CN107384327A - Organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding and preparation method thereof - Google Patents
Organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding and preparation method thereof Download PDFInfo
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- CN107384327A CN107384327A CN201710613151.8A CN201710613151A CN107384327A CN 107384327 A CN107384327 A CN 107384327A CN 201710613151 A CN201710613151 A CN 201710613151A CN 107384327 A CN107384327 A CN 107384327A
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- 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
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Abstract
The invention discloses organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding and preparation method thereof；The organic phase-change microcapsule has core shell structure, and core is core, is organic phase change material；Shell is wall material, be graphene oxide doped silica, graphene oxide doped in silica, organic phase-change microcapsule 55~148J/g of enthalpy of phase change, 35~90 DEG C of phase transition temperature.During preparation, first prepare coated with silica organic material phase-change microcapsule, graphene oxide is soluble in water, stirring, ultrasonic disperse, graphene oxide solution is prepared, by the scattered organic solvent of the organic phase-change microcapsule of graphene oxide solution addition coated with silica, carries out graphene oxide doped；Organic phase-change microcapsule of the present invention has superior photo-thermal, and inorganic wall material can play fire retardation to organic core of internal layer, and the phase transformation hot fluid being made from it application value in solar thermal collector and heat exchanging fluid is big.
Description
Technical field
The present invention relates to organic phase change material field, and in particular to a kind of inorganic wall material cladding of graphene oxide doped has
Machine phase-change microcapsule and preparation method.
Background technology
Since 19 century 70s are utilized first by Nasa, phase-change material has turned into one kind in Solar use
In the renewable energy source material that is widely used.On the whole phase-change material is divided into organic and inorganic two class.Organic phase change material such as stone
Wax, aliphatic acid and fatty alcohol etc., have the advantages that phase transition temperature is constant, phase transformation enthalpy is high, without be separated, without surfusion, so
And when solid-liquid phase change occurs, the hidden danger of liquid leakage be present, organic phase-change material has combustibility in addition, makes it in reality
It is restricted in the application of border.
The problem of being leaked for organic phase change material, it can be resolved by microcapsules encapsulation technology, microcapsules technology makes
Phase-change material is encapsulated in harder housings using small particles form as core, and the presence of shell allows core to undergo phase transition
Frequent change on Shi Tiji, so as to reduce interference of the transformation behavior to external environment condition, and can increase heat transfer area.And for having
The problem of machine phase-change material is flammable, can be by being used as package casing material to solve from the material with anti-flammability.
Traditional paraffin microcapsule phase change storage generally use polymer is shell material, however, these polymeric housing materials
Have the shortcomings that common, for example, it is flammable, mechanical strength is low, thermo-chemical stability is poor, thermal conductivity is low.And most of inorganic material tool
There are more more preferable than polymer a rigidity and intensity；Therefore, high-intensity inorganic shell material not only increases the heat transfer of PCM system
Performance, also improve durability and the reliability of phase-change microcapsule work.Since reporting out sol-gal process in oil-in-water emulsion
Coated with silica organic phase change material has been prepared in system come since preparing microcapsules, many researchers have carried out nothing in succession
The research of case material, silica wall material can not only provide hard shell to organic core, moreover it is possible to improve organic core
Thermal conductivity factor.
For graphene oxide as the presoma for preparing graphene, its property is substantially similar to graphene, has excellent power
Performance and hot property are learned, and graphene oxide has excellent pliability, it is easy to it is compound with other materials, can be firm
Combined with inorganic wall material.Graphene oxide can significantly improve the thermal conductivity of phase-change material because of the high heat conductance of itself.Together
When graphene oxide there is fire resistance, and can and inorganic wall material strong bonded, therefore, graphene oxide can be used as excellent nothing
Machine wall material dopant material.
Publication No. CN104861934A Chinese patent literature discloses the organic phase that a kind of graphene is modified organic wall material
Become the preparation method of material microcapsule.As wall material, solid has the melamine formaldehyde resin that this application is modified using graphene first
Machine phase-change material is core, and phase-change microcapsule is prepared by polymerization.The phase-change microcapsule prepared by above-mentioned literature method, though
Right heat-conductive characteristic increases, but organic wall material hardness is poor, and in long-term use, organic wall material mistake easy to aging
Effect.
