CN102311720A - Phase-change energy storage capsule and preparation method thereof - Google Patents
Phase-change energy storage capsule and preparation method thereof Download PDFInfo
- Publication number
- CN102311720A CN102311720A CN201010215964XA CN201010215964A CN102311720A CN 102311720 A CN102311720 A CN 102311720A CN 201010215964X A CN201010215964X A CN 201010215964XA CN 201010215964 A CN201010215964 A CN 201010215964A CN 102311720 A CN102311720 A CN 102311720A
- Authority
- CN
- China
- Prior art keywords
- capsule
- phase change
- phase
- polymer
- change material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a phase-change energy storage capsule and a preparation method thereof. Polymer emulsion is firstly prepared in a pre-polymer solution, and the generation speed of a shell layer of the polymer is controlled by controlling the reaction temperature and the dosage of additives to coat inorganic hydrous salt phase change materials after surface treatment. Inorganic hydrous salt after surface treatment is used as capsule-core phase-change materials and accounts for 40-80% of the total weight of the capsule, and high polymer is used as a capsule wall and approximately accounts for 20-60% of the total weight of the capsule. The preparation of phase-change microcapsules is completed through the processes of capsule core material surface treatment, capsule wall high polymer material pre-polymerization, functional coupler cross-linked coating and the like.
Description
Technical field
The present invention relates to the capsular technology of preparing of a kind of employing polymer dispersed polymeric method synthesizing inorganic phase-change accumulation energy phase transformation, specifically is that the inorganic hydrated salt that is coated in the polymer shell layer material is the preparation method of the composite phase-change material of phase change material.
Background technology
Phase change material has that energy storage density is big, the approximate isothermal outstanding advantage of phase transition process, all is applied in fields such as sun power utilization, building energy conservation, waste heat recovery, temperature-regulating fiber, electronics temperature control, functional thermal fluids.There is leakage in use in the solid-liquid phase change material, is separated, volumetric expansion, be corrosive, problem such as poor heat stability; Using microencapsulation technology seals it can effectively to address these problems; Can avoid simultaneously phase change material and ambient substance reaction, increase heat transfer area, improve its use properties; Be the compound reliable approach that provides of solid support materials such as solid-liquid phase change material and polymer, gypsum, cement, mortar, help expanding phase change material Application Areas (Xue's equality, the preparation of micro-encapsulated phase change material and evaluation method [J]. fine chemistry industry; 2007,24 (9): 843-847).
Micro-encapsulated phase change material (MCPCM) is to adopt microcapsulary that solid-liquid phase change material (core) is coated stable solid particulate under the normality of processing with synthesized polymer material or mineral compound (wall material) with physics or chemical process; This solia particle can be in very narrow TR the considerable latent heat of phase change of absorption/release, have significant heat-accumulation temperature-adjustment function.In recent years; For obtain size distribution more evenly, tough and tensile, the compactness of cyst wall and good flame resistance, thermal conductivity and wetting ability meet the demands, encapsulation rate is higher, latent heat is bigger MCPCM; The researchist adopts some new film forming materials in succession both at home and abroad; Preparing method and preparation technology are also constantly perfect, and various quality product evaluation meanses are able to use.Wherein USP is nearly 60; 23 of Chinese patents.
The suitable at present method for preparing MCPCM mainly contains interfacial polymerization, situ aggregation method, spray-drying process and complex coacervation, and plating method and sol-gel method also obtain certain application simultaneously.
Interfacial polymerization prepares MCPCM; At first will be with PCM emulsification or dispersion in being dissolved with the external phase that forms shell material monomers; Then the aqueous solution of the water-soluble monomer organic solvent of oil soluble reactant (or contain) is distributed to organic phase or aqueous phase; Add emulsifying agent simultaneously and obtain W/O emulsion or O/W emulsion; Add water-soluble monomer (or add oil-soluble monomer to the O/W emulsion) to the W/O emulsion again, then these two kinds of monomers can be respectively from disperse phase (PCM emulsion droplet) and external phase to its interface movement and polymerization reaction take place on the interface rapidly, the polymeric film of generation coats back formation MCPCM with PCM.
Chinese patent (CN101045857) has reported with paraffin to be phase change material; With tolylene diisocyanate and two kinds of materials of urea-formaldehyde resin is cyst material; Carry out the microcapsule parcel with the method for interfacial polymerization and in-situ polymerization, prepare bilayered microcapsule encapsulation paraffin phase change material.Prepare paraffin from 1% up to 70%, transformation temperature is adjustable microencapsulated phase change material from 0 ℃ to 70 ℃.
