CN101717618A - Preparation method of phase-change material microcapsule - Google Patents
Preparation method of phase-change material microcapsule Download PDFInfo
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Abstract
The invention discloses a preparation method of a phase-change material microcapsule, comprising the following steps of: mixing the core material and the monomer of a phase-change material designed with a phase-change temperature according to a certain proportion, uniformly stirring and heating to the temperature higher than the phase-change point of the core material of the phase-change material to enable the core material and the monomer to be fully dissolved and prepared into an oil phase; dissolving a functional surface active agent in water, heating the mixture to the temperature higher than the phase-change point of the phase-change material and then preparing the mixture into a water phase, wherein an oil-solubility initiating agent is only added in the oil phase preparing process or a water-solubility initiating agent is only added in the water phase preparing process; adding the oil phase in the water phase, preparing an emulsion with a high-shear emulsifying method or a pre-emulsifying and ultrasonic emulsifying method and then deoxidizing, wherein the water-solubility initiating agent is added, the emulsion is polymerized at a certain temperature, the polymerization reaction directionally occurs on the surface of the emulsion drip by adopting a emulsion polymerizing method, and then the phase-change material microcapsule with the required phase-change temperature is obtained.
Description
Technical field
The present invention relates to the functional materials manufacturing technology, be specially a kind of preparation method of phase-change material micro-capsule of environment-friendly type.
Background technology
Phase transformation (energy storage) material is a kind of rapidly environmental protection and energy saving material of development in recent years, and is in field widespread uses such as building, clothes, Heating,Ventilating and Air Conditioning (HVAC), sun power utilizations, significant.
S.K.Roy etc. are (referring to S.K.Roy etc., use the laminar flow forced-convection heat transfer device of phase change material emulsion, international caloic conversion communication magazine: S.K.Roy, B.L.Avanic, Laminar Forced convectionheat Transfer with Phase change material emulsions, Int.Comm.HeatMass Transfer, 1997,24 (5): prove by experiment that 653-662) heat transfer property of phase change material is similar to the heat transfer property that coats the back phase change material by microcapsule.
M.Farid etc. are (referring to M Farid etc., the floor heating system of using latent heat to store, electric power and energy magazine: M Farid, W J Kong, Underfloor heating with latent heat storage, Proc InstnMech Engrs, Part A, 2001,601-609) reported and a kind ofly utilize phase change material heat accumulation microcapsule, but its phase change material need use in special container.Phase change material is applied in the floor, and room temp is had certain regulating effect.
Jeong-Sook Cho etc. report (referring to Jeong-Sook Cho etc., utilize the emulsion interfacial polymerization to carry out the encapsulated of phase change material octadecane, colloidal polymer science: Jeong-Sook Cho, Aahvra Kwan, Chang-Gi Cho, Microencapsulation of octadecane as a phase-change material byinterfacial polymerization in an emulsion system, Colloid polymer science, 2002,280:260-266) prepare phase change material octadecane microcapsule by the emulsion interface polymerization reaction.The particle diameter of microcapsule is about 1 micron, but this microcapsule are applied to the preparation temperature-regulating fiber.
Chinese patent " granular composition and manufacturing thereof " (CN 1946475A) has been reported a kind of grains of composition that comprises.The said composition shell is by the formed multipolymer of the monomer mixture that comprises following component: A) the unsaturated water-soluble monomer of 5-90 weight % alkene class, B) 5-90 weight % polyfunctionality monomer, and C) other monomer of 0-55 weight %; Wherein, the amount of composition shell and A, the ratio of B and C makes the particulate thermogravimetric measure curve and partly highly is at least 350 ℃, and this composition grain is used for fabric and coating composition, is particularly suited for doing the coating composition of textiles.
Chinese patent (being illustrated in big east etc. synthesizing microcapsules of storing energy through phase change by using method of emulsion polymerization, application number 200510024707.7 2005.3.29) discloses a kind of technology that adopts the synthetic microcapsules of storing energy through phase change of method of emulsion hud polymerization.This technology is to be core with oil-soluble transformation temperature at 10-90 ℃ organic phase change material, with vinyl and bi-vinyl type free base monomer is the outer cover polymer source, with water is polymerisation medium, with nonionic and anion surfactant is emulsifying agent, the redox couple that persulphate, percarbonate, perborate, hydrogen peroxide or these superoxide and reductive agent are formed is an initiator, under 0-100 ℃ temperature, carry out emulsion hud polymerization parcel, make phase-change microcapsule.
