CN1482204A - Energy-accumulating temp-controlled thermoplastic cross-link high-molecular composite material with solid-solid phase change and its preparing process - Google Patents
Energy-accumulating temp-controlled thermoplastic cross-link high-molecular composite material with solid-solid phase change and its preparing process Download PDFInfo
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Abstract
The present invention features that the material has crosslinked crystalline polyolefin as base body and crystalline alkyl hydrocarbon dispersed inside the crosslinked net as the composite material for phase change energy accumulation. In the composite material, the phase change energy accumulating component accounting for 40-80 % has solid-solid phase conversion at phase change temperature of 20-80 deg.c and phase change enthalpy greater than 80 J/g. The composite phase change material has relatively high energy accumulating density and excellent heat stability, may be used as energy accumulating material for the accumulation of solar energy and industrial afterheat, constant temperature in building and energy saving in air conditioner and as temperature control material in electronic instrument, machinery, etc. widely.
Description
Technical field
The present invention relates to the phase-changing energy storage material technical field, the preparation method of the energy storage of cross-linked type macromolecule solid-to-solid transition specifically temperature control matrix material.
Background technology
It absorbs the phase changing energy storage material use in the reversible transformation process or the characteristics of emitting a large amount of heats can be carried out the storage and the release of energy under constant temp.Compare with sensible heat energy storage mode, utilize phase-change accumulation energy to have energy storage density height, thermo-efficiency height and suction, exothermic process is advantages such as constant temperature, therefore this class functional materials can be widely used in the every field of military and civilian, comprising: (1) storage of solar energy; (2) industrial exhaust heat utilization; (2) electric power low-load period energy storage; (3) air conditioner system energy saving; (4) temperature-constant building and heat preservation construction material; (5) temperature is controlled (electronic instrument, precision optical machinery, space flight and aviation etc.) automatically.
Traditional phase-changing energy storage material comprises various crystalline hydrate salt, inorganic molten salt and some organic compound (as paraffin, polyoxyethylene glycol, lipid acid etc.).They mainly utilize solid-liquid phase transition regime to carry out energy storage and release.Because the solid-liquid phase change materials liquid state occurs in the phase change process, so need container in use phase change material and heat-transfer fluid are separated, by the heat exchange between interchanger realization heat-transfer fluid and the phase change material.This has increased the cost of system on the one hand, has also limited the range of application of phase change material on the other hand.It is solid-state that the solid-to-solid transition material still can keep when undergoing phase transition, and then do not need container in use; Some solid-to-solid transition material itself has certain intensity in addition, can be used as structured material and uses; Therefore the solid-to-solid transition material has bigger advantage than the solid-liquid phase change materials.
Present existing solid-to-solid transition material mainly comprises: the organic composite phase-change material of (1) metal (Perovskite laminated composites); Small molecules solid-to-solid transition polyvalent alcohol and polymkeric substance composite phase-change material (Achard P., Mayer D., U.S.pat.No.4,616,173); Organic acid/SiO
2Composite phase-change material (Salyer I.O., U.S.pat.5,370,814); Microencapsulated composite phase-change material (Chen, U.S.pat.4,504,402); And poly-7 glycol/compound solid-to-solid transition material of Mierocrystalline cellulose (CN 99116109.2 for Guo Yuanqiang, beam sea of learning .CN 96121468.6).It is original solid-state that these materials all keep when undergoing phase transition, but have different defectives in performance with using.The organic composite phase-change material of metal has higher heat-conduction coefficient and stable phase transformation performance, but price is very expensive, and material is frangible powder, can only be as filler and the compound use of polymkeric substance.Polyvalent alcohol and polymkeric substance composite phase-change material have higher energy storage density (enthalpy of phase change is greater than 50 joule/gram), but the volatility of material is big, and thermostability is bad, influences its use properties.Organic acid/SiO
2Although the composite phase-change material cost is lower, the organic acid decomposition of volatilizing easily makes and the phase transformation unstable properties of material has limited the application of such material.The enthalpy of phase change of microencapsulated phase change material is bigger, but the thermal conductivity of material is lower, preparation cost is higher; And the volume change during phase transformation is very big, and pucker ﹠ bloat repeatedly makes the work-ing life of material shorter.The complicated process of preparation of polyoxyethylene glycol/cellulose family composite high-molecular solid-to-solid transition material, the solvent system price of use is high and reclaim difficulty, and the preparation cost of material is very high.
