CN104962242A - Low super-cooling degree phase-change material microcapsule and preparation method thereof - Google Patents
Low super-cooling degree phase-change material microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN104962242A CN104962242A CN201510359606.9A CN201510359606A CN104962242A CN 104962242 A CN104962242 A CN 104962242A CN 201510359606 A CN201510359606 A CN 201510359606A CN 104962242 A CN104962242 A CN 104962242A
- Authority
- CN
- China
- Prior art keywords
- change material
- phase
- capsule
- preparation
- material micro
- 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.)
- Granted
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a low super-cooling degree phase-change material microcapsule and a preparation method thereof. The microcapsule is composed of, by weight, 35-70% of a capsule core and 30-65% of a capsule wall, the capsule core is composed of, by weight, 81.1%-97.6% of an organic phase-change material, 0.1-16.9% of a super-cooling inhibitor and 1.2-2.7% of initiator, and the super-cooling inhibitor is at least one of N,N-diethyl acrylamide and N-isopropyl acrylamide; the capsule wall comprises, by weight, copolymer of 80-95% of methacrylic acid alkyl ester/aryl ester and 5-20% of an alkene propyl ester cross-linking agent; the low super-cooling degree phase-change material microcapsule is prepared by preparing, mixing and reacting of a water-phase mixture and an oil-phase mixture. The phase-change material microcapsule has the advantages that the coating rate is high, the heat storage quantity is high, the thermal performance is excellent, and the super-cooling crystallization phenomenon is particularly improved significantly; the technology is simple, the operation is convenient, the application range is wide, and the industrial implementation is facilitated.
Description
Technical field
The present invention relates to phase change material technical field, specifically a kind of low condensate depression phase-change material micro-capsule and preparation method thereof.
Background technology
Phase change material refers to and varies with temperature and change the class material that physical properties also can provide a large amount of latent heat.Microcapsulary being introduced the microencapsulated phase change material that phase change material obtains is a kind of circulation energy-storage composite material of good performance, can as energy accumulator, have in energy saving building, heat exchange, temperature control, fiber and textiles, aerospace and military field etc. and act on (Cui Jinfeng widely, Cui Zhuo, Zhou Yingping, Deng. Review of mcroencapsulated phase change materials [J]. Chinese coating, 2013,28 (9): 005.).Microencapsulated phase change material phase change material is enclosed in microcapsule the particulate forming nucleocapsid structure, shape mostly is spherical, particle diameter is generally between 1 ~ 1000 μm, the thickness of shell between 0.2 ~ 10 μm not etc., its efficiently solve phase change material leakage, be separated and the problem such as corrodibility, make phase change material persistent solid-state, and widen the Application Areas of phase-change heat storage technology.The phase change material being applicable to doing core is generally solid-liquid phase change material, can be divided into inorganic phase-changing material, organic phase change material and combined phase-change material three kinds.Inorganic phase-changing material mainly comprises the inorganicss such as crystalline hydrate salt, melting salt, metal (comprising alloy), there is applied widely, that thermal conductivity large, low price is easy to get advantage, but it is serious that it crosses cold-peace phenomenon of phase separation, has certain corrodibility; Organic phase change material mainly comprises paraffin, carboxylic acid, carboxylicesters, polyvalent alcohol, sugar alcohol, polyethers etc., relative to inorganic phase-changing material, organic phase change material has that solid forming is good, surfusion and very serious, the steady performance that is separated, wherein paraffin class phase change material latent heat is large, transition temperature range is wide, price is low, so paid attention to widely in the research of phase-changing energy storage material uses.
Suppress microencapsulated phase change material excessively cold method mainly outer Added Nucleating Agents impel its heterogeneous nucleation crystallization, so far, the nucleator developed has 1-pentadecanol, 1-tetradecyl alcohol, NaCl, 1-stearyl alcohol, paraffin, tripoli, nano Ag particles, multi-walled carbon nano-tubes, polyaniline, polypyrrole (Xu Debin, Song Qingwen, Wang Jinmei. the superfusibility [J] of carbon nano-tube compound phase transformation microcapsule. Tianjin University of Technology's journal, 2011,30 (4): 15-18.).But, the content adding phase change material in membership reduction microcapsule of nucleator, and decline further along with the increase of add-on; Linear alcohols (hydroxyl has wetting ability) and sodium-chlor (having breakdown of emulsion) etc. are as microencapsulated phase change material can be made during nucleator easily to reunite; Nanoparticle, because considering that between itself and core, mutual solubility is poor, is not a kind of desirable nucleator; The microcapsule color blackening that polyaniline is prepared as nucleator two-step approach is to unfavorable (the southern blink of following process, Wang Jianping, Wang Yan, etc. comprise preparation and the performance [J] thereof of the phase change material Na capsule of polyaniline. Acta PhySico-Chimica Sinica, 2014,2:021.).Chinese invention patent (CN 102876297A) discloses a kind ofly prepares the low condensate depression phase-change material micro-capsule that two step synthesis take polypyrrole as nucleator, and preparation technology is not all roses, the problem that also there is color change of same microcapsule.