Chinese patent discloses " a kind of microcapsule coated phase-change material and preparation method thereof " (referring to CN1513938A), will make microcapsule coated phase-change material through polyreaction as the phase change material of core with as the aminoresin polymkeric substance of wall material and emulsifier polyoxyethylene type emulsifying agent NP-10, dispersion agent styrene-maleic anhydride, deionized water.This material structure densification, particle diameter is even, and prolong work-ing life, can be applied to the face of plastering in the construction wall, regulates room temp, save energy.
Yet may there be following shortcomings in above-mentioned these methods: the microcapsule cyst wall of (1) most methods adopts melamine-formaldehyde resin, and formaldehyde wherein may cause the injury to the user, does not also possess the feature of environmental protection; (2) the polyurea microcapsule speed of response of interfacial polymerization preparation is exceedingly fast, and reacts restive, causes the loose easy leakage of microcapsule wall material; (3) thus the used emulsifying agent function singleness of emulsion polymerization prepared phase-change material micro-capsule is unfavorable for that the formation of microcapsule has caused lower encapsulated productive rate; (4) microcapsule coated phase-change material only limits to be applied in inner wall of building (phase change material that is used for exterior wall does not appear in the newspapers).
In the scope of applicant's retrieval, the preparation method of phase-change material micro-capsule of the present invention yet there are no report.
Summary of the invention
Technical problem to be solved by this invention is to overcome deficiency of the prior art, and a kind of preparation method of phase-change material micro-capsule is provided.This preparation method has characteristics such as do not contain in the material that formaldehyde, reaction process are controlled easily, regular, the encapsulated productive rate height of microcapsule pattern, surface hydrophilicity are good; The phase-change material micro-capsule of gained can be used for the exterior coating of construction wall or the face of plastering, and can regulate indoor temperature, has the characteristics of energy-saving, emission-reducing, environment friendly.
The technical scheme that the present invention solve the technical problem is as follows: design a kind of preparation method of phase-change material micro-capsule, this preparation method adopts following technology:
The phase change material core and the monomer of design transformation temperature are mixed in proportion, stir, and be heated to more than the phase point temperature of phase change material core, make it to dissolve fully, be prepared into oil phase; The functional surface promoting agent is dissolved in the water, and is heated to more than the phase point temperature of phase change material, be prepared into water, and only in preparation oil phase process, add oil-soluble initiator, perhaps only in preparation water process, add water soluble starter; Then described oil phase is joined aqueous phase, utilize high-shear emulsifying method or pre-emulsification to add the ultrasonic emulsification method and prepare emulsion, deoxygenation then, add water soluble starter, polyreaction at a certain temperature, adopt emulsion polymerisation process that the polyreaction orientation is occurred on the surface of emulsion droplet, promptly obtain the phase-change material micro-capsule of required transformation temperature;
The required transformation temperature of described phase change material core is 20～80 ℃; Described phase change material core is meant the aliphatic hydrocarbon compounds, comprises the uniform mixture of one or more compounds in alkane compound, alcohol compound and the ester compound; Described alkane compound comprises n-dodecane, n-tetradecane, n-hexadecane, Octadecane, NSC 77136 and eicosane; Described alcohol compound comprises lauryl alcohol, hexalin and the trimethyl carbinol; Described ester compound comprises n-butyl stearate; Described phase change material weight part as core is 10～60;
Described monomer is meant mixed ethylene type free base monomer, comprises (1) a kind of lipophilicity vinyl free radical monomer, comprises vinylbenzene, vinyl toluene, vinyl acetate, (methyl) methyl acrylate and Jia Jibingxisuanyizhi; (2) a kind of general formula is C
mH
2m+1-CH=CH-C
nH
2n-COOH (m, n=0,1,2 ...) hydrophilic ethylene base free radical monomer, comprise (methyl) vinylformic acid and derivative thereof and oleic acid; (3) a kind of oil-soluble monomer with diene key comprises Vinylstyrene and diacrylate butanediol ester, and monomeric mixed weight ratio is: (1): (2)=5～10: 0.1～5, or (1): (2): (3)=5～10: 0.1～5: 0～5;
Described functional surface promoting agent is the tensio-active agent that contains at least a polymerisable surfactant, and polymerisable surfactant is meant as sodium oleate, two ten diester of maleic anhydride or methylacryoyloxyethyl dodecyl dimethyl brometo de amonio; The weight part of functional surface promoting agent is 0.1～5.
