CN101530772A - Preparing method for phase transited stored energy microcapsule covered with an organic polymer material - Google Patents
Preparing method for phase transited stored energy microcapsule covered with an organic polymer material Download PDFInfo
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Abstract
A preparing method for phase transited stored energy microcapsule covered with an organic polymer material adopts the following steps: (1) mixing the 10 weight organic phase transited material and 0.5-2.5 weight nonionic surfactant under the condition of heating and blending; (2) picking the organic polymer material monomer A, B 2-3 weight to add to 40-60 weight water, blending and mixing as the water phase; (3) adding the oil phase to the water phase, blending the material as the creaming liquid at 30-50 centigrade, adding the free radical to the initiator for the poly-reaction 1-8h at 35-90 centigrade; then adjusting the low temperature as blending the material and adding the cross linker, filtering, washing and drying to obtain the finished products. The organic polymer material achieves the phase transited capsule envelopment via the creaming polymer reaction of the wall material; the microcapsule is the spherical; the granule is distributed evenly; the polymer wall material has a stable intensity, great tightness and great mechanical performance.
Description
Technical field
The present invention relates to the technology of preparing of phase-changing energy storage material, specifically be a kind of be the microcapsules of storing energy through phase change of the microcapsules of storing energy through phase change preparation method of wall material and the preparation of this method with the high-molecular organic material.
Background technology
Current, one of key areas of Study on energy saving is efficient, the long-life phase-changing energy storage material of exploitation, realizes solar energy, the exploitation of industrial exhaust heat homenergic, utilization by this material.The operation principle of phase-changing energy storage material is: utilize the phase transformation reaction of material, absorb (release) latent heat of phase change, realize the absorption (release) to energy in the environment, and then reach the energy storage purpose.Phase-changing energy storage material can alleviate even solve heat energy confession-need in the space, on the time unmatched contradiction; Thereby in the society that highlights the energy and environmental problem now, phase-changing energy storage material receives much attention in fields such as building materials, weaving, aviation, solar energy utilization, national defence, aerospace, large-size air conditionings.Yet the loss of phase-changing energy storage material in the use, and promote phase-changing energy storage material and other materials compound must be improved its encapsulation/support technology.
Microencapsulation technology is meant a kind of technology with small solid particle, drop or bubble of coated film or shell material spreading.Utilize microencapsulation technology can realize as the physical property (change density, phase etc.) of improving the core material; Improve Stability of Substance, make core avoid the influence of environment, improve reactivity, durability (prolonging the period of storage of volatile materials), pressure-sensitive, thermal sensitivity and the light sensitivity of core; Reduce the adverse effect that noxious material causes environment; Make by the coating core and have slowly-releasing and target function; Odor barrier; Reduce excitant; Reduce many purposes such as material toxicity.At present, several typical problems of microencapsulation technology are: the elasticity of microcapsule shell material, permeability, weather-proof and chemical mediator-resitant property, degradability; The pattern of microcapsules, particle diameter, loading etc.
The microencapsulation of phase-changing energy storage material is meant in the phase-changing energy storage material surface ratio and coats one deck solid cyst material more equably, thereby reaches the effect of sealing, compares its sealing property with settingization and will get well.Publication number be disclose in the patent application of CN1161364A a kind of with the phase-changing energy storage material micro-capsule of melamine resin as cyst wall, but because melamine resin is more crisp, make the mechanicalness of its phase-changing energy storage material micro-capsule that makes poor, be not durable.Publication number is that the patent application of CN1500714A improves above-mentioned micro-capsule, adopts double-deck cyst wall structure, but adopts the organic amine resin, and its poor chemical stability can not be used for a long time.The general employed organic polymer cyst material of disclosed phase-changing energy storage material micro-capsule, because organic polymer self, its chemical stability is generally relatively poor.
Recently publication number be CN1844296A patent disclosure a kind of be the silicon source with the ethyl orthosilicate, with the preparation method of inorganic silicon dioxide as the phase-changing energy storage material micro-capsule of wall material, at first with after the phase-changing energy storage material heating and melting with emulsifier, add the small amount of alkali slaine again as additive, adding under the thermal agitation, making phase-change material evenly be dispersed into emulsion; In above-mentioned emulsion, add ethyl orthosilicate and little amount of catalyst, under 20～70 ℃ of water-baths, react 3～12h and make.This method flow is simple, but because the stability of phase-changing energy storage material emulsion is not enough, prepared product pattern is rule scarcely, the particle size distribution broad, have shortcomings such as the relatively poor and organic substrate sympathy of wall material mechanical property is bad simultaneously, thereby its range of application is restricted.