Therefore, develop the nucleator that a kind of amount neither affecting effective constituent phase change material is not separated with phase change material again, and prepare the difficult point that the simple and efficient phase-change material micro-capsule reducing condensate depression of production technique remains current phase-change material micro-capsule research field, the breakthrough in this direction has important strategic importance to the application promoting phase-change material micro-capsule.
Summary of the invention
The object of the present invention is to provide a kind of low condensate depression phase-change material micro-capsule and preparation method thereof, the phase-change material micro-capsule clad ratio utilizing the method obtained is high, and quantity of heat storage is high, and thermal characteristics is superior, particularly significantly improves cold crystallization phenomenon.And this preparation method's technique is simple, easy to operate, applied widely, be convenient to industrial implementation.
For achieving the above object, the invention provides following technical scheme:
A kind of low condensate depression phase-change material micro-capsule, comprises the ideal that a kind of nothing is separated, mutual solubility is good with organic solid-liquid phase change material cross cold inhibitor for core.This phase-change material micro-capsule is made up of capsule-core 35 ~ 70% and cyst wall 30 ~ 65% by weight percentage, described capsule-core is made up of organic phase change material 81.1 ~ 97.6%, excessively cold inhibitor 0.1 ~ 16.9% and initiator 1.2 ~ 2.7% according to the raw material of weight percent, the cold inhibitor of described mistake is at least one in N, N-acrylamide and NIPA; Described cyst wall component by weight percentage comprises the multipolymer of alkyl methacrylate/aryl ester 80 ~ 95% and allyl ester class linking agent 5 ~ 20%.
As the further scheme of the present invention: described organic phase change material is with general formula C
nh
2n+2the normal paraffin compounds that (n=12 ~ 32) represent, with general formula C
nh
2n+2the halo normal paraffin compounds that X (n=12 ~ 32) represents and with general formula C
mh
2m+1cOOCH
2c
ph
2P+1at least one in the fatty acid ester that (n=12 ~ 32, m=10 ~ 20, p=4 ~ 10) represent.
As the further scheme of the present invention: described initiator is Diisopropyl azodicarboxylate.
As the further scheme of the present invention: described alkyl methacrylate/aryl ester is with general formula:
1 ~ 3 kind in the acrylate of (in formula, R is methyl, ethyl, propyl group, butyl, hexyl, decyl, lauryl, cyclohexyl, methylcyclohexyl, phenyl, benzyl).
As the further scheme of the present invention: described allyl ester class linking agent is allyl methacrylate(AMA), Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), TEGDMA, dimethacrylate TEG ester, dimethacrylate 1,3-butanediol ester, dimethacrylate 1, at least one in the acid of 4-butanediol ester, dimethacrylate 1,6-hexylene glycol ester, trimethacrylate three light methylpropane esters, neopentyl glycol dimethacrylate and Ethoxylated bisphenol A dimethacrylate.
The preparation method of described condensate depression phase-change material micro-capsule, comprises following steps:
(1) preparation of aqueous mixture:
Be dispersed in water by emulsifying agent as aqueous phase, wherein emulsifying agent solid content is 0.5 ~ 4%, and is heated to the melt temperature of organic phase change material, not make oil mixture solidify when mixing with oil mixture, makes aqueous mixture;
(2) preparation of oil mixture:
Organic phase change material, excessively cold inhibitor, initiator, alkyl methacrylate/aryl ester, allyl ester class linking agent are mixed in proportion, be heated to above melt temperature 10 ~ 20 DEG C of scopes of organic phase change material, stirring makes it to dissolve completely and presents water white mixed solution, makes oil mixture;
(3) preparation of emulsion:
Shear with refiner, the oil mixture of step (2) is dispersed in the aqueous mixture of step (1) and forms O/W emulsion, velocity of shear is 3000-10000rpm;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
The O/W emulsion that step (3) obtains is transferred in reactor; employing paddle stirs; stirring velocity is 30-500rpm; after reacting 4 ~ 7h under heating in water bath to 68 ~ 80 DEG C of temperature; keep nitrogen protection in reaction process, nitrogen flow is constant, obtains low condensate depression phase-change material micro-capsule suspension; breakdown of emulsion suction filtration, in 50 DEG C of loft drier, namely dry 48h obtains phase-change material micro-capsule.
As the further scheme of the present invention: in described step (1), emulsifying agent is styrene-maleic anhydride copolymer sodium salt.
As the further scheme of the present invention: in described step (2), oil mixture accounts for 8 ~ 30% of the emulsion gross weight of step (3).