Described initiator is meant oil-soluble initiator Diisopropyl azodicarboxylate or benzoyl peroxide, perhaps water miscible initiator potassium persulfate, Sodium Persulfate or ammonium persulphate; When using oil-soluble initiator, it is dissolved in the oil phase; When using water soluble starter, it is dissolved in the water; The weight part of initiator is 0.05～1;
Described polymeric reaction temperature is 20～100 ℃; Described polymerization reaction time is 2～12 hours.
Compared with prior art, preparation method's of the present invention characteristics are: (1) preparation whole process is not used aldehyde material, is a kind of environment-friendly preparation method; (2) adopted the functional surface promoting agent as emulsifying agent, when emulsification, the functional surface promoting agent is orientable to be arranged on the interface of emulsion droplet and water, and the polyreaction orientation is occurred on the drop interface, has characteristics such as speed of response productive rate height easy to control, encapsulated, pattern be regular; (3) selected the acrylic monomer that has functional groups for use, make the polymkeric substance of generation have nonlinear cross-linked structure and hydrophilic surface, can improve the compactness and the wetting ability of cyst wall, the core phase change material is difficult for leaking, gained phase-change material micro-capsule and sand-cement slurry have good consistency, are fit to the exterior wall concrete mortar and smear etc.; (4) resulting phase-change material micro-capsule also has characteristics such as adjustable grain.
Description of drawings
Fig. 1 is the formed emulsion droplet shape and structure of a preparation method of the present invention synoptic diagram; Among Fig. 1: the 1-emulsion droplet; 2-functional surface promoting agent; Reactive behavior point in the 3-functional surface promoting agent;
Fig. 2 is the phase-change material micro-capsule shape and structure synoptic diagram of preparation method's gained of the present invention; Among Fig. 2: 2-functional surface promoting agent; 4-phase-change material micro-capsule cyst wall; 5-phase change material core;
Fig. 3 is the scanning electron photomicrograph figure of the phase-change material micro-capsule of preparation method embodiment 1 preparation of the present invention;
Fig. 4 is the differential thermal analysis curve of the phase-change material micro-capsule of preparation method embodiment 1 preparation of the present invention;
Fig. 5 is the thermogravimetric analysis figure of the phase-change material micro-capsule of preparation method embodiment 1 preparation of the present invention.
Embodiment:
Further specify the present invention below in conjunction with embodiment and accompanying drawing thereof:
The phase-change material micro-capsule of the present invention's design (or claiming phase-change microcapsule) this preparation method of preparation method (abbreviation preparation method) adopts following technology:
The phase change material core and the monomer of design transformation temperature are mixed in proportion, stir, and be heated to more than the phase point temperature of phase change material core, add oil-soluble initiator, make it to dissolve fully, be prepared into oil phase; The functional surface promoting agent is dissolved in the water, and is heated to more than the phase point temperature of phase change material, be prepared into water, and only in preparation oil phase process, add oil-soluble initiator, perhaps only in preparation water process, add water soluble starter; Then described oil phase is joined aqueous phase, utilize high-shear emulsifying method or pre-emulsification to add the ultrasonic emulsification method and prepare emulsion; Deoxygenation then adds water soluble starter, and polyreaction adopts emulsion polymerisation process that the polyreaction orientation is occurred on the surface of emulsion droplet at a certain temperature, obtains the phase-change material micro-capsule of design transformation temperature.
The required transformation temperature of described phase change material core is 20～80 ℃; Described phase change material core is meant the aliphatic hydrocarbon compounds, comprises the uniform mixture of one or more compounds in alkane compound, alcohol compound and the ester compound; Described alkane compound comprises n-dodecane, n-tetradecane, n-hexadecane, Octadecane, NSC 77136 and eicosane; Described alcohol compound comprises lauryl alcohol, hexalin and the trimethyl carbinol; Described ester compound comprises n-butyl stearate; Described phase change material weight part as core is 10～60.