Publication No. CN103752234A Chinese patent literature discloses a kind of system of graphene oxide phase-change microcapsule
Preparation Method.This application is mixed graphene oxide, organic phase change material, water by certain mass ratio, by the pH value for adjusting solution
Directly obtain the phase-change microcapsule of graphene oxide cladding.Although phase-change microcapsule heat-conductive characteristic prepared by this method has carried
Height, but its wall material fixed effect is poor, and be present the incomplete problem of cladding in the graphene oxide cladding that lamella be present, applying
In liquid leakage, the potential safety hazard such as flammable be present.
The existing technology that inorganic wall material cladding is carried out to organic phase change material and prepares microcapsules, its shortcoming mainly due to
Itself thermal conductivity factor of inorganic wall material is not high, and causes after being coated by inorganic wall material, phase-change microcapsule and extraneous heat exchange speed
Rate reduces.
The content of the invention
Present invention aims at propose that carrying out graphene oxide doped silica inorganic wall material cladding prepares organic phase-change
Microcapsules.The inorganic wall material cladding that the present invention carries out graphene oxide carbon doping using situ aggregation method prepares the micro- glue of organic phase-change
Capsule, while improve the heat conductivility and light thermal property of organic phase change material microcapsules.
The organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding, has nucleocapsid structure, core is
Core, it is organic phase change material；Shell is wall material, is the silica of graphene oxide doped, graphene oxide doped is in dioxy
In SiClx, the mass percent of doping is 0.2%~10%；The organic phase-change microcapsule particle diameter is 15~50 microns, phase transformation
Enthalpy is 55~148J/g, and phase transition temperature is 35~90 DEG C.
The preparation method of the organic phase-change microcapsule of the inorganic wall material of graphene oxide doped, comprises the following steps：
1) coated with silica organic material phase-change microcapsule is prepared：
The polymer for being dissolved in water and solvent are mixed, obtain the solution of polymer；The polymer for being dissolved in water is poly- second
Enol, polyacrylic acid, polymethyl methacrylate, polystyrolsulfon acid, polyacrylamide or polyoxyethylene；
Core material solution is melted into obtain in organic phase change material heating；The organic phase change material is solid-liquid organic phase change material；
The core material solution and emulsifying agent are mixed, adds in the solution of the polymer and emulsifies, control the HLB of emulsion
It is worth for 8~18；The mass ratio of the core material solution and the emulsifying agent is 10：0.1~1；
Silicic acid ester solution is prepared, is added drop-wise in the solution emulsified, continues to stir, pH is to alkalescence for regulation, carries out contracting in situ
Poly- reaction, filter, washing, dry after coated with silica organic phase change material microcapsules；The esters of silicon acis is with being dissolved in water
Polymer mass ratio be 10：5~20；
2) phase-change microcapsule of the inorganic wall material cladding of graphene oxide doped modification is prepared；
The organic phase-change microcapsule of coated with silica is distributed in organic solvent；
Graphene oxide is soluble in water, stirring, ultrasonic disperse, graphene oxide solution is prepared, graphene oxide is molten
In the organic solvent that the organic phase-change microcapsule that liquid adds coated with silica is disperseed, graphene oxide doped, reaction production are carried out
The organic phase-change microcapsule of the post-treated coated with silica for obtaining graphene oxide doped modification of thing；The graphene oxide
Solution and the organic phase-change microcapsule mass ratio of coated with silica are 2~100：5000.
Further to realize the object of the invention, it is preferable that the step 1) solvent is deionized water, ethanol, ethanol/water body
System, acetone or acetone/water system.
Preferably, the mass ratio of the polymer for being dissolved in water and solvent is 1:50~90.It is furthermore preferred that the polymer
Mass ratio with solvent is 1:75~90.
Preferably, the mass ratio of the organic phase change material and the polymer for being dissolved in water is 5：0.5~1.5；The emulsification
The dosage of agent is the 1~10% of organic phase change material quality.
Preferably, the solid-liquid organic phase change material is one in organic alcohols, organic acid, esters, alkanes and paraffin
Kind is a variety of.
Preferably, the emulsifying agent is Span class, Tweens, neopelex and cetyl trimethyl bromination
One or more in ammonium.It is furthermore preferred that the emulsifying agent is Span-60, Span-80, addition is core inorganic-phase variable material
Expect the 1~10% of quality.