It is that nuclear, polyureas are the microcapsule of shell that Cho etc. have synthesized with the Octadecane through interfacial polymerization, and used one-tenth shell monomer is respectively tolylene diisocyanate (TDI) and diformazan ethyl triamine (DETA), and emulsifying agent is NP-10.At first Octadecane and TDI are dissolved in the aqueous solution of impouring NP210 behind the hexanaphthene, high-speed stirring obtains the O/W emulsion.The DETA aqueous solution is slowly joined in the above-mentioned emulsion, be heated to 60 ℃, interfacial polymerization takes place in TDI and DETA; Behind washing and drying, obtain MCPCM, particle diameter is about 1 μ m, and transformation temperature is 28～30 ℃; Enthalpy of phase change is 241.2J/g (Cho J S, KwonA, ChoC G.Colloid Polym Sci [J]; 2002,280,260-266).
Choi etc. use situ aggregation method, with n-tetradecane emulsification in SMA (Styrene2maleic anhydride-monomethylmaleate-copolymer), stir with the speed of 8000r/min and to obtain stable emulsion; Then it is joined in the carbamide prepolymerization system, 60 ℃ with 600r/min under polyase 13～4h, obtaining with the n-tetradecane is nuclear; Melamine formaldehyde resin is a shell, and median size is 4.25 μ m, and enthalpy of phase change is MCPCM (the Choi J K of 291J/g; Lee J; Kim JH.J of Indus and Engin Chem [J], 2001,7 (6): 3582362.).
Zhang etc. are core with the octadecane, and the urea-melamine-formaldehyde multipolymer is a cyst wall, have processed the MCPCM that can be used for processing the specific function fiber with situ aggregation method.The particle diameter of microcapsule is in 0.2～5.6 mu m range, and core content is 65%～78%, and fusing point is about 37 ℃, and latent heat of phase change is 180J/g; Maximum heatproof can reach 160 ℃ of (Zhang X X, Tao X M, Yick K L; Et al.Colloid Polym Sci [J], 2004,282:330-336).
Masato is respectively Pentadecane through situ aggregation method with newsprinting paper fiber and capsule-core; Octadecane and n-hexacosane are that organic phase change material synthesizes micro encapsulation energy storage phase change material (the Masato T that median size is 30～50 μ m; Yoshinari T; Natsukaze S.Proceedings the first Joint China-Japan Chemical Engieering Symposium [M] .2000,552-556).
As stated, at present the micro encapsulation energy storage phase change material of oneself report focuses mostly on paraffin, polyvalent alcohol, long linear alkane, higher fatty acid, and materials such as polyoxyethylene glycol are the research of phase-change material micro-capsuleization.Research with microencapsulation inorganic hydrous salt phase transition material still rarely has report.It is big that inorganic hydrated salt has a latent heat of phase change as phase change material; The capacity of heat transmission is strong; Kind is many, advantages such as low price, but since in its dissolution-crystallization process cold excessively, be separated and with the drawbacks limit such as uncompatibility of organic materials its application as the micro-encapsulated phase change material.Utilize microcapsulary phase change material to be wrapped in the mistake cold-peace phenomenon of phase separation that can significantly reduce the inorganic salt phase change material in the film forming material; Compare with the phase change material of equal in quality or volume, it is little that MCPCM has a particle diameter, and specific surface area is big; Contact area is big during heat exchange; Advantages such as rate of heat exchange is fast make it at material of construction, lagging material, functional fibre, and functional fluid becomes one of focus of research in recent years.
Dispersion polymerization is a kind of novel polymerization method, and what be different from general precipitation polymerization is that the polymer chain that precipitating is come out is not to form powder or blocky polymkeric substance, but is agglomerated into small-particle, stably is suspended in the medium by means of dispersion agent; This moment, polymer beads inside was transferred at the polyreaction center from medium, carried out grain growth, finally formed stable polymer microballoon dispersion system.Obviously, adopt the method for polymer dispersed polymeric method synthesizing inorganic hydrous salt phase transition accumulation energy microcapsule also not see similar document or similar patent report.
The present invention is a kind of technology that adopts the synthetic micro-encapsulated phase change energy storage material of polymer dispersed polymeric method.
Summary of the invention
The present invention mainly is the technology that adopts the diffuse-aggregate method synthesizing inorganic of polymers soln microcapsules of storing energy through phase change, and its purpose is to provide a kind of phase-change accumulation energy capsule and preparation method thereof.
Change through selecting different solvents, additive etc. that the inorganic hydrated salt crystalline is brilliant to be practised to different inorganic hydrated salts, through silane coupling agent to the plane of crystal processing that organises.
That key problem in technology of the present invention is to select is suitable, can dissolve the encystation monomer; The solvent that does not dissolve monomer-polymer is as disperse phase; The interpolation tensio-active agent makes the inorganic hydrated salt capsule-core stable dispersion of surface organic processing in solvent system, makes monomer polymerization coating capsule-core and obtains micro encapsulation energy storage phase change material through free radical reaction.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of phase-change accumulation energy capsule; With the capsule-core of the even grained of crystalline hydrate salt after recrystallization, surperficial coupling processing as phase-change microcapsule; With the cyst wall of polymer performed polymer, coat the formation micro-encapsulated phase change energy storage material through functional coupling agent and capsule-core coupling polymerization as phase-change microcapsule;
The capsule-core phase change material is that transformation temperature is 60～80 ℃ a crystalline hydrate salt, and its components by weight percent is 40～80% of a capsule contents;
Cyst wall is vinyl-based radical polymer of monomers, and it accounts for 20～60% of capsules weight component.
