CN1321734C - Synthesizing inorganic microcapsules of storing energy through phase change by using method of solution precipitation polymerization - Google Patents
Synthesizing inorganic microcapsules of storing energy through phase change by using method of solution precipitation polymerization Download PDFInfo
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Abstract
The present invention relates to a technology for synthesizing a phase-change energy storing microcapsule by a method of the precipitation polymerization of a polymer solution. The present invention uses water-soluble organic polyethenoxy ether with a melting point of 10 to 90 DEG C as the core of a phase-change material, uses vinyl free-radical monomers and divinyl free-radical monomers as the sources of shell polymers, uses hydrocarbon organic solvent, alcohol organic solvent, ketone organic solvent, ether organic solvent and ester organic solvent as polymerizing media, uses a nonionic surface active agent as a dispersing protective agent for phase-change substances and uses peroxide or an azo compound as an initiating agent for carrying out precipitation polymerization and wrapping to obtain a phase-change microcapsule at the temperature of 20 to 100 DEG C. The microcapsule is especially suitable for the mixture, the compounding, the layer coating and the perfusion of flexible textile materials.
Description
Technical field:
The present invention relates to a kind of technology that adopts the method synthesizing inorganic microcapsules of storing energy through phase change of polymer solution precipitation polymerization.
Background technology:
Phase-changing energy storage material is to improve capacity usage ratio, and the intellectual material of heat release adaptively and heat accumulation, aspect environmental temperature regulate and control, demonstrated application prospect (old love English river is learned English Cao Xue and is increased. the progress of phase-changing energy storage material and application. material Leader .2003,17 (5): 42-44).Make building inner decorative material with phase-changing energy storage material, can make full use of environmental energy, obtain effect cool in summer and warm in winter (the beam yellow Xiang of just navigating, phase-change material application under construction. building heat-energy air conditioner .2004,23 (4): 23-26).The interior trim that is used for space station and manned spaceship, not only can reduce the fluctuation of temperature in the cabin, obtain comfortable space environment, and can effectively reduce dissipation of energy, (strong Lu of leaf Four Modernizations Guo Yuan brightness Chen Ming of society just to save the energy, microencapsulated phase change material and application thereof, polymer material science and engineering .2004,20 (5): 6-9).
Along with people to increasing and diversification that clothes require, except clothes due external attractive in appearance and comfortable and easy to wear, there is also a desire for multiple function, such as functions such as far infrared, uvioresistant, anion, antibiotic, antimite, fire-retardant, radiation shield, thermal isolations.And microcapsules of storing energy through phase change is a kind of coating of dress materials or stock of filler of can be used for, can be used for regulating adaptively the human body environment temperature, be truly produce comfortable function and even intelligence effect take material (Cai Lihai opens emerging auspicious. the research of phase-change material micro-capsule and application. material Leader .2002,16 (12): 61-64).After wearing the clothes that this class contains microcapsules of storing energy through phase change, and when general room temperature environment entered the higher environment of temperature, the effect of the phase-change material Yin Wendu in the microcapsules absorbed heat by solid-state liquefy, thus the rising of reducing human table temperature.Otherwise when when general room temperature environment enters lower temperature environment, phase-change material changes from liquid to solid again, emits heat, thus the reduction of reducing human table temperature.Thus, automatically make human body under high and low temperature, still keep comfort.