The method preparation that Salyer utilizes crosslinked polyethylene to flood in the solid-liquid phase change material contains the polyolefine composite phase-change material (U.S.Pat.5,053,446) of phase transformation composition.There is following shortcoming in this preparation method: (1) uses radiation crosslinking or the crosslinked method crosslinked polyethylene of organo-peroxide, and facility investment is very big, and production cost is very high; (2) great changes will take place for crosslinked polyethylene dipping back shape of products and size; (3) sample dipping back is cleaned with pentane or hexane and is had solvent recuperation and problem of environmental pollution; (4) phase change material is difficult to make the goods of various complicated shapes.
Summary of the invention
The purpose of this invention is to provide a kind of cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material and preparation method thereof with energy storage and temperature controlled function.This material has good thermostability in the transformation temperature scope, and transformation temperature and enthalpy of phase change do not change with times of thermal cycle, and material absorbed heat, and each is consistent with the transformation temperature of exothermic process, does not in use have weightlessness.
Cross-linking type phase-changing energy storage material of the present invention be a kind of with crosslinked crystalline polyolefin as matrix, be dispersed with the matrix material of crystalline alkyl hydrocarbon polymer in the cross-linked network as the phase-change accumulation energy composition.The phase-change accumulation energy composition is between 40-80% in this matrix material, and this material has the solid-to-solid transition behavior, and phase transition temperature is 20 ℃-80 ℃, and enthalpy of phase change is greater than 80 joule/gram.
The preparation method of above-mentioned cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material has two kinds:
(1). polyolefin resin carries out the polyolefine that the fusion-grafting preparation has crosslinkable groups with vinyl silanes earlier, put into hot water this graft product is made the goods of various desired shapes by the forming method of thermoplastic resin after, in the presence of catalyzer, carry out crosslinked.Crosslinked products is carried out swelling on the fusing point of crystallinity alkyl hydrocarbon polymer and polyolefinic fusing point can obtain composite phase-change energy storage material.Can make the cross-linked type macromolecule solid-to-solid transition energy-storage composite material of solid-liquid phase change material content by controlling polyolefinic crosslinking degree (gel content) and swollen time at 40-80%.
(2). polyolefin resin and vinyl silanes carry out the polyolefine that the fusion-grafting preparation has crosslinkable groups, this graft product is dissolved in forms the homodisperse thing in paraffin or other crystallinity alkyl hydrocarbon polymer.This product is made the goods of various desired shapes by the forming method of thermoplastic resin, put into hot water then and in the presence of catalyzer, carry out crosslinkedly, make the cross-linked type macromolecule solid-to-solid transition energy-storage composite material of 40-80% phase transformation component content.
From thermodynamic (al) angle, the solid-liquid that is still material that in fact the solid-solid phase-change energy-accumulating material great majority of having developed at present utilize changes mutually, solid-liquid phase change materials and some structured materials is compounded to form the compound phase change material by special structural design that is:.When the solid-liquid in the matrix material changed composition mutually and is attended by the transformation mutually of heat absorption or release, structured material held onto them, did not allow their take place to flow; Structured material plays the effect of skeleton in matrix material simultaneously, makes matrix material keep certain shape and intensity.
Be dissolved in the solid-liquid phase change materials by the crystalline polymer that will have crosslinkable groups, and then polymkeric substance is cross-linked to form cross-linked network, a large amount of solid-liquid phase change materials can be dispersed in the crosslinked polymer grid, a kind ofly be support frame and coating layer, be the polymer solid-to-solid transition matrix material of phase-change accumulation energy composition with dispersive solid-liquid phase change materials with the crosslinked polymer network thereby form.In this matrix material, the solid-liquid phase change materials still can be by changing absorption or releasing energy mutually, and the crosslinked polymer network will be dispersed on the one hand inner solid-liquid and change composition mutually and wrap, make it be in liquid state and also can not ooze out, guarantee that on the other hand material has the shape of enough strength maintenance self.