Capsule-core phase change material crystalline hydrate salt is hydrazine aluminum sulfate potassium, hydrated sodium silicate, nitric hydrate nickel or hydration sodium-acetate;
Be used for the polymkeric substance performed polymer that microcapsule coat, its synthon is one or more the monomeric mixtures in vinylformic acid, methylacrylic acid, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Jia Jibingxisuanyizhi, the vinyl cyanide.
Wherein in the polymerization system of cyst wall, the coupling agent consumption is the 0.5%-1% of cyst wall gross weight, and emulsifier content is the 0.3%-1% of cyst wall gross weight; The polymerization-stable agent content is the 0.5%-1% of cyst wall gross weight;
Said capsular preparation method may further comprise the steps:
The surface treatment of step 1) phase change material:
With crystalline hydrate salt, under greater than its transformation temperature condition, be made into saturated solution, under agitation add strong polar hydrophilic solvent; Strong polar hydrophilic solvent and crystalline hydrate salt part by weight are 2-5; Naturally after reducing to normal temperature, add with respect to behind crystalline hydrate salt (down with) 0.3%-0.5% nucleator and/or the thickening material with behind the 1%-2% silane coupling agent processing crystal surface, suction filtration; Washing, drying for standby;
Above-mentioned dry thing added contain in the strong polar hydrophilic solvent that its mass ratio is the 0.3%-1% nonionogenic tenside emulsification 0.5-1 hour in advance; Wherein the part by weight of solvent and dry thing is 2-5;
Step 2) performed polymer preparation:
A certain amount of vinyl monomer is added with respect in its weight (down together) 100-300% dispersion medium, under the nitrogen atmosphere, add the 0.3%-0.5% initiator, be warming up to temperature of reaction 60-80 ℃, be incubated reaction in 1-3 hour and promptly get the polymkeric substance performed polymer;
The polymer overmold of step 3) inorganic hydrated salt:
Phase change material that will be after step 1) is handled, join with its mass ratio be in the monomer performed polymer of 50%-150%, add polymerization stabilizer simultaneously with respect to phase change material weight 0.5%-1%; High-speed stirring emulsification; Continue to add with respect to the initiator of phase change material weight 0.2%-0.5% with respect to the coupling agent of phase change material weight 0.5%-1%, insulation reaction 1-3 hour, discharging; Filter, washing, drying get final product micro-encapsulated phase change energy storage material.
In the step 1), strong polar hydrophilic solvent is ethanol or acetone;
Be used for preventing or reduce the capsule-core inorganic phase-changing material nucleator that cold-peace is separated and/or thickening material took place is one or more mixtures that boric acid, zeyssatite, modification cover holder soil, dextrin, gelatin, CMC 99.5, hydroxypropylcellulose;
Being used for crystalline hydrate salt surface-treated is silane coupling agent N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, aminoethyl-aminomethyl Trimethoxy silane, vinyltrimethoxy silane or vinyl trimethoxy Ethoxysilane.
Step 2) in, dispersion medium is deionized water, ethanol, ethanol/water system, acetone or acetone system;
The used initiator of prepolymerization is the redox system that Diisopropyl azodicarboxylate, ABVN, ammonium persulphate, Potassium Persulphate or above-mentioned persulphate and reductive agent are formed;
In the step 3), polymerization stabilizer is Z 150PH, polyoxyethylene glycol, the mixture of one or more components in Vinylpyrrolidone polymer, CMC 99.5, hydroxypropylcellulose, SEPIGEL 305, the ZX-I;
Initiator is the redox system that Diisopropyl azodicarboxylate, ABVN, ammonium persulphate, Potassium Persulphate or above-mentioned persulphate and reductive agent are formed;
It is one or more mixtures in N-N '-methylene-bisacrylamide, N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, thiazolinyl Trimethoxy silane, the vinyl trimethoxy Ethoxysilane that performed polymer and capsule-core coupling polymerization coat the coupling agent that forms microcapsule.
Characteristics of the present invention:
1. use inorganic hydrated salt to be the micro encapsulation core materials, it is big to have a latent heat of phase change, characteristics such as thermal conductivity height.
2. through recrystallization, add the crystalline substance habit of means change inorganic hydrated salts such as nucleator.
3. add coupling agent to processings that organise of inorganic hydrated salt crystal face, increased the consistency of capsule-core phase change material and cyst wall high molecular polymer, help formation densification, stable polymer coating layer.
Description of drawings
Fig. 1 handles front and back DSC graphic representation for inorganic hydrated salt.
Embodiment
To help to understand the present invention through following instance, but not limit content of the present invention.
Embodiment 1
1) 10g potassium aluminium sulfate salt hydrate is dissolved in 80 ℃ of deionized waters is made into saturated solution, add the 50ml absolute ethyl alcohol, under agitation naturally cool to normal temperature.