Summary of the invention
Above-mentioned problems at the prior art existence, the invention provides the preparation method of the phase-transition energy-storage microcapsules that a kind of high-molecular organic material coats and the microcapsules of storing energy through phase change of preparation thereof, it is that the wall material is realized the microencapsulation encapsulation of phase-changing energy storage material or supported formation regular shape, good dispersion, even particle size distribution, cyst wall good airproof performance and the good phase-transition energy-storage microcapsules material of chemical stability by emulsion polymerization way with the high-molecular organic material.
The microcapsules of storing energy through phase change preparation method that high-molecular organic material of the present invention coats, take following steps:
(1), with 10 mass parts organic phase change materials and 0.5～2.5 mass parts nonionic surface active agent, under 30～50 ℃ of heating, 400～600r/min stirring condition, mix and make oil phase;
(2), get organic polymer monomer A and organic polymer monomers B meter 2～3 mass parts, add in 40～60 mass parts water (distilled water or deionized water), at room temperature, 400～600r/min mixes and make water; Wherein, the mass ratio of described organic polymer monomer A and organic polymer monomers B is 1:0.25～1;
(3), described oil phase is added to described aqueous phase, stir 10～60min down at 30～50 ℃ and make the described oil phase formation emulsion that is uniformly dispersed; Add the radical initiator that is equivalent to described organic polymer monomer mass 0.5～2.5% and cause the high polymer monomer polymerization in this emulsion, polymerisation is 1～8 hour under 35～90 ℃ of water-baths; Slowly temperature adjustment to 3 under agitation～35 ℃ then, it is crosslinked to add crosslinking agent, filters, washs, is drying to obtain finished product.
When step (1) preparation oil phase, 0.3～0.5 mass parts oleophylic class organic polymer monomer C can also be added in the organic phase change material in advance.
Described three kinds of organic polymer monomer A, B, C choose from acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, acrylamide, epoxychloropropane and styrene.The preferred acrylic acid of organic polymer monomer A wherein.
Described organic phase change material can adopt phase transformation paraffin, C
14-C
22N-alkane, C
8-18Fatty alcohol, C
8-18Aliphatic acid or C
8-18Fatty acid ester is wherein preferentially selected lightweight paraffin, 25# phase transformation paraffin, 30# phase transformation paraffin, 35# paraffin, hexadecane, octadecane, eicosane or BS for use.
Described nonionic surface active agent selects for use sorbitol anhydride oleate 80 (Span80) and Tween-81 80 (Tween80) press the mixture of mass ratio 0.4:0.6～0.6:0.4 composition, or existing other nonionic surface active agent.
Described radical initiator is selected at least a in ammonium persulfate, potassium peroxydisulfate, sodium hydrogensulfite and the azodiisobutyronitrile for use.
Described crosslinking agent is selected at least a in aluminum sulfate, aluminium chloride, magnesium chloride, ethylenediamine, the water-soluble epoxy resin crosslinking agent usually for use, and crosslinking agent adds with aqueous solution form.
Adopt a kind of microcapsules of storing energy through phase change of method for preparing, constitute by cyst wall and the organic phase change material that is coated in the cyst wall, described cyst wall is a high-molecular organic material, the quality percentage composition (loading) of organic phase change material is 60～80% in the microcapsules, whole spherical in shape, average grain diameter is 1.0～5.0 μ m; Wherein, described high-molecular organic material is two or three in acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, acrylamide, epoxychloropropane and the styrene.