It is crystalline long chain alkane hydrocarbon, for example paraffin, lipid acid, fatty acid ester etc. that solid-liquid in the solid-to-solid transition composite energy-storage material provided by the present invention changes composition mutually.The solid-liquid phase change materials should have stable chemistry, physicals, still has stable transformation behavior after the long term thermal circulation; And environment and ecology are not worked the mischief.
Polymkeric substance among the present invention is crystalline polyolefine, for example polyethylene, polypropylene, polypropylene, crystalline ethene and acetate ethylene copolymer, crystalline ethene and propylene copolymer etc.They should have consistency preferably with the solid-liquid phase change materials, and have suitable crystalline melt point with guarantee crosslinked matrix material can be in the comparatively high temps scope life-time service.
The present invention has the polyolefine of crosslinkable reactive group by the method preparation of grafted silane on the molecular polyolefin chain.This method is carried out grafting with melt extrusion with polyolefine and vinyl silanes, organo-peroxide and oxidation inhibitor uniform mixing earlier.Organo-peroxide decomposes the elementary free radical of generation in extrusion, the dehydrogenation from the polyolefine macromolecular chain of these elementary free radicals generates macromolecular radical, and vinyl silanes just can obtain having on the molecular chain polyolefine of siloxanes side group carrying out addition on the macromolecular radical.This polyolefine that has the siloxanes side group still has flowability, can carry out moulding by the various method for processing forming of thermoplastic resin; Yet in the presence of catalyzer and water, hydrolysis reaction takes place earlier and forms silanol in the siloxanes side group, and mutual condensation forms crosslinked network structure between the silanol then.Therefore the fusion-grafting of polyolefine and vinyl silanes can carry out on common extrusion equipment (twin screw extruder or single screw extrusion machine), has advantages such as less investment, flexible operation, technology are simple.Vinyl silanes among the present invention comprises vinyltrimethoxy silane (A171), vinyltriethoxysilane (A151), vinyl trimethoxy Ethoxysilane etc., and its consumption is the 0.5-5% of polyolefin resin consumption.Organo-peroxide among the present invention comprises dicumyl peroxide (DCP), t-tutyl cumyl peroxide (TBPB), benzoyl peroxide (BPO), 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexanes (L130) etc., its consumption is the 0.03-0.5% of polyolefin resin consumption.Oxidation inhibitor among the present invention comprises various Hinered phenols antioxidants, for example 2,6 ditertiary butyl p cresol (BHT), antioxidant 1010, antioxidant 1076 etc., and consumption is the 0.3-0.8% of polyolefin resin consumption.The catalyzer of silane hydrolyzate condensation is organic tin compound and anhydrides compound among the present invention, comprises dibutyl tin laurate, stannous octoate etc.The range of reaction temperature of fusion-grafting is 150-240 ℃.
Cross-linked polyolefin after the swelling end, still is adsorbed with a large amount of paraffin at product surface in paraffin wax, Salyer (U.S.Pat.5,053,446) uses the pentane of heat or hexane that goods are carried out three washings.The problem that this brings separated from solvent and recovery on the one hand increases preparation cost; Also produce environmental problem on the other hand.Preparation process of the present invention is utilized the density difference and the immiscible property of paraffin and water, removes surface adsorption paraffin by using a hot wash tripping device.Not only eliminated the problem of using solvent to bring, paraffin 100% can also have been reclaimed.
Its enthalpy of phase change of the matrix material of prepared of the present invention is all greater than 80 joule/gram, by selecting to use the paraffin of different crystalline melt points, can so that the transformation temperature of composite phase-change material between 20-80 ℃.This composite phase-change material has higher energy storage density and good thermostability, can be used as energy storage material and be used for storage, constant temperature building materials, air-conditioning energy-conservation of sun power and industrial exhaust heat, also can be used as the temperature control material and be used for fields such as the higher electronic instrument of temperature control requirement, machinery, automatic control, have broad application prospects.
Composite phase-change energy storage material of the present invention can be made particulate state, plate, sheet and various complex construction shape, and directly contacts with other polar heat-transfer medium with water, air and to carry out heat exchange.Therefore phase change material of the present invention can be used for various specific application field boundary institutes, and for example: the heat exchanger that granular composite phase-change material can be used for heat-storing device directly carries out heat exchange with water; Sheet or tabular composite phase-change material can be used as the materials for wall or the flooring material of building, are used for preserving heat or cooling.Phase change material also can be made beverage bottle, makes the beverage of splendid attire keep required temperature.