2) 1) 0.5g borax in the inorganic salt crystal suspension-s of gained, treat its dissolving after, add 5ml N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, 25 ℃, 300rpm is reaction suction filtration after 30 minutes down, the solids washing with alcohol, seasoning is subsequent use.
3) with 2) gained coupling processing phase change material adds and to be dissolved with in the 50ml absolute ethyl alcohol of 0.5g nonionogenic tenside Span80, and it is changed in the three-necked bottle that has whisking appliance with the preparatory emulsification of the rotating speed of 2000rpm 30 minutes;
4) in the 250ml three-necked bottle of 40ml absolute ethyl alcohol is housed, under the nitrogen filled protection, add 10ml vinylformic acid; The 10ml TEB 3K; Disperse 15min, when temperature rose to 70 ℃, Dropwise 5 ml was dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator; Drip off insulation reaction 30 minutes in 15 minutes.
5) after insulation reaction finishes, add 3 to system) gained emulsion, 0.5g Vinylpyrrolidone polymer, 1000rpm disperses to add the 5ml vinyltrimethoxy silane behind the 15min; Dropwise 5 ml is dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator simultaneously, drips off in 15 minutes, is cooled to 60 ℃; Insulation reaction discharging after 120 minutes; Suction filtration, washing, the dry inorganic hydrated salt micro-encapsulated phase change energy storage material that gets.
Investigate the phase-changing energy storage material energy-storage property through TA Q1000 type scanning differential calorimeter.Test this inorganic hydrated salt respectively, inorganic salt and microencapsulation inorganic salt phase transformation latent heat after the coupling processing.Test condition is: about amount of samples 10mg, and 50ml/min argon gas atmosphere, 10 ℃/min of temperature rise rate; 20-110 ℃ of experiment warm area; Its transformation temperature is respectively 94.21 ℃, 92.70 ℃, 95.13 ℃, and enthalpy change is respectively 189.2J/g, 109.6J/g and 114.4J/g, after the result shows micro encapsulation; The latent heat of phase change of phase change material decreases, but that transformation temperature is kept is constant.The result is shown in accompanying drawing 1.
Embodiment 2
1) 20g potassium aluminium sulfate salt hydrate is dissolved in 80 ℃ of deionized waters is made into saturated solution, add the 50ml absolute ethyl alcohol, under agitation naturally cool to normal temperature.
2) 1) 0.5g borax in the inorganic salt crystal suspension-s of gained, treat its dissolving after, add 5ml aminoethyl-aminomethyl Trimethoxy silane, 25 ℃, 300rpm is reaction suction filtration after 30 minutes down, washing with alcohol, seasoning is subsequent use.
3) with 2) gained coupling processing phase change material adds and to be dissolved with in the 50ml absolute ethyl alcohol of 1g nonionogenic tenside Span80, and it is changed in the three-necked bottle that has whisking appliance with the preparatory emulsification of the rotating speed of 2000rpm 30 minutes;
4) in being dissolved with the 250ml three-necked bottle of 40ml absolute ethyl alcohol, under the nitrogen filled protection, add 15ml vinylformic acid; The 15ml TEB 3K; Disperse 15min, when temperature rose to 70 ℃, Dropwise 5 ml was dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator; Drip off insulation reaction 30 minutes in 15 minutes.
5) after insulation reaction finishes, add 3 to system) gained emulsion, 0.5g ZX-I, 1000rpm disperses to add the 5ml vinyltrimethoxy silane behind the 15min; Dropwise 5 ml is dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator simultaneously, drips off in 15 minutes, is cooled to 60 ℃; Insulation reaction discharging after 120 minutes; Suction filtration, washing, the dry inorganic hydrated salt micro-encapsulated phase change energy storage material that gets.
Embodiment 3
1) 10g sodium-acetate salt hydrate is dissolved in 80 ℃ of deionized waters is made into saturated solution, add the 50ml absolute ethyl alcohol, under agitation naturally cool to normal temperature.
2) 1) 0.5g borax in the inorganic salt crystal suspension-s of gained, treat its dissolving after, add 5ml N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, 25 ℃, 300rpm is reaction suction filtration after 30 minutes down, washing with alcohol, seasoning is subsequent use.
3) with 2) gained coupling processing phase change material adds and to be dissolved with in the 50ml absolute ethyl alcohol of 0.5g nonionogenic tenside Span80, and it is changed in the three-necked bottle that has whisking appliance with the preparatory emulsification of the rotating speed of 2000rpm 30 minutes;
4) in being dissolved with the 250ml three-necked bottle of 40ml absolute ethyl alcohol, under the nitrogen filled protection, add 10ml vinylformic acid; The 10ml TEB 3K; Disperse 15min, when temperature rose to 50 ℃, Dropwise 5 ml was dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator; Drip off insulation reaction 30 minutes in 15 minutes.