Macromolecule coated phase-change accumulation energy microcapsule of the present invention is through emulsification, polymerization, coating, crosslinked forming by organic polymer monomer and oleophylic organic phase change material.The acrylic monomer that is adopted is to use a class monomer very widely in the emulsion polymerisation industry.It is very active, not only polymerization separately, and can with other monomer copolymerization.Acrylic copolymer has characteristics such as resistance to water, weatherability, acid resistance, oxygen resistence, ozone resistance, light resistance and smell are few, good with sympathies such as ester class, chlorohydrocarbon and aromatic hydrocarbons, with the bonding force height of pigment and other adhesive, can be widely used in the microencapsulation of materials such as function building materials, dyeing and finishing material, household chemicals, functional paint, thermally indicating material, adhesive and fire proofing.
Compared with prior art, the present invention is owing to adopt the wall material of the copolymer of two or more organic polymer monomer as microcapsules of storing energy through phase change, the advantage of multiple high molecular polymer is combined, and use chemical method to make crosslinked polymer, make the wall of microcapsules finer and close, physicochemical property is more stable.Thereby increased the loading of phase-change material in the microcapsules of storing energy through phase change (the quality percentage composition is greater than 60.0%), the useful life longevity of microcapsules of storing energy through phase change is significantly improved.
In addition, because having environmental friendliness, acrylic copolymer reaches and the good characteristics of multiclass material sympathy, prepared in addition microcapsules of storing energy through phase change is spherical in shape, particle diameter is little and be evenly distributed (1.0～5.0 μ m), therefore can be widely used in functional fluid, functional temperature-regulating fiber, fabric and the construction material.
The present invention has adopted emulsion polymerization technique; but obvious difference is arranged with common process; conventional high polymer monomer emulsion polymerisation usually needs to carry out under the inert atmosphere protection condition of isolated oxygen; the present invention does not need the inert atmosphere protection condition of isolated oxygen can carry out polymerization; it is wide in range to have reaction condition; reaction process is stable, the monomer conversion advantages of higher.
In addition, macromolecule coated phase-change accumulation energy microcapsule of the present invention, high-molecular copolymer wall material is form compact and stable, can adopt advanced drying process with atomizing drying, not only improved production efficiency greatly, and the products therefrom shape more approaches desirable sphere, and particle diameter distributes and more reaches unanimity, and is applicable to that industrial-scale production promotes.
The microcapsules of storing energy through phase change of the inventive method preparation is spherical in shape, regular shape, and good dispersion, even particle size distribution, its high-molecular copolymer wall material is form compact and stable, good airproof performance, good mechanical property.
Description of drawings
Fig. 1 is SEM3500 times of photo of acrylic copolymer microcapsules of storing energy through phase change of the present invention;
Fig. 2 is SEM20000 times of photo of acrylic copolymer microcapsules of storing energy through phase change of the present invention;
Fig. 3 a, b are 25# phase transformation paraffin DSC collection of illustrative plates and acrylic copolymer microcapsules of storing energy through phase change DSC collection of illustrative plates.
The specific embodiment
The present invention is further described below in conjunction with embodiment.
Organic polymer monomer A among the embodiment 1, organic polymer monomers B and organic polymer monomer C select acrylic acid, acrylamide and epoxychloropropane respectively for use, and organic phase change material is that phase transition temperature is 30 ℃ a 25# phase transformation paraffin, and preparation process is as follows:
Get the 10g phase transition temperature and be 30 ℃ 25# phase transformation paraffin and 0.5g epoxychloropropane, add the blended emulsifier that 2g Span80 and Tween80 press mass ratio 0.4:0.6 composition, heat 45 ℃ of water-baths, mix under the 500r/min stirring condition and make oil phase;
Add 1g acrylic acid and 1g acrylamide under the room temperature in 50g or 40g distilled water, 500r/min stirring 10min mixes and makes water.
The water-bath heating slowly is added drop-wise to above-mentioned oil phase the aqueous phase under the stirring down, and 35 ℃ of insulated and stirred emulsification 45min get stable emulsion.Take by weighing each 0.02g of potassium peroxydisulfate and sodium hydrogensulfite, add 2g distilled water respectively and be made into two kinds of initiator solutions.Two kinds of initiator solutions are respectively taken out 1/3, slowly splash in the above-mentioned emulsion, stir and be warming up to 45 ℃, remaining initiator solution divides 4 addings, polymerisation 4h in 1h.Slowly being cooled to 5 ℃ under stirring fast, is 5.0% sodium hydrate aqueous solution rapid adjustment pH value to 11～12 with mass percent concentration, adds mass percent concentration and be 10.0% aluminum sulfate aqueous solution 60g, continuation stirring 8h.Slowly drip mass percent concentration and be 1.0% ethylenediamine solution 25g, adjust the temperature to 35 ℃ and continue to stir 2h; Filtration, washing, drying promptly obtain acrylic acid copolymerization microcapsules of storing energy through phase change.