Preferably, the preparation silicic acid ester solution is to use ethanol, the tert-butyl alcohol, isopropanol, hexamethylene or acetone solution silicon
Acid esters is formed.
Preferably, the esters of silicon acis generates the esters of silicon acis of silica for hydrolysis in the basic conditions；Silicon of the present invention
Acid esters is that can select suitable esters of silicon acis according to the reagent handbook of correlation.It is furthermore preferred that the esters of silicon acis is tetraethyl orthosilicate
Or aminopropyl triethoxysilane.
The scattered organic solvent of the organic phase-change microcapsule of the coated with silica is ethanol, the tert-butyl alcohol, isopropanol, ring
Hexane or acetone.
Preferably, the post processing is the sodium chloride solution demulsification that use quality concentration is 1%~5%, makes aqueous phase and oil
It is separated, then decompression filters, and with organic solvent and water alternately washing 3~5 times, organic solvent is from ethanol, chloroform, petroleum ether
Or acetone, finally it is put in oven drying 10~20 hours, drying temperature is low compared with phase transition temperature 5~10 DEG C.
Inventive polymers should be the polymer that can be dissolved in water, and oil-soluble polymer is not particularly suited for the present invention；
The present invention additionally adds emulsifying agent, in the presence of emulsifying agent, by adjusting breast to form specific oil-in-water structure
Change the hydrophilic lipophilic balance of liquid, the regulation and control to oil-in-water structure can be achieved, therefore need polymeric water-soluble good herein.
The present invention mixes core material solution and emulsifier solution, and heating emulsification obtains emulsion.Aqueous solutions of polymers adds
In emulsion, continue to emulsify, form the oil-in-water structures of O/W；
Chinese invention patent application CN103752234A discloses directly cladding organic phase change material, and the graphite oxide of lamella
Alkene cladding, which exists, coats incomplete problem, the potential safety hazard such as liquid leakage, flammable in the application be present；Inventor has found that stone will be aoxidized
Black alkene is used to adulterate inorganic wall material, and the phase-change microcapsule after graphene oxide doped has excellent photo-thermal；The present invention uses
The organic phase-change microcapsule that situ aggregation method prepares the inorganic wall material of graphene oxide doped has heat absorption, three kinds of work(of heat accumulation and heat transfer
It can use it for being remarkably improved thermal-arrest and heat exchange efficiency in solar energy heating fluid and heat exchanger heat exchanging fluid in one, dash forward
The limitation of existing microcapsules technology application is broken.
Emulsion system structure of the present invention is O/W oil-in-water systems, and the present invention will meet that HLB value is situated between when choosing emulsifying agent
In 8~18, it is easy to build oil-in-water type emulsion system, emulsifying agent is a kind of conventional surfactant, by lipophilic group and parent
Water base group is formed, and wherein lipophilic group is combined with oil phase, and hydrophilic group is combined with water, and organic phase change material paraffin aliphatic acid etc. is hydrocarbon
Class and its derivative category organic matter, it is oil phase, therefore organic phase change material is core.The mechanism of in situ Polycondensation method synthesis microcapsules is just
It is so as to envelope internal core, so silica is in emulsification interface esters of silicon acis dehydrating condensation into silica inorganic wall material
Shell material in core shell structure is wall material.
Relative to prior art, the invention has the advantages that：
1) present invention prepares the organic phase-change microcapsule of the inorganic wall material of graphene oxide doped using situ aggregation method, passes through
The inorganic wall material of graphene oxide doped, this doping can improve the thermal conductivity of organic phase-change microcapsule, and thermal conductivity can improve 20%
~50%, thermal conductivity improves notable.
2) the existing technology directly coated using lamella graphene oxide is not due to reaching seamless connection between piece and piece,
Thus coat incomplete.Chinese invention patent application CN103752234A is disclosed and is directly coated organic phase change material, and lamella
Graphene oxide cladding, which exists, coats incomplete problem, the potential safety hazard such as liquid leakage, flammable in the application be present；The present invention is inorganic
Wall material silica is to react to be formed by interfacial polycondensation, and Nano particles of silicon dioxide is easy to reunite forms fine and close wall together
Material, the organic phase-change microcapsule cladding of graphene oxide doped silica inorganic wall material cladding of the present invention is complete, is solved
Prior art liquid leakage problem；And wall material silica is inorganic oxide, without combustibility, thus can solve burning
Potential safety hazard.