5) after insulation reaction finishes, add 3 to system) gained emulsion, 0.5g Vinylpyrrolidone polymer, 1000rpm disperses to add the 5ml vinyltrimethoxy silane behind the 15min; Dropwise 5 ml is dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator simultaneously, drips off in 15 minutes, is incubated 50 ℃; React discharging after 120 minutes; Suction filtration, washing, the dry inorganic hydrated salt micro-encapsulated phase change energy storage material that gets.
Embodiment 4
1) 10g nitric hydrate nickel salt hydrate is dissolved in 80 ℃ of deionized waters is made into saturated solution, add the 50ml absolute ethyl alcohol, under agitation naturally cool to normal temperature.
2) 1) 0.5g borax in the inorganic salt crystal suspension-s of gained, treat its dissolving after, add 5ml N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, 25 ℃, 300rpm is reaction suction filtration after 30 minutes down, washing with alcohol, seasoning is subsequent use.
3) with 2) gained coupling processing phase change material adds and to be dissolved with in the 50ml absolute ethyl alcohol of 0.5g nonionogenic tenside Span80, and it is changed in the three-necked bottle that has whisking appliance with the preparatory emulsification of the rotating speed of 2000rpm 30 minutes;
4) in being dissolved with the 250ml three-necked bottle of 40ml absolute ethyl alcohol, under the nitrogen filled protection, add 10ml vinylformic acid; The 10ml TEB 3K; Disperse 15min, when temperature rose to 70 ℃, Dropwise 5 ml was dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator; Drip off in 15 minutes, insulation reaction got the polymkeric substance performed polymer in 30 minutes.
5) after insulation reaction finishes, add 3 to system) gained emulsion, 0.5g ZX-I, 1000rpm disperses to add the 5ml vinyltrimethoxy silane behind the 15min; Dropwise 5 ml is dissolved with the ethanolic soln that the 0.25g Diisopropyl azodicarboxylate is an initiator simultaneously, drips off in 15 minutes, is cooled to 50 ℃; Insulation reaction discharging after 120 minutes; Suction filtration, washing, the dry inorganic hydrated salt micro-encapsulated phase change energy storage material that gets.
Claims (6)
1. phase-change accumulation energy capsule; It is characterized in that: with the capsule-core of the even grained of crystalline hydrate salt after recrystallization, surperficial coupling processing as phase-change microcapsule; With the cyst wall of polymer performed polymer, coat the formation micro-encapsulated phase change energy storage material through functional coupling agent and capsule-core coupling polymerization as phase-change microcapsule;
The capsule-core phase change material is that transformation temperature is 60～80 ℃ a crystalline hydrate salt, and its components by weight percent is 40～80% of a capsule contents;
Cyst wall is vinyl-based radical polymer of monomers, and it accounts for 20～60% of capsules weight component.
2. micro-encapsulated phase change energy storage material according to claim 1 is characterized in that:
Capsule-core phase change material crystalline hydrate salt is hydrazine aluminum sulfate potassium, hydrated sodium silicate, nitric hydrate nickel or hydration sodium-acetate;
Be used for the polymkeric substance performed polymer that microcapsule coat, its synthon is one or more the monomeric mixtures in vinylformic acid, methylacrylic acid, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Jia Jibingxisuanyizhi, the vinyl cyanide.
3. said capsular preparation method of claim 1 is characterized in that: may further comprise the steps,
The surface treatment of step 1) phase change material:
With crystalline hydrate salt, under greater than its transformation temperature condition, be made into saturated solution, under agitation add strong polar hydrophilic solvent; Strong polar hydrophilic solvent and crystalline hydrate salt part by weight are 2-5; Naturally after reducing to normal temperature, add nucleator and/or thickening material with respect to crystalline hydrate salt quality 0.3%-0.5% after, use handle crystal surface with respect to crystalline hydrate salt quality 1%-2% silane coupling agent after, suction filtration; Washing, drying for standby;
Above-mentioned dry thing added contain in the strong polar hydrophilic solvent that its mass ratio is the 0.3%-1% nonionogenic tenside emulsification 0.5-1 hour in advance; Wherein the part by weight of solvent and dry thing is 2-5;
Step 2) performed polymer preparation:
A certain amount of vinyl monomer adding is equivalent under the nitrogen atmosphere, add the 0.3%-0.5% initiator in monomer weight (down together) the 100-300% dispersion medium, is warming up to temperature of reaction 60-80 ℃, be incubated reaction in 1-3 hour and promptly get the polymkeric substance performed polymer;
The polymer overmold of step 3) inorganic hydrated salt:
Phase change material that will be after step 1) is handled, join with its mass ratio be in the monomer performed polymer of 50%-150%, add polymerization stabilizer simultaneously with respect to phase change material weight 0.5%-1%; High-speed stirring emulsification; Continue to add with respect to the initiator of phase change material weight 0.2%-0.5% with respect to the coupling agent of phase change material weight 0.5%-1%, insulation reaction 1-3 hour, discharging; Filter, washing, drying get final product micro-encapsulated phase change energy storage material.