Embodiment
Embodiment 1:
With 1000 gram high density polyethylene(HDPE) (HDPE, 2200J, melting index: 7), 15 gram vinyltrimethoxy silane (A171, U.S. Ao Sijia product), 0.08 gram dicumyl peroxide (DCP, industrial goods), and 4 carry out fusion-grafting at a screw extrusion press behind the gram antioxidant 1010 uniform mixing, and extrusion temperature is 220 ℃.The melting index of graft product is 1.8, and gel content is zero.This graft product is cut into granular, in the water miscible liquid that contains 0.05% dibutyl tin laurate (80 ℃), soaked 6 hours, obtain gel content and be 58.6% crosslinked polyethylene.
Vinyltrimethoxy silane in the last example (A171) is replaced with vinyl trimethoxy Ethoxysilane (A172), and the melting index of gained graft product is 0.6, and gel content is 3.8%.This graft product is cut into granular, in the water miscible liquid that contains 0.05% dibutyl tin laurate (80 ℃), soaked 6 hours, obtain gel content and be 67.7% crosslinked polyethylene.
Embodiment 2:
With crystalline melt point is that 80 ℃ paraffin adds in the container have heating and to stir, is heated to 160 ℃.With resulting grafted polyethylene among the embodiment 1 (melting index 1.8) according to the paraffin ratio be that 30: 70 ratio adds in the container, apply to stir to allow the grafted silane polyethylene be dissolved in paraffin fully.Will the heavy-gravity melt be hot pressed into the thin slice of 2.5 mm thick after the cooling, put into hot water emulsion (80 ℃) immersion that contains 0.05% dibutyl tin laurate and promptly obtained cross-linked type polyethylene/paraffin polymer solid-to-solid transition material in 4 hours.The transformation temperature of this material is 80 ℃ (melt temperature of differential scanning calorimeter mensuration is 81.5 ℃, and Tc is 79.6 ℃), and enthalpy of phase change is 137 joule/gram.
Use hot machine analyser (TMA) that the resulting cross-linked type polyethylene/paraffin polymer solid-to-solid transition material that contains 70% paraffin among the embodiment 2 is carried out thermo-mechanical analysis, and compare with the thermo-mechanical analysis collection of illustrative plates of paraffin.
The thermo-mechanical analysis curve of paraffin and crosslinked composite phase-change material
Arrive about 80 ℃ (transformation temperature) when paraffin is heated, its hot mechanical paths changes suddenly, and deformation increases rapidly and development in time and constantly development shows typical solid-liquid and changes mutually.Cross-linking type paraffin/vinyl polymer solid-to-solid transition material then shows diverse hot deformation behavior.A very little variation has taken place in its hot mechanical paths near 80 ℃, this variation is corresponding with the fusion of contained paraffin in the phase change material.The shape of curve remains unchanged substantially subsequently, even phase change material is still the solid with certain intensity after showing the paraffin fusion.When temperature is elevated to about 160 ℃, curve begins to take place obvious distortion, and this distortion is corresponding with the poly fusion of skeleton structure in the phase change material.Owing to still can keep original shape after the crosslinked polyethylene fusion, not flow, so can occur second platform again with the after heat mechanical paths.Take out phase change material this moment, finds that phase change material becomes transparent, soft and flexible, oozes out with the no paraffin of glass stick extruding.The transformation mutually that shows cross-linked type polyethylene of the present invention/paraffin polymer solid-to-solid transition material is solid-to-solid transition.
Embodiment 3:
Resulting grafted polyethylene among the embodiment 1 (melting index 1.8) is cut into granular, in the water miscible liquid that contains 0.1% dibutyl tin laurate (80 ℃), soaked 6 hours, obtain gel content and be 58.6% crosslinked polyethylene pellet.It is swelling in 60 ℃ the paraffin that this crosslinked polyethylene pellet is immersed in 160 ℃, crystalline melt point, and swelling was separated swollen particles with filter screen after 4 hours with heated paraffin, then the swelling body is put into the paraffin that the hot wash tripping device removes surface adsorption.Promptly obtain cross-linked type polyethylene/paraffin polymer solid-to-solid transition material after the drying.This material contains 80% paraffin, and enthalpy of phase change is 141 joule/gram.Transformation temperature is 60 ℃ (melt temperature of differential scanning calorimeter mensuration is 61.7 ℃, and Tc is 59.3 ℃).