Relevant for phase-changing energy storage material and Material Used thereof patent report is arranged, only United States Patent (USP) just has nearly 750 more; Domestic have nearly 150.About microcapsules of storing energy through phase change material and Material Used thereof and technology also have patent report, United States Patent (USP) has nearly 60; Domestic have only 6～7.Wherein, the report of the technology of preparing of relevant microcapsules of storing energy through phase change, quite limited both at home and abroad.Refusing aqueous solution separating husk as humans such as external K.K.Mistry is that polymer, core are the microparticle of phase transformation thing, method (the Mistry K K for preparing microcapsules, Preston J A, Symes K C, Particles, USP-6,753,083.Ciba SpecialtyChemicals Water Treatments Ltd., June 22,2004); The hot phase-change microcapsule of humans such as M.C.Magill is as compound processing multicomponent phase change fiber (the Magill M C of fiber, Hartmann M H, Haggard J S.Multi-component fibers having enhanced reversible thermal properties andmethods of manufacturing thereof, USP-6,855,422.February 15,2005); Human large capsules such as D.A.Davis coat the solid-solid phase change material that microcapsules form stable form, but yardstick 2～50 μ m and the content of only having carried microcapsules briefly can reach 80% (Davis D A, Hart R L, Work D E, et al., Macrocapsules containing microencapsulated phase change materials, USP-6,835,334.Microtek Laboratories, Inc., December 28,2004); R.C Weston and H.R Dungworth have introduced with the methacrylic acid polymer blend and have made shell, phase-change material or other functional materials are made microcapsule preparation method (the Weston R C of sandwich layer, Dungworth H R, Particulate compositions and theirmanufacture, USP-6,716,526.Ciba Specialty Chemicals Water Treatments Ltd., April 6,2004); People such as D.P.Colvin have just stated, and can to prepare diameter be 1～100 μ m phase-change microcapsule material, and be used for absorbing heat and the hard and epoxy resin (the Colvin D P of heat release occasion, Bryant Y G, Mulligan J C, Method of using thermal energy absorbing and conducting potting materials, USP-5,224,356.Triangle Research ﹠amp; Development Corp., July 6,1993); Chen and Eichelberger have introduced size at microcapsules 1/8～1 inch, that contain phase-change material, and preparation method (the Chen J C H of machinery separation, Eichelberger J L, Encapsulated phase changethermal energy storage materials and process, USP-4,513,053.Pennwalt Corporation, April 23,1985).As " a kind of microcapsules coated phase-change material and preparation method thereof (number of patent application: 03130587.3, open day: 2004.07.21) " of people such as domestic Wang Lixin, be with the technology of emulsification method with the polymer overmold phase-change material; People's such as Zhang Xingxiang " autoamtic temp-regulating fibre and goods thereof (Chinese patent-ZL00105837.1, Granted publication day: on 03 19th, 2003) " is the cyst wall that adopts situ aggregation method synthetic, and phase change material is the microcapsules of capsule-core, the preparation temperature-regulating fiber; People such as YG Bryant " adiabatic coating of use microencapsulated phase change material and method (Chinese patent-ZL98804081.6, open day: 2000.05.03) ", be method based on coating, be not the preparation method of microencapsulated phase change material.Obviously, adopt the method for the method synthesizing inorganic microcapsules of storing energy through phase change of polymer solution precipitation polymerization not see similar or similar patent report.
The present invention is a kind of method synthesizing inorganic microcapsules of storing energy through phase change that adopts the polymer solution precipitation polymerization.
The phase-changing energy storage material that microcapsule method makes has the feature and the performance of solid-solid phase-change on the form.In general, the solid-solid phase-change energy-storage material of low temperature because the end group of its strand one or both ends is fixed, its phase transition temperature can change, its unit mass phase transformation heat is lower than the phase-change material of solid-liquid phase.Though and solid-liquid phase change material phase-change energy is bigger, the inefficacy of the leakage of easy generating material and whole mechanical property when liquid state, this is in particular for the application scenario of flexible textile material.
Utilize microcapsules technology will in, low-temperature phase-change material is fixed on microcapsules inside, phase-change material still freely, its phase transition temperature and phase transformation calorific value can not change.Can not only keep the material appearance form, and bigger phase-change energy can be arranged.The present invention's inorganic compound is a phase-changing energy storage material, adopts the technology of the synthetic microcapsules of method of polymer solution precipitation polymerization.Inorganic phase-changing material has the characteristic higher than the organic phase change material thermal efficiency.
Solution precipitation polymerization technology is to utilize polymer not dissolve in solvent, and a kind of polymer synthetic technology that monomer can dissolve in this solvent.The present invention utilizes this polymer synthetic technology, produces phase-change microcapsule.Key problem in technology of the present invention is to have a kind of solvent can dissolve the monomer that synthetic polymer uses and do not dissolve polymer that is synthesized into and the phase-change material that is wrapped.
Summary of the invention:
The objective of the invention is to relate to a kind of technology that adopts the method synthesizing inorganic microcapsules of storing energy through phase change of polymer solution precipitation polymerization.
Adopt inorganic phase-changing material that the characteristic higher than the organic phase change material thermal efficiency arranged; The method of polymer solution precipitation polymerization prepares the vinyl monomer that microcapsules can adopt multiple radical polymerization, the monomer wide material sources; Also can use the features monomer.Microcapsule size can be regulated arbitrarily.
Main technique of the present invention can be expressed as follows:
The inorganic-phase variable core of required phase transition temperature; be dissolved with in the organic solvent of surfactant in its temperature dispersion more than phase transition temperature; add the monomer that contains initator that measures; polymerization at a certain temperature; make the surface of polymer deposition, obtain the phase-change microcapsule of required phase transition temperature to inorganic phase-changing material granule or drop.