4. preparation method according to claim 3 is characterized in that:
In the step 1), strong polar hydrophilic solvent is ethanol or acetone;
Be used for preventing or reduce the capsule-core inorganic phase-changing material nucleator that cold-peace is separated and/or thickening material took place is one or more mixtures that boric acid, zeyssatite, modification cover holder soil, dextrin, gelatin, CMC 99.5, hydroxypropylcellulose;
Being used for crystalline hydrate salt surface-treated is silane coupling agent N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, aminoethyl-aminomethyl Trimethoxy silane, vinyltrimethoxy silane or vinyl trimethoxy Ethoxysilane.
5. preparation method according to claim 3 is characterized in that:
Step 2) in, dispersion medium is deionized water, ethanol, ethanol/water system, acetone or acetone system;
The used initiator of prepolymerization is the redox system that Diisopropyl azodicarboxylate, ABVN, ammonium persulphate, Potassium Persulphate or above-mentioned persulphate and reductive agent are formed.
6. preparation method according to claim 3 is characterized in that:
In the step 3), polymerization stabilizer is Z 150PH, polyoxyethylene glycol, the mixture of one or more components in Vinylpyrrolidone polymer, CMC 99.5, hydroxypropylcellulose, SEPIGEL 305, the ZX-I;
Initiator is the redox system that Diisopropyl azodicarboxylate, ABVN, ammonium persulphate, Potassium Persulphate or above-mentioned persulphate and reductive agent are formed;
It is one or more mixtures in N-N '-methylene-bisacrylamide, N-(β-aminoethyl)-r-aminopropyl trimethoxysilane, thiazolinyl Trimethoxy silane, the vinyl trimethoxy Ethoxysilane that performed polymer and capsule-core coupling polymerization coat the coupling agent that forms microcapsule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010215964XA CN102311720A (en) | 2010-07-02 | 2010-07-02 | Phase-change energy storage capsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010215964XA CN102311720A (en) | 2010-07-02 | 2010-07-02 | Phase-change energy storage capsule and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102311720A true CN102311720A (en) | 2012-01-11 |
Family
ID=45425296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010215964XA Pending CN102311720A (en) | 2010-07-02 | 2010-07-02 | Phase-change energy storage capsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102311720A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468217A (en) * | 2013-08-30 | 2013-12-25 | 贵州中益能低碳节能科技股份有限公司 | High-temperature inorganic nano phase change energy storage material and preparation method thereof |
| CN103468221A (en) * | 2013-08-30 | 2013-12-25 | 贵州中益能低碳节能科技股份有限公司 | Composite inorganic nano phase change energy storage material and preparation method thereof |
| CN103468218A (en) * | 2013-08-30 | 2013-12-25 | 贵州中益能低碳节能科技股份有限公司 | Inorganic nano phase change energy storage material and preparation method thereof |
| CN104937066A (en) * | 2013-01-10 | 2015-09-23 | 吉坤日矿日石能源株式会社 | Microcapsule heat storage material, production method thereof and use thereof |
| CN105754554A (en) * | 2016-02-02 | 2016-07-13 | 中南林业科技大学 | Nano TiO2-containing cellulose-based low-temperature phase change energy storage microcapsule and preparation method thereof |
| CN106010456A (en) * | 2016-06-01 | 2016-10-12 | 成都新柯力化工科技有限公司 | Phase change energy storage powder for building energy saving and preparation method thereof |
| CN106917154A (en) * | 2017-02-26 | 2017-07-04 | 浙江峰赫纺织有限公司 | A kind of preparation method of inflammable low cigarette polypropylene fiber |
| CN107567243A (en) * | 2017-08-17 | 2018-01-09 | 深圳天珑无线科技有限公司 | Housing and preparation method thereof, electronic installation |
| CN108192573A (en) * | 2018-03-08 | 2018-06-22 | 佛山市熙华科技有限公司 | A kind of preparation method of environmental protection and energy saving phase-change microcapsule |
| CN108300428A (en) * | 2018-03-22 | 2018-07-20 | 云南省交通规划设计研究院 | It is a kind of to inhibit phase-change microcapsule and preparation method icy on road |
| CN108410430A (en) * | 2018-02-26 | 2018-08-17 | 苏州甫众塑胶有限公司 | A kind of preparation method of intelligent building phase-changing energy storage material |
| CN108410429A (en) * | 2018-02-26 | 2018-08-17 | 苏州甫众塑胶有限公司 | A kind of preparation method of spherical shape phase-change microcapsule |
| CN108795390A (en) * | 2018-07-31 | 2018-11-13 | 青海大学 | A kind of phase-changing energy storage material containing thickener |
| CN109674085A (en) * | 2017-10-18 | 2019-04-26 | 湖南中烟工业有限责任公司 | It is a kind of for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature and its preparation and application |