To gel content among the embodiment 1 is that another crosslinked polyethylene sample of 67.7% carries out swelling under identical condition, the cross-linked type polyethylene that obtains/paraffin polymer solid-to-solid transition material paraffinicity is about 70%, enthalpy of phase change is 125 joule/gram, and transformation temperature is 60 ℃.
The environment for use and the condition of energy storage material in the imitation interchanger (is heat-transfer medium with water) are accurately weighed the back with 100 order copper mesh parcel with embodiment 3 resulting granules shape composite phase-change materials, put into 95 ℃ of hot water and soak.Experimentize in two ways: (1) is immersed in sample in 95 ℃ of water always, and every interval certain hour takes out a sample and weighs, and observes phase change material and whether has the migration of paraffin to hot water.(2) every 2 minutes sample is taken out, put into 20 ℃ of cold water again and soaked 2 minutes, form a thermal cycling, behind at interval certain times of thermal cycle sample is weighed with this.And measure the variation of phase change material enthalpy of phase change with differential scanning calorimeter.The results are shown in Table 1, table 2.
Transformation behavior after table 1 composite phase-change material soaks in hot water
Soak time (hr) 0 50 100 200 300 500
Material loss of weight (%) 0 0.05 0.10 0.02 0.10 0.10
Transformation temperature (℃) 61.7 61.5 61.1 61.2 61.2 61.4
Latent heat of phase change (J/g) 140.7 140.1 140.2 140.5 140.3 140.5
The transformation temperature and the latent heat of phase change of phase change material after many thermal cyclings of table 2
Cycle index 0 60 120 180 240 300
Material loss of weight (%) 0 0.10 0.05 0.10 0.10 0.10
Transformation temperature (℃) 61.7 61.2 61.4 61.2 61.2 61.6
Latent heat of phase change (J/g) 140.7 140.2 140.3 140.3 140.5 140.7
The material loss of weight data that obtain from two kinds of experiment methods show that the migration to hot water does not take place the paraffin the composite phase-change material; The transformation temperature and the enthalpy of phase change of phase change material do not change with times of thermal cycle.Show that this phase change material has stable use properties.
Claims (11)
1, a kind of cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material with energy storage and temperature controlled function, it is characterized in that this material is as matrix with crosslinked crystalline polyolefin, cross-linked network inside is dispersed with the matrix material of crystalline alkyl hydrocarbon polymer as the phase-change accumulation energy composition, the phase-change accumulation energy composition is between 40-80% in the matrix material, this material has the solid-to-solid transition behavior, phase transition temperature is 20 ℃-80 ℃, and enthalpy of phase change is greater than 80 joule/gram.
2, material according to claim 1 is characterized in that crystalline polyolefin is polyethylene, polypropylene, crystalline ethene and acetate ethylene copolymer, crystalline ethene and propylene copolymer etc.
3,, it is characterized in that crystalline alkyl hydrocarbon polymer is paraffin, lipid acid, fatty acid ester etc. according to claim 1 described material.
4, the preparation method of cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material according to claim 1, it is characterized in that earlier vinyl silanes and polyolefine being carried out the polyolefine that the fusion-grafting preparation has crosslinkable groups, then this graft product is dissolved in and forms the homodisperse thing in paraffin or other crystallinity alkyl hydrocarbon polymer, forming method by thermoplastic resin will disperse thing to make the goods of various desired shapes, put into hot water and carry out crosslinked can making in the presence of catalyzer.
5, the preparation method of cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material according to claim 1, it is characterized in that earlier vinyl silanes and polyolefine being carried out the polyolefine that the fusion-grafting preparation has crosslinkable groups, put into hot water this graft product is made the goods of various desired shapes by the forming method of thermoplastic resin after, in the presence of catalyzer, carry out crosslinked; Crosslinked products is carried out swelling on the fusing point of the fusing point of paraffin or other crystallinity alkyl hydrocarbon polymer and cross-linked polyolefin, to making after the swelling body washing dewaxing.