3) the inorganic wall material of the present invention can play a protective role to the organic phase change material of internal layer, be inhaled simultaneously as it has
Photosensitiveness is good, phase transformation enthalpy greatly and the hot thing characteristic conducted heat of the heat accumulation such as thermal conductivity factor height (enthalpy of phase change is 55~148J/g, phase transition temperature
For 35~90 DEG C), can significantly collection hot fluid and heat exchanging fluid in make the most of the advantage, use it for solar energy heating fluid and
Thermal-arrest and heat exchange efficiency are remarkably improved in heat exchanger heat exchanging fluid.
Brief description of the drawings
Fig. 1 is the phase-change microcapsule SEM pictures of the gained graphene oxide doped coated with silica of embodiment 1.
Fig. 2 is the phase-change microcapsule DSC curve of the gained graphene oxide doped coated with silica of embodiment 1.
Fig. 3 is the gained phase transformation hot fluid photo-thermal curve of embodiment 1.
Fig. 4 is the SEM pictures after the phase-change microcapsule of the gained coated with silica of embodiment 1 is broken.
Fig. 5 is the SEM figures after the phase-change microcapsule of the gained graphene oxide doped coated with silica of embodiment 1 is broken.
Fig. 6 is that the TEM of graphene oxide used in embodiment 1 schemes.
Fig. 7 is embodiment 1 gained phase-change microcapsule UV-Visible absorption (UV-vis) curve.
Fig. 8 is the gained phase-change microcapsule thermal conductivity factor figure of embodiment 1.
Embodiment
To more fully understand the present invention, the present invention is further elaborated with embodiment below in conjunction with the accompanying drawings, but implemented
Example does not form limiting the scope of the invention.
Embodiment 1
The preparation method of the organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding, including it is as follows
Step：
1) 0.75g polyvinyl alcohol at room temperature, is weighed, adds 49.25g water to dissolve, obtains poly-vinyl alcohol solution；
2) 5.6gRT62 organic phase change materials at room temperature, are weighed, are melted under 70 DEG C of waters bath with thermostatic control into liquid core；
3) by 5.6g liquid core and 1.5g emulsifying agents mixed liquor, (emulsifying agent is mass ratio 45:55 Spans 80 and Tween 80
Mixture) it is added to together in poly-vinyl alcohol solution, under 70 DEG C of waters bath with thermostatic control, agitating paddle 600r/min stirs, and is formed
Emulsion；
4) in whipping process, 1.0g 2.5mol/L physiological saline is added dropwise, continues to stir under 70 DEG C of waters bath with thermostatic control
30min；
5) 7.5g teos solutions and 0.1g mass fractions is added dropwise as 10% acetum, 70 DEG C of thermostatted waters
After the lower stirring 5h of bath, Temperature fall continues to stir 5h；
6) sodium chloride solution for being 10wt% with mass fraction is demulsified, and decompression filters, acetone and water alternately wash 3 times, will
Screening obtains the phase-change microcapsule of coated with silica in 50 DEG C of oven drying 6h；
7) phase-change microcapsule of coated with silica obtained by upper step is scattered in n-butanol；
8) it is 0.5mg/L graphene oxide solutions to prepare mass concentration, measures 3ml and is added dropwise in step dispersion liquid, 55 DEG C
6h is stirred under water bath with thermostatic control；
9) after the completion of reacting, decompression filters, and screening is alternately washed 3 times with absolute ethyl alcohol and water, finally by sediment in 50
Dried at DEG C, produce the organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding.
10) it 6) will be dispersed in water with the phase-change microcapsule 9) obtained, the phase transformation hot-fluid that mass fraction is 10% be made
Body.
The organic phase-change microcapsule that is coated to above-mentioned resulting graphene oxide doped silica inorganic wall material and its
Phase transformation hot fluid carries out the sign of relevant nature：
Referring to accompanying drawing 1, sample microscopic appearance is in field emission scanning electron microscope (SEM) (model：LEO 1530VP,
Netherlands observed in), institute making alive 10kV, multiplication factor 10K, the measure through SEM, capsule grain diameter is about 25 μm.