| CN110183142A (en) * | 2019-07-05 | 2019-08-30 | 廖伟 | A kind of porcelain tendre production technology of compression molding |
| CN110790953A (en) * | 2019-11-08 | 2020-02-14 | 上海创始实业（集团）有限公司 | Phase-change composite microcapsule hydrogel and antipyretic patch |
| CN111013509A (en) * | 2019-12-11 | 2020-04-17 | 中国科学院化学研究所 | Inorganic salt phase change energy storage microcapsule and preparation method and application thereof |
| CN113845888A (en) * | 2021-11-09 | 2021-12-28 | 北京斯迪莱铂油气技术有限公司 | Phase change microcapsule and heat exchange fluid containing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396841A (en) * | 2000-01-27 | 2003-02-12 | 西巴特殊化学水处理有限公司 | Particulate compositions and their manufacture method |
| US20040026659A1 (en) * | 2002-07-08 | 2004-02-12 | China Textile Institute | Composition for fabricating phase-change-material microcapsules and a method for fabricating the microcapsules |
| CN1513938A (en) * | 2003-08-21 | 2004-07-21 | 河北工业大学 | Microcapsule coated phase change material and its preparation method |
| CN1695787A (en) * | 2005-03-29 | 2005-11-16 | 东华大学 | Synthesizing inorganic microcapsules of storing energy through phase change by using method of solution precipitation polymerization |
-
2010
- 2010-07-02 CN CN201010215964XA patent/CN102311720A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396841A (en) * | 2000-01-27 | 2003-02-12 | 西巴特殊化学水处理有限公司 | Particulate compositions and their manufacture method |
| US20040026659A1 (en) * | 2002-07-08 | 2004-02-12 | China Textile Institute | Composition for fabricating phase-change-material microcapsules and a method for fabricating the microcapsules |
| CN1513938A (en) * | 2003-08-21 | 2004-07-21 | 河北工业大学 | Microcapsule coated phase change material and its preparation method |
| CN1695787A (en) * | 2005-03-29 | 2005-11-16 | 东华大学 | Synthesizing inorganic microcapsules of storing energy through phase change by using method of solution precipitation polymerization |
Non-Patent Citations (1)
| Title |
|---|
| 刘建明: "《微胶囊技术对无机盐的改性研究》", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104937066A (en) * | 2013-01-10 | 2015-09-23 | 吉坤日矿日石能源株式会社 | Microcapsule heat storage material, production method thereof and use thereof |
| CN103468221A (en) * | 2013-08-30 | 2013-12-25 | 贵州中益能低碳节能科技股份有限公司 | Composite inorganic nano phase change energy storage material and preparation method thereof |
| CN103468218A (en) * | 2013-08-30 | 2013-12-25 | 贵州中益能低碳节能科技股份有限公司 | Inorganic nano phase change energy storage material and preparation method thereof |
| CN103468217B (en) * | 2013-08-30 | 2015-10-21 | 贵州中益能低碳节能科技股份有限公司 | A kind of High-temperature inorganic nano phase change energy storage material and preparation method thereof |
| CN103468221B (en) * | 2013-08-30 | 2015-10-21 | 贵州中益能低碳节能科技股份有限公司 | A kind of Composite inorganic nano phase change energy storage material and preparation method thereof |
| CN103468218B (en) * | 2013-08-30 | 2015-10-21 | 贵州中益能低碳节能科技股份有限公司 | A kind of Inorganic nano phase change energy storage material and preparation method thereof |
| CN103468217A (en) * | 2013-08-30 | 2013-12-25 | 贵州中益能低碳节能科技股份有限公司 | High-temperature inorganic nano phase change energy storage material and preparation method thereof |
| CN105754554B (en) * | 2016-02-02 | 2019-02-19 | 中南林业科技大学 | One kind containing nano-TiO2Cellulose base low temperature phase change accumulation energy microcapsule and preparation method thereof |
| CN105754554A (en) * | 2016-02-02 | 2016-07-13 | 中南林业科技大学 | Nano TiO2-containing cellulose-based low-temperature phase change energy storage microcapsule and preparation method thereof |
| CN106010456B (en) * | 2016-06-01 | 2019-05-03 | 宁波运通新材料科技有限公司 | A kind of phase-change accumulation energy powder and preparation method thereof for building energy conservation |
| CN106010456A (en) * | 2016-06-01 | 2016-10-12 | 成都新柯力化工科技有限公司 | Phase change energy storage powder for building energy saving and preparation method thereof |
| CN106917154A (en) * | 2017-02-26 | 2017-07-04 | 浙江峰赫纺织有限公司 | A kind of preparation method of inflammable low cigarette polypropylene fiber |
| CN107567243A (en) * | 2017-08-17 | 2018-01-09 | 深圳天珑无线科技有限公司 | Housing and preparation method thereof, electronic installation |
| CN109674085A (en) * | 2017-10-18 | 2019-04-26 | 湖南中烟工业有限责任公司 | It is a kind of for reducing the heat accumulation capsule of cigarette mainstream flue gas temperature and its preparation and application |
| CN108410429A (en) * | 2018-02-26 | 2018-08-17 | 苏州甫众塑胶有限公司 | A kind of preparation method of spherical shape phase-change microcapsule |
| CN108410430A (en) * | 2018-02-26 | 2018-08-17 | 苏州甫众塑胶有限公司 | A kind of preparation method of intelligent building phase-changing energy storage material |