Wherein, ethylenediamine solution can substitute with the water-soluble epoxy resin cross-linking agent aqueous solution of mass percent concentration 1.0%, and consumption is 50g.
With reference to Fig. 1-3, Fig. 1 is the low range SEM photo that embodiment 1 has coated the acrylic acid copolymer microcapsules of low temperature phase change ergastic substances 25# phase transformation paraffin, and the particle that can be observed microcapsules in photo is for spherical, and particle diameter is evenly distributed.Fig. 2 is the high magnification SEM photo that embodiment 1 has coated the acrylic acid copolymer microcapsules of low temperature phase change ergastic substances 25# phase transformation paraffin, can be observed grain diameter 1.0～5.0 μ m of microcapsules in photo, and the surface is comparatively fine and close.
Fig. 3 a, b illustrate the collection of illustrative plates of the temperature indicating differential thermal analyzer of pure low temperature phase change ergastic substances 25# phase transformation paraffin and acrylic acid copolymer coating low temperature phase change ergastic substances 25# phase transformation paraffin microcapsule, inhale (putting) heat enthalpy value according to phase transformation and calculate, the quality percentage composition of phase-change accumulation energy material is 67.6% in Fig. 3 b microcapsules.
Embodiment 2
Organic polymer monomer A among the embodiment 2 and organic polymer monomers B are selected acrylic acid, methyl-prop butyl ester respectively for use, and organic phase change material is that phase transition temperature is 29 ℃ a octadecane, and preparation process is as follows:
Get the 10g phase transition temperature and be 29 ℃ octadecane, add 0.8g Span80, Tween80 and press the composite emulsifying agent of mass ratio 0.5:0.5, heat 45 ℃ of water-baths, mix under the 500r/min stirring condition and make oil phase;
Take by weighing 1.5g acrylic acid under the room temperature and 1g methyl-prop butyl ester mixes, add 50g distilled water, 500r/min stirs 10min and makes water.
The water-bath heating slowly is added drop-wise to oil phase the aqueous phase under the stirring down, and 45 ℃ of insulated and stirred emulsification 45min get stable emulsion.Take by weighing ammonium persulfate 0.02g, add 4g distilled water and be made into initiator solution.This initiator solution is taken out 1/3, slowly splash in the above-mentioned emulsion, stir and be warming up to 45 ℃, remaining initiator solution divides 4 addings, polymerisation 4h in 1h.Slowly be cooled to below 10 ℃ under stirring fast, the adding mass percent concentration is 10.0% aluminum chloride aqueous solution 20g, continues to stir 8h.Filtration, washing, drying promptly obtain acrylic acid/esters copolymerization microcapsules of storing energy through phase change.
Embodiment 3
Organic polymer monomer A, B and C among the embodiment 3 select acrylic acid, methyl methacrylate and styrene respectively for use, and organic phase change material is that phase transition temperature is 22 ℃ a BS, and preparation process is as follows:
Get the 10g phase transition temperature and be 22 ℃ BS and 0.5g styrene, add the blended emulsifier that 1.5g Span80 and Tween80 press mass ratio 0.4:0.6 composition, heat 35 ℃ of water-baths, mix under the 600r/min stirring condition and make oil phase;
Take by weighing 2g acrylic acid under the room temperature, the 0.5g methyl methacrylate mixes, add 60g distilled water and stir and makes water.
Under 40 ℃ of the water-bath heating oil phase slowly is added drop-wise to the aqueous phase under the stirring, 40 ℃ of insulated and stirred emulsification 45min get stable emulsion.Take by weighing azodiisobutyronitrile 0.04g, add the positive butanone of 4g and be made into initiator solution.Initiator solution is taken out 1/3, slowly splash in the above-mentioned emulsion, stir and be warming up to 90 ℃, remaining initiator solution divides 8 addings, polymerisation 8h in 2h.Slowly be cooled to below 10 ℃ under stirring fast, the adding mass percent concentration is 10.0% magnesium chloride brine 20g, continues to stir 8h.Filtration, washing, drying promptly obtain acrylic acid/esters/styrene terpolymer microcapsules of storing energy through phase change.