Referring to Fig. 2, the phase transition temperature and latent heat of phase change of sample use differential scanning calorimeter (DSC) (model：Q20,TA)
Measurement, 5~8 milligrams of samples are sealed in an aluminum pot, 10 DEG C/min of heating rate, the constant ml/min of nitrogen flow 50,
The phase-change microcapsule determines through DSC, and its enthalpy of phase change is 77.82J/g, and phase transition temperature is 57.32 DEG C.
Referring to Fig. 3, illumination is carried out to phase transformation hot fluid with solar simulator, temperature is recorded and changes over time curve,
The light output of input is heat, and heat is embodied by temperature, so photo-thermal is embodied in temperature, and does not add graphene oxide
Doping is compared, and the phase transformation hot fluid programming rate after doping significantly increases, therefore adds the microcapsules of graphene oxide doped
The phase transformation hot fluid of gained has more excellent photo-thermal；
Fig. 4 is the scanning electron microscope (SEM) photograph after the phase-change microcapsule of coated with silica that embodiment 1 obtains is broken, tester
Device：Field emission scanning electron microscope (SEM) (model：LEO 1530VP, Netherlands), institute making alive 10kV, multiplication factor 20K,
It can be seen that clearly nucleocapsid structure, silicon dioxide granule reunion form inorganic wall material together.
Fig. 5 is the Electronic Speculum after the phase-change microcapsule for the graphene oxide doped coated with silica that embodiment 1 obtains is broken
Figure, tester：Field emission scanning electron microscope (SEM) (model：LEO 1530VP, Netherlands), institute making alive 10kV, put
Big multiple 20K, equally visible nucleocapsid structure, and capsule surface is more smooth.
Accompanying drawing 6 is the transmission electron microscope picture of graphene oxide in embodiment 1, tester：Flied emission transmission electron microscope (TEM)
(model：JEM-2100F, Japan), it is known that graphene oxide has lamellar structure.
Fig. 7 is the phase-change microcapsule and graphene oxide doped coated with silica that coated with silica is made in embodiment 1
Phase-change microcapsule UV-Visible absorption curve, tester：Ultraviolet-visible spectrophotometer (model：Agilent
Cary60), absorbing wavelength scope 400nm~800nm, the results showed that the microcapsules of graphene oxide doped compared with undoped with micro- glue
Capsule has higher absorptance, so as to apply in phase transformation hot fluid (Fig. 3) so that phase transformation hot fluid can absorb more light productions
Raw more heat, photo-thermal greatly enhance, and illustrate the Photothermal characterisation that microcapsules can be effectively improved after graphene oxide doped.
Fig. 8 is the phase-change microcapsule and graphene oxide doped coated with silica that coated with silica is made in embodiment 1
Phase-change microcapsule thermal conductivity factor figure, tester：Thermal constant tester (model：Hot Disk TPS 2500), thermocouple
For K-type, the results showed that the microcapsules thermal conductivity ratio of graphene oxide doped undoped with thermal conductivity factor it is big, thermal conductivity factor is got over
Greatly, heat-conductive characteristic (heat transfer property) is better.
By Fig. 1 and Fig. 5 understand graphene oxide doped coated with silica phase-change microcapsule surface it is more smooth, this be by
Oxygen-containing functional group such as carboxyl in graphene oxide produces conjugation (also referred to as delocalization effect) with silicon oxygen bond so that oxidation
Graphene is doped in silica.With existing inventive technique CN103752234A disclosed in graphene oxide directly coat it is organic
Phase-change material is compared, and the graphene oxide cladding of lamella, which exists, coats incomplete problem, liquid leakage, flammable etc. in the application be present
Potential safety hazard；Meanwhile existing inorganic wall material microcapsules technology poor thermal conductivity.And the present embodiment graphene oxide doped titanium dioxide
The organic phase-change microcapsule cladding of the inorganic wall material cladding of silicon completely (accompanying drawing 2 is visible), solves prior art liquid leakage problem, and
Graphene oxide also can reinforcing material thermal conductivity；Meanwhile wall material silica is inorganic oxide, without combustibility, solution
Prior art of having determined security hidden trouble.
The present invention is combined graphene oxide doped with phase-change microcapsule technology, and acquisition has heat absorption, heat accumulation and heat transfer work(concurrently
Can in the energy storage material of one, it is such the characteristics of it is used as excellent collection thermal medium additive for solar thermal collector etc.
In practical application, thermal-arrest and heat exchange efficiency are remarkably improved.