| CN108192573A (en) * | 2018-03-08 | 2018-06-22 | 佛山市熙华科技有限公司 | A kind of preparation method of environmental protection and energy saving phase-change microcapsule |
| CN108300428A (en) * | 2018-03-22 | 2018-07-20 | 云南省交通规划设计研究院 | It is a kind of to inhibit phase-change microcapsule and preparation method icy on road |
| CN108300428B (en) * | 2018-03-22 | 2020-11-03 | 云南省交通规划设计研究院 | Phase change microcapsule for inhibiting road icing and preparation method thereof |
| CN108795390A (en) * | 2018-07-31 | 2018-11-13 | 青海大学 | A kind of phase-changing energy storage material containing thickener |
| CN110183142A (en) * | 2019-07-05 | 2019-08-30 | 廖伟 | A kind of porcelain tendre production technology of compression molding |
| CN110790953A (en) * | 2019-11-08 | 2020-02-14 | 上海创始实业（集团）有限公司 | Phase-change composite microcapsule hydrogel and antipyretic patch |
| CN111013509A (en) * | 2019-12-11 | 2020-04-17 | 中国科学院化学研究所 | Inorganic salt phase change energy storage microcapsule and preparation method and application thereof |
| CN111013509B (en) * | 2019-12-11 | 2021-08-10 | 中国科学院化学研究所 | Inorganic salt phase change energy storage microcapsule and preparation method and application thereof |
| CN113845888A (en) * | 2021-11-09 | 2021-12-28 | 北京斯迪莱铂油气技术有限公司 | Phase change microcapsule and heat exchange fluid containing same |
| CN113845888B (en) * | 2021-11-09 | 2024-05-07 | 北京斯迪莱铂油气技术有限公司 | Phase-change microcapsule and heat exchange fluid containing same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311720A (en) | Phase-change energy storage capsule and preparation method thereof | |
| Milián et al. | A review on encapsulation techniques for inorganic phase change materials and the influence on their thermophysical properties | |
| Wang et al. | Organic-inorganic hybrid shell microencapsulated phase change materials prepared from SiO2/TiC-stabilized pickering emulsion polymerization | |
| Chang et al. | Review on the preparation and performance of paraffin-based phase change microcapsules for heat storage | |
| Qiu et al. | Microencapsulated n-alkane with p (n-butyl methacrylate-co-methacrylic acid) shell as phase change materials for thermal energy storage | |
| CN101555401B (en) | Microcapsule of organic phase change energy storage material and preparation method thereof | |
| Singh et al. | Microencapsulation of a eutectic PCM using in situ polymerization technique for thermal energy storage. | |
| Al-Shannaq et al. | Emulsion stability and cross-linking of PMMA microcapsules containing phase change materials | |
| Li et al. | Morphology, structure and thermal stability of microencapsulated phase change material with copolymer shell | |
| CN104357019B (en) | A kind of low temperature thermal control phase-change microcapsule and preparation method thereof | |
| CN106367031B (en) | A kind of high heat conductance composite phase-change microcapsules and preparation method thereof | |
| Chaiyasat et al. | Preparation and characterization of poly (divinylbenzene) microcapsules containing octadecane | |
| Tseng et al. | Preparation of microencapsulated phase-change materials (MCPCMs) by means of interfacial polycondensation | |
| TW200934860A (en) | Heat storage compositions and their manufacture | |
| CN102719227A (en) | Preparation method for high stable phase transition emulsion | |
| Németh et al. | Fully bio-originated latent heat storing calcium alginate microcapsules with high coconut oil loading | |
| CN104629690A (en) | Organic-inorganic substance compounded phase change energy storage microcapsule and preparation method thereof | |
| Zhang et al. | Preparation and Characterization of High Content Paraffin Wax Microcapsules and Micro/Nanocapsules with Poly Methyl Methacrylate Shell by Suspension‐Like Polymerization | |
| CN102391839B (en) | Supercooling phase change-inhibiting alkane microcapsule and preparation and application thereof | |
| Chen et al. | Size-tunable CaCO3@ n-eicosane phase-change microcapsules for thermal energy storage | |
| Wu et al. | The influence of emulsifiers on preparation and properties of microencapsules of melamine–urea–formaldehyde resins with n‐dodecanol as phase‐change material | |
| JP2988765B2 (en) | Cool storage material | |
| Han et al. | Fabrication and characterization of a new enhanced hybrid shell microPCM for thermal energy storage | |
| CN108587573A (en) | A kind of synthetic method of phase-changing energy storage material | |
| CN108624292A (en) | A kind of composite phase-change energy storage material for microcapsule and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120111 |