It is characterized in that being the source of phase-change material and preventing that cryogen, anti-phase separation agent constituted the phase transformation core together with the inorganic hydrate of phase transition temperature at 10-90 ℃; With vinyl and bi-vinyl type free base monomer is the outer cover polymer source; With hydrocarbon, alcohol, ketone, ether, ester class organic solvent is polymerisation medium; With the non-ionic surface active agent is the dispersion protective agent of phase change material; With peroxide or azo-compound is initator, under 10-100 ℃ temperature, carry out precipitation polymerization parcel and phase-change microcapsule.This polymerization is radical polymerization, and what at high temperature adopt is overactivity energy initator, adopts the low-activation energy initator at low temperatures, so polymerization time is basic identical, all between 4-8 hour.
Described phase transformation core is by inorganic hydrate, prevented that cryogen and anti-phase separation agent constituted.
Described inorganic hydrate is a hydration sodium sulphate, the hydration potassium sulfate, hydration ammonium sulfate, the hydration niter cake, the hydration sodium acetate, the hydration potassium acetate, the hydration ammonium acetate, hydration calcium chloride, hydrated sodium carbonate, hydration potash, the hydration ammonium carbonate, hydration carbonic hydroammonium, the hypophosphite monohydrate disodium hydrogen, hypophosphite monohydrate hydrogen dipotassium, hypophosphite monohydrate hydrogen two ammoniums, the hypophosphite monohydrate sodium dihydrogen, the hypophosphite monohydrate potassium dihydrogen, the hypophosphite monohydrate ammonium dihydrogen, hypophosphite monohydrate sodium, hypophosphite monohydrate potassium, the hypophosphite monohydrate ammonium, nitric hydrate sodium, nitric hydrate potassium, the mixture of nitric hydrate ammonium and above-mentioned hydrate.
Describedly prevented that cryogen was borax, zinc acetate, lead acetate, six lithium fluoride titaniums, barium sulphide, hypophosphite monohydrate calcium, hydration sodium metaphosphate, calcium monohydrogen phosphate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate or graphite.
Described anti-phase separation agent is high hydroscopic resin, neopelex, lauryl sodium sulfate, odium stearate, ammonium stearate, potassium stearate, polyethylene glycol, polyvinyl alcohol, PAM, PVP, Sodium Polyacrylate, gelatin, carboxymethyl cellulose, silica, bentonite or attapulgite.
Above-mentioned three kinds of materials constitute the phase transformation core jointly, wherein inorganic hydrate, prevented that the percentage by weight of cryogen, anti-phase separation agent was 90-99: 0.5-6: 0.5-4.
Described organic solvent is C
6～40Straight or branched alkane, C
1～6Fatty alcohol, benzene,toluene,xylene, benzinum, acetone, butanone, ethyl acetate, butyl acetate or pentyl acetate.
Described monomer is styrene, methyl styrene, vinylacetate, acrylonitrile, methyl methacrylate, EMA, divinylbenzene, GDMA or diallyl p phthalate, can be the mixture of one or more monomers wherein.
Described dispersion protective agent is that molecular formula is R (OCH
2CH
2)
nThe multiple non-ionic surface active agent of OH, wherein R is C
8-18Alkyl phenol, alkyl and acyl alkyl, n is 3-20, and the non-ionic surface active agent of taking charge of this series and tween series, can use separately or compound use.
Described initator is benzoyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile or ABVN.
The dispersion temperature of described inorganic phase-changing material in polymerisation medium is 20-100 ℃.
Described polymerization temperature of plate is 10-100 ℃.
The average dimension of resulting microcapsules of storing energy through phase change can be adjusted arbitrarily between 0.2-10 μ m, sees shown in the accompanying drawing 1.Being specially adapted to the mixing of flexible textile material, compound, coating, perfusion uses.
The weight ratio of described core, vinyl monomer, dispersion protective agent and initator is 10～30: 10～20: 0.05～0.5: 0.01～0.3, and the weight ratio of core and organic solvent is 10～30: 50～90.
Description of drawings:
Fig. 1 is the transmission electron microscope picture of phase-change microcapsule
The specific embodiment:
To help to understand the present invention by following examples, but not limit content of the present invention.
The inorganic-phase variable core of required phase transition temperature; be dissolved with in the organic solvent of surfactant in its temperature dispersion more than phase transition temperature; add the monomer that contains initator that measures; polymerization at a certain temperature; make the surface of polymer deposition, obtain the phase-change microcapsule of required phase transition temperature to inorganic phase-changing material granule or drop.Concrete phase transformation core prescription, polymerization parcel prescription and technology and result are as shown in the table.