Embodiment 2
1) 1.5g polyacrylamides at room temperature, are weighed, adds 99.25g water to dissolve, obtains polyacrylamide solution；
2) 6.4gRT44 organic phase change materials at room temperature, are weighed, are melted under 50 DEG C of waters bath with thermostatic control into liquid core；
3) by 6.4g liquid core and 1.6g emulsifying agents mixed liquor (mass ratio 65:35 neopelex and
Cetyl trimethylammonium bromide) it is added to together in polyacrylamide solution, under 50 DEG C of waters bath with thermostatic control, agitating paddle 800r/
Min stirs, and forms emulsion；
4) in whipping process, 1.0g 2.5mol/L physiological saline is added dropwise, continues to stir under 50 DEG C of waters bath with thermostatic control
30min；
5) acetum of 7.5g teos solutions and 0.1g mass fractions for 10wt%, 50 DEG C of constant temperature are added dropwise
After stirring 5h under water-bath, Temperature fall continues to stir 5h；
6) sodium chloride solution for being 10wt% with mass fraction is demulsified, and decompression filters, acetone and water alternately wash 3 times, will
Screening produces the microcapsules of coated with silica in 50 DEG C of oven drying 6h；
7) phase-change microcapsule of coated with silica obtained by upper step is scattered in ethyl acetate；
8) it is 0.5mg/L graphene oxide solutions to prepare mass concentration, measures 10ml and is added dropwise in step dispersion liquid, 40 DEG C
6h is stirred under water bath with thermostatic control；
9) after the completion of reacting, decompression filters, and screening is alternately washed 3 times with absolute ethyl alcohol and water, finally by sediment in 40
Dried at DEG C, produce the organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding.
Organic phase-change microcapsule obtained by above-mentioned determines through differential scanning calorimetry, and its enthalpy of phase change is 75.58J/g, phase
Temperature is 43.19 DEG C, and the measure of scanned Electronic Speculum, Microcapsules Size is about 20 μm.
Embodiment 3
1) 1.0g polystyrolsulfon acids at room temperature, are weighed, adds 90g water to dissolve, obtains polystyrolsulfon acid solution
2) 9.6gRT56 organic phase change materials at room temperature, are weighed, are melted under 65 DEG C of waters bath with thermostatic control into liquid core；
3) 9.6g liquid core and the emulsifying agent of 1.2g Spans 60 are added in poly-vinyl alcohol solution together, in 65 DEG C of constant temperature
Under water-bath, agitating paddle 1000r/min stirs, and forms emulsion；
4) in whipping process, 1.2g 2.5mol/L physiological saline is added dropwise, continues to stir under 65 DEG C of waters bath with thermostatic control
60min；
5) acetum of 5.0g teos solutions and 0.2g mass fractions for 10wt%, 50 DEG C of constant temperature are added dropwise
1h is stirred under water-bath；
6) sodium chloride solution for being 10wt% with mass fraction is demulsified, and decompression filters, acetone and water alternately wash 3 times, will
Screening produces the microcapsules of coated with silica in 50 DEG C of oven drying 12h；
7) phase-change microcapsule of coated with silica obtained by upper step is scattered in n-butanol；
8) it is 0.5mg/L graphene oxide solutions to prepare mass concentration, measures 15ml and is added dropwise in step dispersion liquid, 50 DEG C
8h is stirred under water bath with thermostatic control；
9) after the completion of reacting, decompression filters, and screening is alternately washed 3 times with acetone and water, finally by sediment at 50 DEG C
Drying, produce the organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding.
Organic phase-change microcapsule obtained by above-mentioned determines through differential scanning calorimetry, and its enthalpy of phase change is 120.54J/g, phase
Temperature is 55.46 DEG C, and the measure of scanned Electronic Speculum, Microcapsules Size is about 50 μm.
For above-described embodiment, the phase-change material of selection can also be the mixture of different melting points paraffin, these equal not shadows
Follow-up reaction result is rung, here is omitted.
Claims (10)
1. the organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding, it is characterised in that the organic phase
Becoming microcapsules has nucleocapsid structure, and core is core, is organic phase change material；Shell is wall material, is the dioxy of graphene oxide doped
SiClx, in silica, the mass percent of doping is 0.2%~10% to graphene oxide doped；The organic phase-change is micro-
Capsule grain diameter is 15~50 microns, and enthalpy of phase change is 55~148J/g, and phase transition temperature is 35~90 DEG C.