Compared with prior art, the invention has the beneficial effects as follows:
The present invention added the effect that cold inhibitor has assistant for emulsifying agent concurrently in the preparation process (2) of microcapsule, due to the existence of initiator in preparation process, the polymkeric substance crossing the generation of cold inhibitor NIPA has Thermo-sensitive, poly N-isopropyl acrylamide oligopolymer is because of Thermo-sensitive at the reaction temperatures, by free radical grappling and to interfacial migration, significantly improve the efficiency of initiation of initiator Diisopropyl azodicarboxylate, significantly improve the coating efficiency of microcapsule, improve the heat storage capacity of phase-change material micro-capsule, the polymkeric substance generated produces temperature sensitive phenomenon and moves to water-oil interface, major part forms the cold inhibitor particle of small mistake inside cyst wall, the crystallization of phase change material is carried out towards the direction of heterogeneous nucleation, inhibit serious cold crystallization excessively, small portion and cyst wall monomer generation copolyreaction.Be generate when microcapsule are formed owing to crossing cold inhibitor simultaneously, avoid the problems such as the micro encapsulation productive rate that the cold inhibitor of additional mistake brings is low, particle adhesion.Operating process of the present invention is simple, does not lump, and the microcapsule obtained after using allyl ester class linking agent have more pliable and tougher shell, and surface has and subsides and gauffer, can alleviate volume change when phase change material undergoes phase transition to the pressure of wall material.
The phase-change material micro-capsule clad ratio that the present invention obtains is high, and quantity of heat storage is high, and thermal characteristics is superior, particularly significantly improves cold crystallization phenomenon.And this preparation method's technique is simple, easy to operate, applied widely, be convenient to industrial implementation.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph figure of the cold phase-change material micro-capsule embodiment 2 of the low mistake of the present invention;
Fig. 2 is the transmission electron microscope photo of the cold phase-change material micro-capsule embodiment 5 of the low mistake of the present invention;
Fig. 3 is the electron scanning micrograph figure of the cold phase-change material micro-capsule embodiment 7 of the low mistake of the present invention;
Fig. 4 is the DSC figure of the cold phase-change material micro-capsule embodiment 3 ~ 7 of the low mistake of the present invention;
Fig. 5 is the DSC partial enlarged drawing of the cold phase-change material micro-capsule embodiment 5 of the low mistake of the present invention;
In figure: a-N-N-isopropylacrylamide 0%; B-N-N-isopropylacrylamide 4.7%; C-N-N-isopropylacrylamide 8.9%; D-N-N-isopropylacrylamide 12.8%; E-N-N-isopropylacrylamide 16.9%; The pure phase change material of f-(experiment condition: N
2atmosphere, sweep velocity 10 DEG C/min).
Embodiment
Below in conjunction with the embodiment of the present invention and accompanying drawing, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 110.5g, wherein organic phase change material n-hexadecane 100g, crosses cold inhibitor NIPA 7.5g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.
The preparation method of described low condensate depression phase-change material micro-capsule, comprises the following steps:
(1) preparation of aqueous mixture: take 2000g water, 100gTA (the styrene-maleic anhydride copolymer sodium-salt aqueous solution of 19%, be purchased from Shanghai Leather Chemical Plant) in 5L glass reaction still, stir and heating in water bath to 35 DEG C, not make oil phase solidify when mixing with oil phase, make aqueous mixture;
(2) preparation of oil mixture:
Above-mentioned organic phase change material, excessively cold inhibitor, initiator, alkyl methacrylate/aryl ester, linking agent allyl methacrylate(AMA) are mixed in proportion, are heated to 35 DEG C, fully stir and make it to dissolve completely to present water white transparency, make oil mixture;
(3) preparation of emulsion:
Oil mixture prepared by the aqueous mixture prepare step (1) and step (2) is poured in plastic containers, and refiner cutting head is placed in mixture, and adjustment velocity of shear is 6000rpm, and emulsification times 15min forms even O/W emulsion; In the present embodiment, oil mixture accounts for emulsion gross weight mark is 9.5%;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
O/W emulsion is transferred in reactor, employing paddle stirs, opening blade stirring regulates stirring velocity to be 300rpm, logical nitrogen deoxygenation 20min before reaction, and keeping nitrogen protection in reaction process, nitrogen flow is constant, after reacting 7h under heating in water bath to 75 DEG C of temperature, naturally cooling stops stirring, and obtains low condensate depression phase-change material micro-capsule; Breakdown of emulsion filtering separation, rinses 2 times with hot ethanol, after the deionized water rinsing product of reusable heat 3 times, is dried to constant weight, namely obtains phase-change material micro-capsule dry powder in 50 DEG C of vacuum drying ovens.
After testing, the particle diameter of gained phase-change material micro-capsule is mainly distributed between 0.5-10 μm, and median size is 4.2 μm, endothermic temperature (T
m) be 15.9 DEG C, melting enthalpy (Δ H
m) be 92J/g, exothermic temperature (T
c2) be 15.9 DEG C, crystallization heat content (Δ H
c2) be 79J/g, exothermic temperature (T
c1) be 11.5 DEG C, crystallization heat content (Δ H
c1) be 39J/g; Heat decomposition temperature (T
d) be 165.8 DEG C (initial Weight loss data).