Described monomer is meant mixed ethylene type free base monomer, comprises (1) a kind of lipophilicity vinyl free radical monomer, as vinylbenzene, vinyl toluene, vinyl acetate, (methyl) methyl acrylate and Jia Jibingxisuanyizhi; (2) a kind of general formula is C
mH
2m+1-CH=CH-C
nH
2n-COOH (m, n=0,1,2 ...) hydrophilic ethylene base free radical monomer, as (methyl) vinylformic acid and derivative and oleic acid; (3) a kind of oil-soluble monomer with diene key, as Vinylstyrene, diacrylate butanediol ester, monomeric mixed weight ratio is: (1): (2)=5～10: 0.1～5, or (1): (2): (3)=5～10: 0.1～5: 0～5.
Preparation method's of the present invention phase-change material micro-capsule can adopt the vinyl monomer of multiple radical polymerization, and the monomer wide material sources are suitable for industrialization and use.Microcapsule shell has good water-wetted surface because of having added hydrophilic monomer, be specially adapted to building external paint or plaster, the mixing of textile materials, compound, fill, perfusion uses.
Described functional surface promoting agent is the tensio-active agent that contains at least a polymerisable surfactant, polymerisable surfactant is meant and contains the tensio-active agent that can carry out polyreaction group (mainly being meant two keys) in the molecular structure, polymerisable reactive group comprises allyl (oxygen) base, (methyl) acrylic, acrylamido, styryl and toxilic acid ester group, and tensio-active agent can be any one in anion surfactant, cats product, nonionogenic tenside or the amphoterics.The specifiable example of polymerisable surfactant has: unsaturated fatty acid salt (as sodium oleate), maleic anhydride ester (as two ten diester of maleic anhydride), quaternary (as methylacryoyloxyethyl dodecyl dimethyl brometo de amonio); The weight part of functional surface promoting agent is 0.1～5.
Described initiator comprises oil-soluble initiator and water soluble starter, and oil-soluble initiator is meant the oil soluble azo-compound, as Diisopropyl azodicarboxylate etc., or peralcohol, as benzoyl peroxide etc.; Water soluble starter is meant persulfate initiator, as Potassium Persulphate, Sodium Persulfate and ammonium persulphate etc.The adding mode of described initiator is as follows: when oil-soluble initiator is used in design, in preparation oil phase process, it is dissolved in the oil phase; When water soluble starter is used in design, in preparation water process, it is dissolved in aqueous phase.Use oil-soluble initiator, also be to use water soluble starter, select according to production engineering specifications.Using the weight part of initiator is 0.05～1.
Described polymeric reaction temperature is 20～100 ℃; Described polymerization reaction time is 2～12 hours.
Preparation method's of the present invention technological principle and process are: the phase change material core and the mix monomer of design transformation temperature are mixed in proportion, stir, be heated to more than the phase point temperature of phase change material, add oil-soluble initiator, make it to dissolve fully, form oil phase; The functional surface promoting agent is dissolved in the water, and is heated to more than the phase point temperature of phase change material, form water; Described oil phase is joined aqueous phase, utilize the high-shear emulsifying method to make oil phase under the effect of external force and tensio-active agent, make oil phase form a certain size emulsion droplet (referring to 1 among Fig. 1), this moment, polymerisable surfactant was because the characteristic of hydrophilic and oleophilic structure own can align the surface (referring to 2 among Fig. 1) at emulsion droplet, by feeding the nitrogen deoxygenation, elevated temperature is to making polyreaction begin to carry out more than the decomposition temperature of initiator, unsatisfied chemical bond in the polymerisable surfactant structure (reactive behavior point, shown in 3 among Fig. 1) the participation polyreaction, on emulsion droplet/water termination, form polymeric film, generation along with polyreaction, the continuous polymerization of monomer that is present in the oil phase accumulates in the emulsion droplet surface, cyst wall (referring to 4 among Fig. 2) is thickening constantly, forms phase-change material micro-capsule (referring to shown in Figure 2) at last.