2. the preparation side for the organic phase-change microcapsule that graphene oxide doped silica inorganic wall material described in claim 1 coats
Method, it is characterised in that comprise the following steps：
1) coated with silica organic material phase-change microcapsule is prepared：
The polymer for being dissolved in water and solvent are mixed, obtain the solution of polymer；The polymer for being dissolved in water be polyvinyl alcohol,
Polyacrylic acid, polymethyl methacrylate, polystyrolsulfon acid, polyacrylamide or polyoxyethylene；
Core material solution is melted into obtain in organic phase change material heating；The organic phase change material is solid-liquid organic phase change material；
The core material solution and emulsifying agent are mixed, adds in the solution of the polymer and emulsifies, the HLB value for controlling emulsion is
8~18；The mass ratio of the core material solution and the emulsifying agent is 10：0.1~1；
Silicic acid ester solution is prepared, is added drop-wise in the solution emulsified, continues to stir, regulation pH to alkalescence, it is anti-to carry out in-situ polycondensation
Should, filter, washing, dry after coated with silica organic phase change material microcapsules；The esters of silicon acis is with being dissolved in the poly- of water
The mass ratio of compound is 10：5~20；
2) phase-change microcapsule of the inorganic wall material cladding of graphene oxide doped modification is prepared；
The organic phase-change microcapsule of coated with silica is distributed in organic solvent；
Graphene oxide is soluble in water, stirring, ultrasonic disperse, prepare graphene oxide solution, by graphene oxide solution plus
In the scattered organic solvent of organic phase-change microcapsule for entering coated with silica, graphene oxide doped, reaction product warp are carried out
Post processing obtains the organic phase-change microcapsule of the coated with silica of graphene oxide doped modification；The graphene oxide solution
Organic phase-change microcapsule mass ratio with coated with silica is 2~100：5000.
3. preparation method according to claim 2, it is characterised in that the step 1) solvent is deionized water, ethanol, second
Alcohol/aqueous systems, acetone or acetone/water system.
4. preparation method according to claim 2, it is characterised in that the mass ratio of the polymer and solvent for being dissolved in water
For 1:50~90.
5. preparation method according to claim 2, it is characterised in that the organic phase change material and the polymer for being dissolved in water
Mass ratio be 5：0.5~1.5；The dosage of the emulsifying agent is the 1~10% of organic phase change material quality.
6. the method prepared according to claim 2, it is characterised in that the solid-liquid organic phase change material is alcohols, organic
One or more in acid, esters, alkanes and paraffin.
7. preparation method according to claim 2, it is characterised in that the emulsifying agent is Span class, Tweens, dodecane
One or more in base benzene sulfonic acid sodium salt and cetyl trimethylammonium bromide.
8. preparation method according to claim 2, it is characterised in that the preparation silicic acid ester solution is to use ethanol, uncle
Butanol, isopropanol, hexamethylene or acetone solution esters of silicon acis are formed.
9. preparation method according to claim 2, it is characterised in that the esters of silicon acis is hydrolysis generation in the basic conditions
The esters of silicon acis of silica；The scattered organic solvent of the organic phase-change microcapsule of the coated with silica is ethanol, the tert-butyl alcohol,
Isopropanol, hexamethylene or acetone.
10. the method prepared according to claim 2, it is characterised in that the post processing be use quality concentration be 1%~
5% sodium chloride solution demulsification, makes aqueous phase and separation of oil, and then decompression filters, with organic solvent and water alternately washing 3~5
Secondary, organic solvent selects ethanol, chloroform, petroleum ether or acetone, is finally put in oven drying 10~20 hours, drying temperature relatively phase
Temperature is low 5~10 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710613151.8A CN107384327A (en) | 2017-07-25 | 2017-07-25 | Organic phase-change microcapsule of graphene oxide doped silica inorganic wall material cladding and preparation method thereof |
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| CN108251067A (en) * | 2018-01-23 | 2018-07-06 | 浙江工业大学 | Phase change fluid based on graphene oxide coated by titanium dioxide paraffin and preparation method thereof |
| CN108774499A (en) * | 2018-08-15 | 2018-11-09 | 中国工程物理研究院化工材料研究所 | A kind of graphene-silica compound wall materials phase transformation Nano capsule and preparation method |
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