6, according to the preparation method of the cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material described in claim 4 and 5, it is characterized in that: the polyolefinic method that preparation has crosslinkable groups is that polyolefine and an amount of vinyl silanes, organo-peroxide and oxidation inhibitor uniform mixing are melt extruded on twin screw extruder, vinyl silanes and macromolecular radical carry out addition and can make the polyolefine that has the siloxanes side group on the molecular chain in the extrusion, and the temperature that melt extrudes is 150-240 ℃.
7, the preparation method of cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix material according to claim 5, the method that it is characterized in that swelling body washing dewaxing is to utilize the density difference and the immiscible property of paraffin and water, use a hot wash tripping device that has overflow and stirring to remove surface adsorption paraffin, and paraffin 100% is reclaimed.
8,, it is characterized in that described polyolefine is polyethylene, crystalline ethylene-propylene copolymer according to the preparation method of claim 4 and 5 described cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix materials; Vinyl silanes comprises vinyltrimethoxy silane (A171), vinyltriethoxysilane (A151), vinyl trimethoxy Ethoxysilane etc., and its consumption is the 0.5-5% of polyolefin resin consumption.
9, according to the preparation method of claim 4 and 5 described cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix materials, it is characterized in that described organo-peroxide is dicumyl peroxide (DCP), t-tutyl cumyl peroxide (TBPB), benzoyl peroxide (BPO), 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexanes (L130) etc., its consumption is the 0.03-0.5% of polyolefin resin consumption.
10, according to the preparation method of claim 4 and 5 described cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix materials, it is characterized in that described oxidation inhibitor is 2,6-ditertbutylparacresol (BHT), antioxidant 1010, antioxidant 1076, consumption are the 0.3-0.8% of polyolefin resin consumption.
11, want the preparation method of 4 and 5 described cross-linked type macromolecule solid-to-solid transition energy storage temperature control matrix materials according to right, the catalyzer that it is characterized in that described silane hydrolyzate condensation is dibutyl tin laurate and stannous octoate, and catalyzer and water are mixed with the emulsion that concentration is 0.01-0.2%.
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| CN109837068A (en) * | 2019-01-16 | 2019-06-04 | 浙江理工大学 | A kind of preparation method of cross-linking type phase-changing and temperature-regulating functional agent |
| CN109837068B (en) * | 2019-01-16 | 2021-06-11 | 浙江理工大学 | Preparation method of crosslinking type phase-change temperature-regulating functional agent |
| WO2021098309A1 (en) * | 2019-11-21 | 2021-05-27 | 四川三联新材料有限公司 | Flexible multi-level phase change material having cross-linked network structure and preparation method therefor |
| CN112143462A (en) * | 2020-10-27 | 2020-12-29 | 中国矿业大学 | Composite phase change material taking polystyrene with siloxy functional group as support material, and preparation method and application thereof |
| CN112143462B (en) * | 2020-10-27 | 2021-10-26 | 中国矿业大学 | Composite phase change material taking polystyrene with siloxy functional group as support material, and preparation method and application thereof |
| CN113484469A (en) * | 2021-06-30 | 2021-10-08 | 中国科学院青海盐湖研究所 | In-situ characterization method for nano-scale phase separation of phase change energy storage material of hydrated salt system |
| CN114262870A (en) * | 2021-12-24 | 2022-04-01 | 西安交通大学 | Lead-free thin film with high energy storage density and wide working temperature, capacitor and preparation method thereof |
| CN114907700A (en) * | 2022-05-10 | 2022-08-16 | 武汉中科先进材料科技有限公司 | Cross-linked packaging paraffin type solid-solid phase change material and preparation method thereof |
| WO2024000274A1 (en) * | 2022-06-29 | 2024-01-04 | 浙江大学 | Dual-phase transparent phase change material and preparation method therefor |
| CN115305060A (en) * | 2022-06-30 | 2022-11-08 | 浙江大学 | Double-phase transparent phase-change material and preparation method thereof |
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