Specifically, preparation method's of the present invention processing step comprises:
(1) preparation of oil phase
The phase change material of 10～60 parts of weight, 5～10 parts lipophilicity vinyl free radical monomer, 0.1～5 part hydrophilic ethylene base free radical monomer, 0.1～5 part the oil-soluble monomer with diene key are mixed, if use oil-soluble initiator, then 0.05～1 part oil-soluble initiator is added, dissolves and is heated to more than the phase point temperature of phase change material, promptly get oil phase;
(2) preparation of water
0.1～5 part functional surface promoting agent is dissolved in 100～500 parts the water, and is heated to more than the phase point temperature of phase change material,, then 0.05～1 part water soluble starter is added, promptly get water if use water soluble starter;
(3) preparation of emulsion
In the above temperature of the transformation temperature of phase change material oil phase is joined aqueous phase, under nitrogen protection, utilize high-shear emulsifying method or pre-emulsification to add the ultrasonic emulsification method, the preparation emulsion; Described high speed shear emulsification method is emulsification 10～30 minutes under 1000～9000 rev/mins high speed shear mulser rotating speed; It is earlier pre-emulsification (conventional 100-1000 rev/min stirring at low speed) after 10～20 minutes that described pre-emulsification adds the ultrasonic emulsification method, and emulsification 10～30 minutes on the ultrasonic emulsification machine again obtains emulsion.The size of emulsion drop is 0.1～50 μ m.
The median size of the resulting phase-change material micro-capsule of preparation method of the present invention can be adjusted arbitrarily between 0.1～50 μ m according to not coexisting of high-shear emulsifying method that adopts or ultrasonic emulsification method: when adopting pre-emulsification-ultra-sonic dispersion method, can obtain the microcapsule of median size at 0.1～10 μ m; When adopting the emulsification of high speed shear mulser (2000～9000 rev/mins of rotating speeds), can obtain the microcapsule that median size is 0.5～50 μ m.
(4) preparation of phase-change material micro-capsule
The gained emulsion is in nitrogen protection, adds backflow device, stirring velocity and is under 300～700 rev/mins the condition, is heated to 20～100 ℃, reacts after 2～12 hours, with phase-change material micro-capsule and solution separating, promptly makes the product phase-change microcapsule.
Key problem in technology of the present invention is that employed functional surface promoting agent because of the surface that emulsification is gathered in emulsion droplet polyreaction takes place on the interface; Employed hydrophilic ethylene base monomer is because the hydrophilic radical that exists in its structure, in emulsion process, be in the interface of oil droplet and water, radical polymerization is fashionable taking place, with the phase change material is nuclear, chain initiation, chainpropagation, chain termination all occur in the interface of coating layer and phase change material, and the polymer deposition of generation forms coating layer in the phase change material surface.
Preparation method by phase-change material micro-capsule of the present invention can directly make the phase-change material micro-capsule with described characteristics.
The phase-change microcapsule of the present invention preparation is applicable to the insulating coating material of doing external wall and the melt-spun material of flexible textile material.When phase transformation material capsule of the present invention is used for the insulating coating material of external wall, can be with itself and concrete mortar by 1～4: 10 weight ratio mixes to be made, prepared insulating coating material can reduce building energy consumption, improves indoor thermal environment stability, increase the indoor environment comfortableness, has the characteristics of energy-saving, emission-reducing, environment friendly; When being used for the melt-spun material of flexible textile material, the clothing of manufacturing can be kept the constant of body temperature, creates relatively neither cold, also not hot " a microclimate environment ".
The present invention does not address part and is applicable to prior art.
Below provide specific embodiments of the invention, specific embodiment only is used to be described in further detail the present invention, does not limit claim of the present invention.
Embodiment 1:
(1) preparation of oil phase: with the transformation temperature of 13g is that 24 ℃ phase change material mixes with the methyl methacrylate of 3.7g, the methacrylic acid of 1.9g and the benzoyl peroxide of 0.2g, is heated to 45 ℃, and the dissolving back forms oil phase;
(2) preparation of water: the functional surface promoting agent sodium oleate of 2g is dissolved in the distilled water of 100g and is heated to 45 ℃, form water;
(3) preparation of emulsion: water is placed 1600 rev/mins of high speed shear mulser adjusted rotating speeds, slowly add oil phase, emulsification formed stable emulsion in 15 minutes;
(4) preparation of phase-change material micro-capsule: in nitrogen protection, add and under the stirring velocity of backflow device and 500 rev/mins emulsion is warmed up to 75 ℃ gradually and kept 4.5 hours; stop heating; cool to room temperature; mixture after filtration, 50 ℃ washing, drying, obtain median size 10.2 μ m phase-change material micro-capsules.The first initial thermal weight loss temperature of these microcapsule is 217.8 ℃.