Embodiment 2
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 132g, wherein organic phase change material Octadecane 120g, crosses cold inhibitor NIPA 9g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.
(1) preparation of aqueous mixture: take 2000g water, (styrene-maleic acid of 19% joins multipolymer sodium-salt aqueous solution to 100gTA, be purchased from Shanghai Leather Chemical Plant) in 5L glass reaction still, stir and heating in water bath to 45 DEG C, not make oil phase solidify when mixing with oil phase, make aqueous mixture;
(2) preparation of oil mixture:
Above-mentioned organic phase change material, excessively cold inhibitor, initiator, alkyl methacrylate/aryl ester, linking agent allyl methacrylate(AMA) are mixed in proportion, are heated to 45 DEG C, fully stir and make it to dissolve completely to present water white transparency, make oil mixture;
(3) preparation of emulsion:
Oil mixture prepared by the aqueous mixture prepare step (1) and step (2) is poured in plastic containers, and refiner cutting head is placed in mixture, and adjustment velocity of shear is 8000rpm, and emulsification times 10min forms even O/W emulsion; In the present embodiment, oil mixture accounts for emulsion gross weight mark is 10.3%;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
O/W emulsion is transferred in reactor, employing paddle stirs, opening blade stirring regulates stirring velocity to be 300rpm, logical nitrogen deoxygenation 20min before reaction, and keeping nitrogen protection in reaction process, nitrogen flow is constant, after reacting 7h under heating in water bath to 75 DEG C of temperature, naturally cooling stops stirring, and obtains low condensate depression phase-change material micro-capsule; Breakdown of emulsion filtering separation, rinses 2 times with hot ethanol, after the deionized water rinsing product of reusable heat 3 times, is dried to constant weight, namely obtains phase-change material micro-capsule dry powder in 50 DEG C of vacuum drying ovens.
After testing, the particle diameter of gained phase-change material micro-capsule is mainly distributed between 0.5-5 μm, and median size is 1.8 μm, endothermic temperature (T
m) be 23.3 DEG C, melting enthalpy (Δ H
m) be 121J/g, exothermic temperature (T
c3) be 24.0 DEG C, crystallization heat content (Δ H
c3) be 8.1J/g, exothermic temperature (T
c2) be 21.6 DEG C, crystallization heat content (Δ H
c2) be 70.1J/g, exothermic temperature (T
c1) be 15.1 DEG C, crystallization heat content (Δ H
c1) be 50.7J/g; Heat decomposition temperature (T
d) be 216.8 DEG C (initial Weight loss data).
Embodiment 3
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 123g, wherein organic phase change material Octadecane 120g, crosses cold inhibitor NIPA (NIPA) 0g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.Preparation method is identical with embodiment 2, and wherein oil mixture accounts for emulsion gross weight mark is 10%.
Embodiment 4
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 129g, wherein organic phase change material Octadecane 120g, crosses cold inhibitor NIPA (NIPA) 6g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.Preparation method is identical with embodiment 2, and wherein oil mixture accounts for emulsion gross weight mark is 10.2%.
Embodiment 5
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 135g, wherein organic phase change material Octadecane 120g, crosses cold inhibitor NIPA (NIPA) 12g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.Preparation method is identical with embodiment 2, and wherein oil mixture accounts for emulsion gross weight mark is 10.4%.
Embodiment 6
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 141g, wherein organic phase change material Octadecane 120g, crosses cold inhibitor NIPA (NIPA) 18g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.Preparation method is identical with embodiment 2, and wherein oil mixture accounts for emulsion gross weight mark is 10.7%.
Embodiment 7
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 148g, wherein organic phase change material Octadecane 120g, crosses cold inhibitor NIPA (NIPA) 25g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.Preparation method is identical with embodiment 2, and wherein oil mixture accounts for emulsion gross weight mark is 10.9%.
The different cold phase-change material micro-capsule of low mistake of the cold inhibitor content of mistake prepared embodiment 3 ~ 7 carries out performance test, and test result is as shown in table 1.
Table 1 embodiment 3-7 different content crosses the performance table of cold inhibitor phase-change material micro-capsule
| Embodiment | 3 | 4 | 5 | 6 | 7 |
| NIPA wt%(accounts for capsule-core) | 0 | 4.7 | 8.9 | 12.8 | 16.9 |
| T m (℃) | 23.4 | 22.7 | 22.8 | 23.3 | 22.7 |
| ΔH m (J/g) | 110 | 121 | 123 | 123 | 95 |
| T c1 (℃) | 15.6 | 16.0 | 14.9 | 14.5 | 14.5 |
| ΔH c1 (J/g) | 83 | 79 | 67 | 68 | 52 |
| T c2 (℃) | 21.4 | — | 20.2 | — | 19.1 |
| ΔH c2 (J/g) | 18 | — | 33 | — | 19 |
| T c3 (℃) | 24.0 | 24.4 | 24.0 | 25.2 | 24.0 |
| ΔH c3 (J/g) | 12 | 44 | 25 | 55 | 25 |
| Product | Scattered | Scattered | Scattered | Scattered | Scattered |
Data as can be seen from table 1, along with the increase of crossing cold inhibitor, Δ H
c1in reduction, Δ H
c2, Δ H
c3increase, but account for the increase of emulsion gross weight mark along with oil mixture, the dispersiveness of whole system microcapsule is all good, and clad ratio is high, and and soilless sticking and caking phenomenon.Served as cold inhibitor be added to 16.9% and above after, because the copolymerization ratios increase of crossing cold inhibitor and wall material monomer causes clad ratio to decline to some extent.
