2016-06-03 | 2020-11-10 | 宁海德宝立新材料有限公司 | Phase-change heat storage composite material for hot compress |
| CN106350018A (en) * | 2016-07-29 | 2017-01-25 | 上海应用技术学院 | Water-free microwave heating energy-storing microcapsule with hot compress function and preparation method |
| CN111234740A (en) * | 2020-03-14 | 2020-06-05 | 广东力王新材料有限公司 | Two-component heat storage potting material |
| CN111718573A (en) * | 2020-07-09 | 2020-09-29 | 江苏省特种设备安全监督检验研究院 | Graphene blending modified phase-change foaming thermal insulation material and preparation method thereof |
| CN112680197A (en) * | 2021-01-06 | 2021-04-20 | 华中科技大学 | Inorganic hydrated salt composite phase-change material and preparation method thereof |
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| CN101822962B (en) | 2012-08-29 |
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