Claims (10)
1, a kind of microcapsules of storing energy through phase change preparation method of high-molecular organic material coating is characterized in that taking following steps:
(1), with 10 mass parts organic phase change materials and 0.5～2.5 mass parts nonionic surface active agent, under 30～50 ℃ of heating, 400～600r/min stirring condition, mix and make oil phase;
(2), get organic polymer monomer A and organic polymer monomers B meter 2～3 mass parts, add in 40～60 mass parts water, at room temperature, 400～600r/min mixes and make water; Wherein, the mass ratio of described organic polymer monomer A and organic polymer monomers B is 1:0.25～1;
(3), described oil phase is added to described aqueous phase, stir down 10～60min at 30～50 ℃ and make the described oil phase formation emulsion that is uniformly dispersed, add the radical initiator that is equivalent to described organic polymer monomer mass 0.5～2.5% and cause the high polymer monomer polymerization in this emulsion, polymerisation is 1～8 hour under 35～90 ℃ of water-baths; Slowly temperature adjustment to 3 under agitation～35 ℃ then, it is crosslinked to add crosslinking agent, filters, washs, is drying to obtain finished product.
2, microcapsules of storing energy through phase change preparation method as claimed in claim 1 is characterized in that: when step (1) preparation oil phase, 0.3～0.5 mass parts oleophylic class organic polymer monomer C is added in the organic phase change material in advance.
3, as the microcapsules of storing energy through phase change preparation method of claim 1 or 2, it is characterized in that: described organic polymer monomer adopts at least two kinds in acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate acrylamide, epoxychloropropane and the styrene.
4, microcapsules of storing energy through phase change preparation method as claimed in claim 3 is characterized in that: described organic polymer monomer A is an acrylic acid.
5, microcapsules of storing energy through phase change preparation method as claimed in claim 1 is characterized in that: described organic phase change material adopts lightweight paraffin, 25# phase transformation paraffin, 30# phase transformation paraffin, 35# paraffin, hexadecane, octadecane, eicosane, BS, C
14-C
22N-alkane, C
8-18Fatty alcohol, C
8-18Aliphatic acid or C
8-18Fatty acid ester.
6, as the microcapsules of storing energy through phase change preparation method of claim 1 or 2, it is characterized in that: described radical initiator is selected at least a in ammonium persulfate, potassium peroxydisulfate, sodium hydrogensulfite and the azodiisobutyronitrile for use.
7, as the microcapsules of storing energy through phase change preparation method of claim 1 or 2, it is characterized in that: described crosslinking agent is selected at least a in aluminum sulfate, aluminium chloride, magnesium chloride, ethylenediamine, the water-soluble epoxy resin crosslinking agent for use.
8, as the microcapsules of storing energy through phase change preparation method of claim 1 or 2, it is characterized in that: described nonionic surface active agent selects for use sorbitol anhydride oleate 80 (Span80) and Tween-81 80 (Tween80) to press the mixture that mass ratio 0.4:0.6～0.6:0.4 forms.
9, adopt the microcapsules of storing energy through phase change of any one described method preparation of claim 1-8, it is characterized in that: these microcapsules are made of cyst wall and the organic phase change material that is coated in the cyst wall, described cyst wall is a high-molecular organic material, the quality percentage composition of organic phase change material is 60～80% in the microcapsules, whole spherical in shape, average grain diameter is 1.0～5.0 μ m; Wherein, described high-molecular organic material is two or three in acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, acrylamide, epoxychloropropane and the styrene.
10, microcapsules of storing energy through phase change as claimed in claim 9 is characterized in that: described organic phase change material is lightweight paraffin, 25# phase transformation paraffin, 30# phase transformation paraffin, 35# paraffin, hexadecane, octadecane, eicosane, BS, C
14-C
22N-alkane, C
8-18Fatty alcohol, C
8-18Aliphatic acid or C
8-18Fatty acid ester.
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