Embodiment 8
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 141g, wherein organic phase change material 1-bromo eicosane 120g, crosses cold inhibitor NIPA 18g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 165g, wherein phenyl methacrylate and linking agent dimethacrylate allyl glycol ester are respectively 150g and 15g.
(1) preparation of aqueous mixture: take 900g water, (styrene-maleic acid of 19% joins multipolymer sodium-salt aqueous solution to 50gTA, be purchased from Shanghai Leather Chemical Plant) in 5L glass reaction still, stir and heating in water bath to 55 DEG C, not make oil phase solidify when mixing with oil phase, make aqueous mixture;
(2) preparation of oil mixture:
Above-mentioned organic phase change material, excessively cold inhibitor, initiator, alkyl methacrylate/aryl ester, linking agent dimethacrylate allyl glycol ester are mixed in proportion, be heated to 55 DEG C, abundant stirring makes it to dissolve completely to present water white transparency, makes oil mixture;
(3) preparation of emulsion:
Oil mixture prepared by the aqueous mixture prepare step (1) and step (2) is poured in plastic containers, and refiner cutting head is placed in mixture, and adjustment velocity of shear is 7000rpm, and emulsification times 15min forms even O/W emulsion; In the present embodiment, oil mixture accounts for emulsion gross weight mark is 24%;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
O/W emulsion is transferred in reactor, employing paddle stirs, opening blade stirring regulates stirring velocity to be 400rpm, logical nitrogen deoxygenation 20min before reaction, and keeping nitrogen protection in reaction process, nitrogen flow is constant, after reacting 7h hour under heating in water bath to 70 DEG C of temperature, naturally cooling stops stirring, and obtains low condensate depression phase-change material micro-capsule; Breakdown of emulsion filtering separation, rinses 2 times with hot ethanol, after the deionized water rinsing product of reusable heat 3 times, is dried to constant weight, namely obtains phase-change material micro-capsule dry powder in 50 DEG C of vacuum drying ovens.
After testing, the particle diameter of gained phase-change material micro-capsule is mainly distributed between 0.5 ~ 10 μm, and median size is 3.2 μm, endothermic temperature (T
m) be 34.1 DEG C, melting enthalpy (Δ H
m) be 115J/g, exothermic temperature (T
c3) be 35.0 DEG C, crystallization heat content (Δ H
c2) be 35J/g, exothermic temperature (T
c2) be 25.2 DEG C, crystallization heat content (Δ H
c2) be 32J/g, exothermic temperature (T
c1) be 19.7 DEG C, crystallization heat content (Δ H
c1) be 51J/g; Heat decomposition temperature (T
d) be 238 DEG C (initial Weight loss data).
Embodiment 9
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 110g, wherein organic phase change material n-butyl stearate 96g, cross cold inhibitor N, N-acrylamide 11g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 204g, wherein phenyl methacrylate and linking agent dimethacrylate 1,3 butylene glycol ester are respectively 163.2g and 40.8g.
(1) preparation of aqueous mixture: take 1850g water, (styrene-maleic acid of 19% joins multipolymer sodium-salt aqueous solution to 50gTA, be purchased from Shanghai Leather Chemical Plant) in 5L glass reaction still, stir and heating in water bath to 55 DEG C, not make oil phase solidify when mixing with oil phase, make aqueous mixture;
(2) preparation of oil mixture:
By above-mentioned organic phase change material, cross cold inhibitor, initiator, alkyl methacrylate/aryl ester, linking agent dimethacrylate 1,3-butanediol ester is mixed in proportion, be heated to 55 DEG C, fully stir and make it to dissolve completely to present water white transparency, make oil mixture;
(3) preparation of emulsion:
Oil mixture prepared by the aqueous mixture prepare step (1) and step (2) is poured in plastic containers, and refiner cutting head is placed in mixture, and adjustment velocity of shear is 3000rpm, and emulsification times 20min forms even O/W emulsion; In the present embodiment, oil mixture accounts for emulsion gross weight mark is 8%;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
O/W emulsion is transferred in reactor, employing paddle stirs, opening blade stirring regulates stirring velocity to be 500rpm, logical nitrogen deoxygenation 20min before reaction, and keeping nitrogen protection in reaction process, nitrogen flow is constant, after reacting 4h hour under heating in water bath to 80 DEG C of temperature, naturally cooling stops stirring, and obtains low condensate depression phase-change material micro-capsule; Breakdown of emulsion filtering separation, rinses 2 times with hot ethanol, after the deionized water rinsing product of reusable heat 3 times, is dried to constant weight, namely obtains phase-change material micro-capsule dry powder in 50 DEG C of vacuum drying ovens.