1, phase transformation core prescription
| Scheme | Inorganic phase-changing material concentration % | Prevented cryogen concentration % | Anti-phase separation agent concentration % |
| 1 | Sal glauberi 95 | Borax 3 | Polyethylene glycol 2 |
| 2 | Sodium acetate trihydrate 96.5 | Zinc acetate 2 | Gelatin 1.5 |
| 3 | Calcium chloride hexahydrate 95.7 | Calcium hydroxide 3.5 | Carboxymethyl cellulose 0.8 |
| 4 | Disodium hydrogen phosphate 95.9 | Graphite 0.9 | Neopelex 3.2 |
| 5 | Six water magnesium sulfates 95.4 | Calcium sulfate 0.6 | Polyvinyl alcohol 4 |
| 6 | Six water dipotassium hydrogen phosphates 96.5 | |
Polyacrylamide 2.5 |
2, polymerization parcel prescription:
| Scheme | Phase transformation core concentration % | Organic solvent concentration % | Disperse protective agent concentration % | Monomer concentration % | Initiator concentration % |
| 1 | 14 | 7# white oil 72.9 | OP-3+OP-10 0.06+0.01 | Acrylonitrile+divinylbenzene 10+3 | Azodiisobutyronitrile 0.03 |
| 2 | 22 | Ethyl acetate 61.68 | JFC+OP-4 0.02+0.25 | Methyl methacrylate+GDMA 15+1 | Di-isopropyl peroxydicarbonate 0.05 |
| 3 | 12 | Butanols 77.75 | MOA-3+MOA-8 0.16+0.02 | Methyl styrene 10 | ABVN 0.07 |
| 4 | 16 | Kerosene 70.61 | MOA-6 0.25 | Styrene 13 | Benzoyl peroxide 0.14 |
| 5 | 12 | Dimethylbenzene 71.7 | AEO-9+MOA-3 0.02+0.2 | Methyl methacrylate 16 | Dilauroyl peroxide 0.08 |
| 6 | 20 | Benzinum 65.64 | T80+S40 0.03+0.27 | Styrene+divinylbenzene 12+2 | Benzoyl peroxide 0.06 |
Raw materials usedly in the prescription be commercial commodity, the title of surfactant is the above the trade name of surfactant of explanation.
3, technology and result:
| Scheme | The dissolving dispersion temperature (℃) | The polymerization temperature of plate (℃) | Polymerization time (time) | Phase transition temperature (℃) | Average grain |
| 1 | 35 | 80 | 4-6 | 32 | 0.35 |
| 2 | 62 | 40 | 5-6 | 58 | 0.6 |
| 3 | 33 | 30 | 4-6 | 29 | 1.8 |
| 4 | 38 | 75 | 5-7 | 35 | 0.75 |
| 5 | 71 | 35 | 4-7 | 67 | 0.8 |
| 6 | 52 | 80 | 4-6 | 48 | 0.5 |
Embodiment 2
Get calcium chloride hexahydrate 15-16 gram, calcium hydroxide 0.1-0.2 gram, carboxymethyl cellulose 0.5-0.7 gram mixes.Under 40 ℃ of temperature; be dispersed in the 70-75 gram butanone that is dissolved with 0.06 gram OP-3 and 0.01 gram OP-10; add the monomer (styrene 10-14 gram and divinylbenzene 1-3 gram) that contains ABVN 0.02-0.07 gram then; the control temperature is carried out polymerization for 35 ℃; make the surface of polymer deposition, obtain phase transition temperature and be 29 ℃ phase-change microcapsule to inorganic phase-changing material granule or drop.
Above-mentioned polymerizate, butanone is removed in decompression distillation.Get dry powder shape material, be pure phase-change microcapsule.The above-mentioned microcapsules of 40 grams are dispersed in the 60 gram 2D resins, then all-cotton knitting cloth are put into above-mentioned resin liquid, after padding, bake to such an extent that contain the looped fabric of phase-change material.
The phase transition temperature of this coating phase transformation knitted fabric is at 31～34 ℃, and the rate of body weight gain of source textile is 11.8% relatively, and the phase-change energy of coated fabric is about 4.6 joule/gram.Rate of body weight gain after 10 standard washings is 10.9%; Phase-change energy is 4.1 joule/gram.Illustrate that the phase-changing and temperature-regulating after the phase-change microcapsule material coating is handled is obvious.
Embodiment 3
Get phase transformation core prescription, polymerization parcel prescription and the microcapsules shaping preparation technology of the scheme 6 among the embodiment 1, the acquisition phase transition temperature is 48 ℃ a phase-change microcapsule.