Above-mentioned phase change material is mixed by 3: 10 weight ratio with concrete mortar, be used for smearing of external wall, can be so that building possesses certain for temperature adjustment function, test shows, by suction, the heat release of phase transition process, under 38 ℃ of envrionment temperatures, can regulate the room temperature between 25～30 ℃
Phase-change material micro-capsule pattern, differential thermal analysis and the thermogravimetric analysis figure of the embodiment of the invention 1 preparation are respectively as Fig. 3, Fig. 4 and shown in Figure 5.Analysis revealed, the phase-change material micro-capsule pattern is regular, heat enthalpy value is high, wall material thermotolerance is because the phase-change material micro-capsule of common urea-formaldehyde resin wall material.
Embodiment 2:
(1) preparation of oil phase: with the transformation temperature of 10.0g is that 24 ℃ phase change material mixes with the vinylbenzene of 5.712g, the methacrylic acid of 0.5085g, the diacrylate butanediol ester of 0.2401g and the Diisopropyl azodicarboxylate of 0.3019g, be heated to 55 ℃, the dissolving back forms oil phase;
(2) preparation of water: the methylacryoyloxyethyl dodecyl dimethyl brometo de amonio of 4g is dissolved in the 200g distilled water, and dissolving post-heating to 55 ℃ forms water;
(3) preparation of emulsion: oil phase is mixed with water, and the pre-emulsification of stirring at low speed kept temperature to be 55 ℃ and places the emulsification of ultrasonic emulsification machine to form stable emulsion in 5 minutes after 10 minute;
(4) preparation of phase-change material micro-capsule: in nitrogen protection, add the backflow device and under 300 rev/mins stirring velocity, emulsion is warmed up to gradually 75 ℃ and kept 3 hours; stopped reaction; cool to room temperature; mixture after filtration, 50 ℃ washing, drying, obtain median size 0.30 μ m phase-change material micro-capsule.The first initial thermal weight loss temperature of these microcapsule is 237 ℃.
Above-mentioned microcapsule are mixed mutually with prezenta, and phase-change microcapsule is scattered in the viscose, prepares the viscose fiber silk by solvent spinning spray silk process, can be used for high-grade weaving, intelligent temperature-regulation garment, has market outlook preferably.
Embodiment 3-8
Embodiment 3-8 adopts processing method of the present invention, phase change material is mixed with lipophilicity vinyl monomer, hydrophilic ethylene base monomer, di-vinyl monomers, in the above temperature of phase change material transformation temperature, be dispersed in the water that is dissolved with the functional surface promoting agent, and adding initiator, carry out polymerization at a certain temperature, behind the certain hour, can obtain the phase-change microcapsule of different grain size, the different first initial thermal weight loss temperature.Embodiment 3-8 parameters is listed as follows:
Table 1 microencapsulated phase change material compositing formula
Table 2 processing parameter and result
| The embodiment sequence number | Dispersion temperature/℃ | Emulsifying manner | Polymerization temperature/℃ | Polymerization time/hour | Median size/μ m | The first initial weightless temperature/℃ |
| ??3 | ??50 | Emulsify at a high speed/1200 | ??75 | ??6 | ??13 | ??185 |
| ??4 | ??55 | Emulsify at a high speed/1600 | ??75 | ??5 | ??9.6 | ??238 |
| ??5 | ??55 | Emulsify at a high speed/1600 | ??80 | ??6 | ??10.0 | ??249 |
| ??6 | ??50 | Emulsify at a high speed/1600 | ??70 | ??4 | ??9.8 | ??230 |
| ??7 | ??40 | Ultrasonic/15 minute | ??80 | ??4 | ??0.8 | ??233 |
| ??8 | ??70 | Ultrasonic/20 minute | ??80 | ??3 | ??0.9 | ??236 |
From embodiments of the invention 3 and 4, embodiment 6 and 7 as can be seen, the monomeric use of hydrophilic ethylene base can effectively improve the first initial thermal weight loss temperature of microcapsule, the crosslinking degree of embodiment 4 and 5, embodiment 7 and 8 explanation bi-vinyl monomeric use can increasing polymkeric substance, thereby the first initial thermal weight loss temperature of raising microcapsule.