After testing, the particle diameter of gained phase-change material micro-capsule is mainly distributed between 0.5 ~ 10 μm, and median size is 6.2 μm, endothermic temperature (T
m) be 17.1 DEG C, melting enthalpy (Δ H
m) be 46J/g, exothermic temperature (T
c3) be 19.6 DEG C, crystallization heat content (Δ H
c2) be 10J/g, exothermic temperature (T
c2) be 16.5 DEG C, crystallization heat content (Δ H
c2) be 8J/g, exothermic temperature (T
c1) be 12.6 DEG C, crystallization heat content (Δ H
c1) be 28J/g; Heat decomposition temperature (T
d) be 241 DEG C (initial Weight loss data).
Embodiment 10
In the embodiment of the present invention, a kind of low condensate depression phase-change material micro-capsule, be made up of capsule-core and cyst wall, capsule-core 257g, wherein organic phase change material n-butyl stearate 236g, crosses cold inhibitor NIPA 18g, initiator Diisopropyl azodicarboxylate (AIBN) 3g, cyst wall 110g, wherein alkyl methacrylate/aryl ester and linking agent neopentyl glycol dimethacrylate are respectively 104.5g and 5.5g.
(1) preparation of aqueous mixture: take 225g water, (styrene-maleic acid of 19% joins multipolymer sodium-salt aqueous solution to 60gTA, be purchased from Shanghai Leather Chemical Plant) in 5L glass reaction still, stir and heating in water bath to 55 DEG C, not make oil phase solidify when mixing with oil phase, make aqueous mixture;
(2) preparation of oil mixture:
Above-mentioned organic phase change material, excessively cold inhibitor, initiator, alkyl methacrylate/aryl ester, linking agent neopentyl glycol dimethacrylate are mixed in proportion, be heated to 55 DEG C, abundant stirring makes it to dissolve completely to present water white transparency, makes oil mixture;
(3) preparation of emulsion:
Oil mixture prepared by the aqueous mixture prepare step (1) and step (2) is poured in plastic containers, and refiner cutting head is placed in mixture, and adjustment velocity of shear is 10000rpm, and emulsification times 10min forms even O/W emulsion; In the present embodiment, oil mixture accounts for emulsion gross weight mark is 30%;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
O/W emulsion is transferred in reactor, employing paddle stirs, opening blade stirring regulates stirring velocity to be 30rpm, logical nitrogen deoxygenation 20min before reaction, and keeping nitrogen protection in reaction process, nitrogen flow is constant, after reacting 7h under heating in water bath to 68 DEG C of temperature, naturally cooling stops stirring, and obtains low condensate depression phase-change material micro-capsule; Breakdown of emulsion filtering separation, rinses 2 times with hot ethanol, after the deionized water rinsing product of reusable heat 3 times, is dried to constant weight, namely obtains phase-change material micro-capsule dry powder in 50 DEG C of vacuum drying ovens.
After testing, the particle diameter of gained phase-change material micro-capsule is mainly distributed between 0.5 ~ 10 μm, and median size is 4.0 μm, endothermic temperature (T
m) be 16.9 DEG C, melting enthalpy (Δ H
m) be 90J/g, exothermic temperature (T
c3) be 19.8 DEG C, crystallization heat content (Δ H
c2) be 68J/g, exothermic temperature (T
c2) be 12.2 DEG C, crystallization heat content (Δ H
c2) be 23J/g; Heat decomposition temperature (T
d) be 237 DEG C (initial Weight loss data).
The phase-change material micro-capsule clad ratio that the present invention obtains is high, and quantity of heat storage is high, and thermal characteristics is superior, particularly significantly improves cold crystallization phenomenon.And this preparation method's technique is simple, easy to operate, applied widely, be convenient to industrial implementation.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (8)
1. one kind low condensate depression phase-change material micro-capsule, it is characterized in that, be made up of capsule-core 35 ~ 70% and cyst wall 30 ~ 65% by weight percentage, described capsule-core is made up of organic phase change material 81.1 ~ 97.6%, excessively cold inhibitor 0.1 ~ 16.9% and initiator 1.2 ~ 2.7% according to the raw material of weight percent, the cold inhibitor of described mistake is at least one in N, N-acrylamide and NIPA; Described cyst wall component by weight percentage comprises the multipolymer of alkyl methacrylate/aryl ester 80 ~ 95% and allyl ester class linking agent 5 ~ 20%.
2. low condensate depression phase-change material micro-capsule according to claim 1, is characterized in that, described organic phase change material is with general formula C
nh
2n+2the normal paraffin compounds that (n=12 ~ 32) represent, with general formula C
nh
2n+2the halo normal paraffin compounds that X (n=12 ~ 32) represents and with general formula C
mh
2m+1cOOCH
2c
ph
2P+1at least one in the fatty acid ester that (n=12 ~ 32, m=10 ~ 20, p=4 ~ 10) represent.