Above-mentioned polymerizate, benzinum is removed in decompression distillation.Get dry powder shape material, be pure phase-change microcapsule.The above-mentioned microcapsules of 40 grams are dispersed in the polyvinyl alcohol water solution of 1000 grams 15%, use the wet spinning technology spinning, obtain containing the polyvinyl composite fibre of phase-change material.Making multiple phase transition temperature with this fibre spinnable is 48 ℃ of temperature adjustment fabrics.
Claims (6)
1, a kind of method that adopts polymer solution precipitation polymerization synthesizing inorganic microcapsules of storing energy through phase change is characterized in that being the source of phase-change material and preventing that cryogen, anti-phase separation agent constituted the phase transformation core together with the inorganic hydrate of phase transition temperature at 10-90 ℃; With vinyl and bi-vinyl type free base monomer is the outer cover polymer source; With hydrocarbon, alcohol, ketone, ether or ester class organic solvent is polymerisation medium; With the non-ionic surface active agent is the dispersion protective agent of phase change material; With peroxide or azo-compound is initator, carry out that precipitation polymerization coats and phase-change microcapsule;
Described polymerization coating is the temperature more than the phase transition temperature of inorganic-phase variable core, with phase transition temperature is that 10-90 ℃ inorganic-phase variable core is dispersed in the organic solvent that is dissolved with surfactant, become inorganic-phase variable core drop, be adjusted to 10～100 ℃ polymerization temperature then, add the monomer that contains initator and carry out polymerization, make polymer deposition generate microcapsules to the surface of inorganic-phase variable core; The temperature that described inorganic-phase variable core is dispersed in the organic solvent is 20-100 ℃;
Wherein inorganic hydrate, prevented that the weight ratio of cryogen and anti-phase separation agent was 90～99: 0.5～6.0: 0.5～4, the weight ratio of core, monomer, dispersion protective agent and initator is 10～30: 10～20: 0.05～0.5: 0.01～0.3, and the weight ratio of core and organic solvent is 10～30: 50～90;
Described monomer is the mixture of one or more monomers in styrene, methyl styrene, vinylacetate, acrylonitrile, methyl methacrylate, EMA, divinylbenzene, GDMA or the diallyl p phthalate; Described organic solvent is carbon number C
6～40Straight or branched alkane, C
1～6Fatty alcohol, benzene,toluene,xylene, benzinum, acetone, butanone, ethyl acetate, butyl acetate or pentyl acetate; Described initator is benzoyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile or ABVN; Described inorganic hydrate is a hydration sodium sulphate, the hydration potassium sulfate, hydration ammonium sulfate, the hydration niter cake, the hydration sodium acetate, the hydration potassium acetate, the hydration ammonium acetate, hydration calcium chloride, hydrated sodium carbonate, hydration potash, the hydration ammonium carbonate, hydration carbonic hydroammonium, the hypophosphite monohydrate disodium hydrogen, hypophosphite monohydrate hydrogen dipotassium, hypophosphite monohydrate hydrogen two ammoniums, the hypophosphite monohydrate sodium dihydrogen, the hypophosphite monohydrate potassium dihydrogen, the hypophosphite monohydrate ammonium dihydrogen, hypophosphite monohydrate sodium, hypophosphite monohydrate potassium, the hypophosphite monohydrate ammonium, nitric hydrate sodium, the mixture of one or more hydrates of nitric hydrate potassium or nitric hydrate ammonium.
2, method according to claim 1 is characterized in that describedly preventing that cryogen was borax, zinc acetate, lead acetate, six lithium fluoride titaniums, barium sulphide, hypophosphite monohydrate calcium, hydration sodium metaphosphate, calcium monohydrogen phosphate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate or graphite.
3, method according to claim 1 is characterized in that described anti-phase separation agent is high hydroscopic resin, neopelex, lauryl sodium sulfate, odium stearate, ammonium stearate, potassium stearate, polyethylene glycol, polyvinyl alcohol, polyacrylamide, PVP, Sodium Polyacrylate, gelatin, carboxymethyl cellulose, silica, bentonite or attapulgite.
4, method according to claim 1 is characterized in that described dispersion protective agent is that molecular formula is R (OCH
2CH
2)
nThe multiple non-ionic surface active agent of OH, wherein R is C
8-18Alkyl phenol, alkyl or acyl alkyl, n is 3-20, and the non-ionic surface active agent of taking charge of this series or tween series, uses separately or compound use.
5, method according to claim 1, the diameter that it is characterized in that described microcapsules are 0.2-10 μ m.
6, method according to claim 1 is characterized in that the microcapsules that described method makes, and is applicable to that the mixing of flexible textile material, compound, coating, perfusion use.
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