Claims (5)
1. the preparation method of a phase-change material micro-capsule, this preparation method adopts following technology: the phase change material core and the monomer of design transformation temperature are mixed in proportion, stir, and be heated to more than the phase point temperature of phase change material core, make it to dissolve fully, be prepared into oil phase; The functional surface promoting agent is dissolved in the water, and is heated to more than the phase point temperature of phase change material, be prepared into water, and only in preparation oil phase process, add oil-soluble initiator, perhaps only in preparation water process, add water soluble starter; Then described oil phase is joined aqueous phase, utilize high-shear emulsifying method or pre-emulsification to add the ultrasonic emulsification method and prepare emulsion; Deoxygenation then adds water soluble starter, and polyreaction adopts emulsion polymerisation process that the polyreaction orientation is occurred on the surface of emulsion droplet at a certain temperature, promptly obtains the phase-change material micro-capsule of required transformation temperature;
The required transformation temperature of described phase change material core is 20～80 ℃; Described phase change material core is meant the aliphatic hydrocarbon compounds, comprises the uniform mixture of one or more compounds in alkane compound, alcohol compound and the ester compound; Described alkane compound comprises n-dodecane, n-tetradecane, n-hexadecane, Octadecane, NSC 77136 and eicosane; Described alcohol compound comprises lauryl alcohol, hexalin and the trimethyl carbinol; Described ester compound comprises n-butyl stearate; Described phase change material weight part as core is 10～60;
Described monomer is meant mixed ethylene type free base monomer, comprises (1) a kind of lipophilicity vinyl free radical monomer, comprises vinylbenzene, vinyl toluene, vinyl acetate, (methyl) methyl acrylate and Jia Jibingxisuanyizhi; (2) a kind of general formula is C
mH
2m+1-CH=CH-C
nH
2n-COOH (m, n=0,1,2 ...) hydrophilic ethylene base free radical monomer, comprise (methyl) vinylformic acid and derivative thereof and oleic acid; (3) a kind of oil-soluble monomer with diene key comprises Vinylstyrene and diacrylate butanediol ester, and monomeric mixed weight ratio is: (1): (2)=5～10: 0.1～5, or (1): (2): (3)=5～10: 0.1～5: 0～5;
Described functional surface promoting agent is the tensio-active agent that contains at least a polymerisable surfactant, and polymerisable surfactant is meant as sodium oleate, two ten diester of maleic anhydride or methylacryoyloxyethyl dodecyl dimethyl brometo de amonio; The weight part of functional surface promoting agent is 0.1～5;
Described initiator is meant oil-soluble Diisopropyl azodicarboxylate or benzoyl peroxide, perhaps water miscible Potassium Persulphate, Sodium Persulfate or ammonium persulphate; When using oil-soluble initiator, it is dissolved in the oil phase; When using water soluble starter, it is dissolved in the water; The weight part of initiator is 0.05～1;
Described polymeric reaction temperature is 20～100 ℃; Described polymerization reaction time is 2～12 hours.
2. the preparation method of phase-change material micro-capsule according to claim 1 is characterized in that described high speed shear emulsification method is emulsification under 1000～9000 rev/mins high speed shear mulser rotating speed 10～30 minutes.
3. the preparation method of phase-change material micro-capsule according to claim 1 is characterized in that it is earlier pre-emulsification after 10～20 minutes that described pre-emulsification adds the ultrasonic emulsification method, emulsification 10～30 minutes on the ultrasonic emulsification machine again.
4. phase-change material micro-capsule, this phase-change material micro-capsule is made by the preparation method of each described phase-change material micro-capsule in the claim 1～3, and the median size of phase-change material micro-capsule is 0.1～50 μ m.
5. the insulating coating material of an external wall, it is characterized in that this insulating coating material by the described phase-change material micro-capsule of claim 4 and concrete mortar by 1～4: 10 weight ratio mixes to be made.
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Cited By (32)
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