3. low condensate depression phase-change material micro-capsule according to claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate.
4. low condensate depression phase-change material micro-capsule according to claim 1, is characterized in that, described alkyl methacrylate/aryl ester is with general formula:
(in formula, R is methyl, ethyl, propyl group, butyl, hexyl, decyl, lauryl, cyclohexyl, methylcyclohexyl, phenyl
, benzyl) acrylate in 1 ~ 3 kind.
5. low condensate depression phase-change material micro-capsule according to claim 1, it is characterized in that, described allyl ester class linking agent is allyl methacrylate(AMA), Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), TEGDMA, dimethacrylate TEG ester, dimethacrylate 1, 3-butanediol ester, dimethacrylate 1, 4-butanediol ester, dimethacrylate 1, 6-hexylene glycol ester, trimethacrylate acid three light methylpropane esters, at least one in neopentyl glycol dimethacrylate and Ethoxylated bisphenol A dimethacrylate.
6., as a preparation method for the condensate depression phase-change material micro-capsule as described in arbitrary according to claim 1-5, it is characterized in that, comprise following steps:
(1) preparation of aqueous mixture:
Be dispersed in water by emulsifying agent as aqueous phase, wherein emulsifying agent solid content is 0.5 ~ 4%, and is heated to the melt temperature of organic phase change material, makes aqueous mixture;
(2) preparation of oil mixture:
Organic phase change material, excessively cold inhibitor, initiator, alkyl methacrylate/aryl ester, allyl ester class linking agent are mixed in proportion, be heated to above melt temperature 10 ~ 20 DEG C of scopes of organic phase change material, stirring makes it to dissolve completely and presents water white mixed solution, makes oil mixture;
(3) preparation of emulsion:
Shear with refiner, the oil mixture of step (2) is dispersed in the aqueous mixture of step (1) and forms O/W emulsion, velocity of shear is 3000-10000rpm;
(4) preparation of the cold phase-change material micro-capsule of low mistake:
Transfer in reactor by the O/W emulsion that step (3) obtains, adopt paddle to stir, stirring velocity is 30-500rpm; after reacting 4 ~ 7h under heating in water bath to 68 ~ 80 DEG C of temperature; keep nitrogen protection in reaction process, nitrogen flow is constant, obtains low condensate depression phase-change material micro-capsule.
7. the preparation method of low condensate depression phase-change material micro-capsule according to claim 6, is characterized in that, in described step (1), emulsifying agent is styrene-maleic anhydride copolymer sodium salt.
8. the preparation method of low condensate depression phase-change material micro-capsule according to claim 6, is characterized in that, in described step (2), oil mixture accounts for 8 ~ 30% of the emulsion gross weight of step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510359606.9A CN104962242B (en) | 2015-06-26 | 2015-06-26 | A kind of low degree of supercooling phase-change material micro-capsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510359606.9A CN104962242B (en) | 2015-06-26 | 2015-06-26 | A kind of low degree of supercooling phase-change material micro-capsule and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104962242A true CN104962242A (en) | 2015-10-07 |
| CN104962242B CN104962242B (en) | 2017-12-01 |
Family
ID=54216343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510359606.9A Expired - Fee Related CN104962242B (en) | 2015-06-26 | 2015-06-26 | A kind of low degree of supercooling phase-change material micro-capsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104962242B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418519A (en) * | 2017-05-16 | 2017-12-01 | 中国科学院过程工程研究所 | A kind of organic phase change material microcapsules of narrow particle diameter distribution and preparation method thereof |
| CN108336048A (en) * | 2018-01-31 | 2018-07-27 | 上海嘉熙科技有限公司 | Hot superconduction fin radiator with phase-transition heat-storage function |
| CN110951465A (en) * | 2019-12-13 | 2020-04-03 | 天津优米优科技有限公司 | Novel phase change capsule and preparation method thereof |
| CN111100604A (en) * | 2019-12-13 | 2020-05-05 | 广州盛色科技有限公司 | Composite color-changing energy storage capsule and preparation method thereof |
| CN113913160A (en) * | 2021-11-09 | 2022-01-11 | 青岛尼希米生物科技有限公司 | Double-layer capsule wall energy storage and temperature regulation microcapsule, polyacrylonitrile fiber and preparation method thereof |
| CN115093833A (en) * | 2022-06-13 | 2022-09-23 | 深圳市兴业卓辉实业有限公司 | Novel multifunctional phase change microcapsule for protective clothing and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701146A (en) * | 2009-10-22 | 2010-05-05 | 天津工业大学 | Phase-change material microcapsule and preparation method thereof |
| CN102876297A (en) * | 2012-10-19 | 2013-01-16 | 天津工业大学 | Microcapsule made from low-supercooling-degree phase-change material and preparation method of microcapsule |
-
2015
- 2015-06-26 CN CN201510359606.9A patent/CN104962242B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701146A (en) * | 2009-10-22 | 2010-05-05 | 天津工业大学 | Phase-change material microcapsule and preparation method thereof |
| CN102876297A (en) * | 2012-10-19 | 2013-01-16 | 天津工业大学 | Microcapsule made from low-supercooling-degree phase-change material and preparation method of microcapsule |
Non-Patent Citations (2)
| Title |
|---|
| 任彦栄等: "温度感应型微胶囊的制备研究", 《化工技术与开发》 * |
| 顾婷等: "自交联法合成相转变温度范围窄的聚(N-异丙基丙烯酰胺)水凝胶微球", 《合成技术及应用》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418519A (en) * | 2017-05-16 | 2017-12-01 | 中国科学院过程工程研究所 | A kind of organic phase change material microcapsules of narrow particle diameter distribution and preparation method thereof |
| CN107418519B (en) * | 2017-05-16 | 2020-04-24 | 中国科学院过程工程研究所 | Organic phase change material microcapsule with narrow particle size distribution and preparation method thereof |
| CN108336048A (en) * | 2018-01-31 | 2018-07-27 | 上海嘉熙科技有限公司 | Hot superconduction fin radiator with phase-transition heat-storage function |
| CN108336048B (en) * | 2018-01-31 | 2020-12-11 | 浙江嘉熙科技有限公司 | Heat superconducting fin radiator with phase change heat storage function |
| CN110951465A (en) * | 2019-12-13 | 2020-04-03 | 天津优米优科技有限公司 | Novel phase change capsule and preparation method thereof |
| CN111100604A (en) * | 2019-12-13 | 2020-05-05 | 广州盛色科技有限公司 | Composite color-changing energy storage capsule and preparation method thereof |
| CN113913160A (en) * | 2021-11-09 | 2022-01-11 | 青岛尼希米生物科技有限公司 | Double-layer capsule wall energy storage and temperature regulation microcapsule, polyacrylonitrile fiber and preparation method thereof |
| CN113913160B (en) * | 2021-11-09 | 2023-08-15 | 青岛尼希米生物科技有限公司 | Double-layer capsule wall energy storage temperature adjustment microcapsule, polyacrylonitrile fiber and preparation method thereof |
| CN115093833A (en) * | 2022-06-13 | 2022-09-23 | 深圳市兴业卓辉实业有限公司 | Novel multifunctional phase change microcapsule for protective clothing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104962242B (en) | 2017-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104962242A (en) | Low super-cooling degree phase-change material microcapsule and preparation method thereof | |
| CN107513375B (en) | Phase-change microcapsule coated with silicon dioxide and preparation method and application thereof | |
| AU2006219884B2 (en) | Microscapsule powder | |
| Yin et al. | Pickering emulsion: A novel template for microencapsulated phase change materials with polymer–silica hybrid shell | |
| CN104449590A (en) | Phase-change energy-storage material nanocapsule and preparation method thereof | |
| CN105399889B (en) | A kind of hydridization wall material Nano capsule of phase-changing energy storage material and preparation method thereof | |
| JP5366972B2 (en) | Method for producing microcapsules | |
| CN108774499B (en) | Graphene-silicon dioxide composite wall material phase change nanocapsule and preparation method thereof | |
| CN102876297B (en) | A kind of low condensate depression phase-change material micro-capsule and preparation method thereof | |
| CN103342991B (en) | Composite nanocapsule phase-change material and preparation method thereof | |
| CN104212416A (en) | Preparation method for paraffin microcapsule phase-change material modified by graphene oxide | |
| CN104069783B (en) | A kind of preparation method of composite micro-capsule of carbon nano-tube modification | |
| CN102676124B (en) | Inorganic hydrous salt phase change energy storage microcapsule and preparation method thereof | |
| CN111621265B (en) | Phase change microcapsule based on inorganic shell layer and manufacturing method and application thereof | |
| CN104629690A (en) | Organic-inorganic substance compounded phase change energy storage microcapsule and preparation method thereof | |
| CN102719227A (en) | Preparation method for high stable phase transition emulsion | |
| CN109294526B (en) | Preparation method of hybrid wall material-coated phase-change submicron capsule based on microemulsion system | |
| CN103537238B (en) | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule | |
| CN112391148A (en) | High-thermal-conductivity and high-enthalpy composite phase change microcapsule and preparation method thereof | |
| CN108854878A (en) | A kind of capric acid microcapsules and preparation method thereof | |
| CN102391839B (en) | Supercooling phase change-inhibiting alkane microcapsule and preparation and application thereof | |
| CN106634857A (en) | Improved microcapsule phase-change material and preparation method thereof | |
| CN106753261A (en) | A kind of microencapsulated phase change material and preparation method thereof | |
| CN106957635A (en) | The microcapsule phase-change particle and preparation method of composite Nano copper and nano-graphene piece | |
| CN102127399B (en) | Phase change material capsule 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171201 Termination date: 20200626 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |