CN102876297A - Microcapsule made from low-supercooling-degree phase-change material and preparation method of microcapsule - Google Patents
Microcapsule made from low-supercooling-degree phase-change material and preparation method of microcapsule Download PDFInfo
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- CN102876297A CN102876297A CN201210397309XA CN201210397309A CN102876297A CN 102876297 A CN102876297 A CN 102876297A CN 201210397309X A CN201210397309X A CN 201210397309XA CN 201210397309 A CN201210397309 A CN 201210397309A CN 102876297 A CN102876297 A CN 102876297A
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 81
- 239000012782 phase change material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 32
- 239000003112 inhibitor Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 35
- 230000008859 change Effects 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 206010011732 Cyst Diseases 0.000 claims description 15
- 208000031513 cyst Diseases 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- 150000007860 aryl ester derivatives Chemical class 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 229920000128 polypyrrole Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- AXISYYRBXTVTFY-UHFFFAOYSA-N Isopropyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC(C)C AXISYYRBXTVTFY-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002775 capsule Substances 0.000 abstract description 7
- 238000004781 supercooling Methods 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 229920000090 poly(aryl ether) Polymers 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 13
- 239000011162 core material Substances 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- CZASMUMJSKOHFJ-UHFFFAOYSA-N 1-bromoicosane Chemical compound CCCCCCCCCCCCCCCCCCCCBr CZASMUMJSKOHFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
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- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a microcapsule made from low-supercooling-degree phase-change materials and a preparation method of the microcapsule. The microcapsule consists of a capsule core and a capsule wall, wherein the capsule core accounts for 30% to 85% of the microcapsule by weight percent, and the capsule wall accounts for 15% to 70% of the microcapsule by weight percent; the capsule core comprises the following components in percentage by weight: 83% to 99.7% of organic phase-change materials, 0.1% to 1.6% of supercooling inhibitor and 0.1% to 0.5% of initiator; and the capsule wall comprises a copolymer comprising the following components in percentage by weight: 80% to 90% of alkyl methacrylate/polyaryl ether, and 5% to 20% of allyl ester cross-linking agent. The microcapsule made from the phase-change materials has the characteristics of low supercooling degree and excellent performance; and the preparation method is simple, convenient to operate and wide in application range, and facilitates industrial implementation.
Description
Technical field
The invention belongs to the phase change material technical field, relate to a kind of phase-change material micro-capsule and preparation method thereof, be specifically related to a kind of low condensate depression phase-change material micro-capsule and preparation method thereof.
Background technology
Phase change material is to utilize the heat absorption and release phenomenon of some exotic materials in phase transition process, thereby carries out control and the temperature regulation of heat.These materials with heat accumulation and adjusting control function are commonly referred to phase change material (Phase Change Material is called for short PCM).Phase transition process is a kind of isothermal or nearly quasi-isothermal process, and is attended by absorption or the release of larger heat in this process.The character that phase-changing energy storage material needs when utilizing these special materials to undergo phase transition to absorb (or emitting) amount of heat is regulated and control energy.According to the difference that material forms, phase change material can be divided into inorganic phase-changing material, organic phase change material and polymeric phase change material; Difference according to the phase transformation mode can be divided into solid-liquid phase change material and solid-solid phase transition material.Different phase change materials respectively have its different characteristics, also have certain limitation in the application.Microencapsulated phase change material is introduced phase change material with microcapsulary, has increased heat transfer area, has prevented the reaction of phase change material and surrounding environment, has controlled the volume change of PCM when changing mutually, has improved the service efficiency of phase change material, has broad application prospects.
Microcapsulary refers to and makes solid and liquid adopt filmogen to be rolled into the method for the particulate of nucleocapsid structure, and product pellet is called microcapsule.The size of general microcapsule is between 2 μ m～1000 mu m ranges, and the thickness of shell does not wait at 0.2 μ m～10 μ m.The surface shape of microcapsule is abundant, mostly is spherical.The method of micro encapsulation originates from the 1950's, after decades in alter a great deal.The solid-liquid phase change material that can be used as at present the microcapsule inner core materials has crystalline hydrate salt, eutectic salt hydrate, straight-chain paraffin, paraffin class, fatty acid and polyoxyethylene glycol etc.The outside coating film for film forming material formation of microcapsule is called wall material (being also referred to as adventitia, cyst wall).The wall material is generally synthesized polymer material, and available wall material has polyethylene, polystyrene, polyureas, polymeric amide, Resins, epoxy, urea-formaldehyde resin, melamine formaldehyde resin etc.In addition, also contain other auxiliary agents such as nucleator in some microencapsulated phase change material, be used for improving the performance of phase change material.At present, phase change material is little/and Na capsule has been applied in sun power and nuclear energy, electronics, aircraft, aerospace craft contour sophisticated technology field and in fields such as heat-accumulation temperature-adjustment textiles, energy-saving building material, coating, and has been expected to it is applied in the biological fields such as moist heat control of plant seed.
The excessively cold method of eliminating at present phase-change material micro-capsule has two kinds: the one, in phase change material, add inspissated wax, and utilize the crystallization of the inspissated wax nucleus induced transformation material that generates first in the crystallisation process; The 2nd, the heterogeneous nucleation agent of adding solid.Yet this two method has distinct disadvantage: (1) add the amount of inspissated wax must be enough greatly (generally needing 10-20 % by weight or more), like this certainly will be take the amount of reduction effective constituent phase change material as cost; (2) problem brought of the adding of heterogeneous nucleation agent is to reduce on the one hand the packing rate of microcapsule, on the other hand, also must solve the problems such as dispersion stabilization of heterogeneous nucleation agent particle in phase change material.
Therefore, prepare a kind of amount that neither affects the effective constituent phase change material and avoid again the phase-change material micro-capsule of the efficient low condensate depression of the loaded down with trivial details dispersion process of heterogeneous nucleation agent in phase change material to remain the difficult point of present phase-change material micro-capsule research field, the breakthrough of this direction has important strategic importance to the application that promotes phase-change material micro-capsule.
Summary of the invention
The object of the invention is to overcome above-mentioned technological deficiency, a kind of low condensate depression phase-change material micro-capsule and preparation method thereof is provided, it is low that the phase-change material micro-capsule of these microcapsule has condensate depression, the characteristics such as excellent property; This preparation method's technique is simple, easy to operate, applied widely, is convenient to industrial implementation.Its technical scheme is:
A kind of low condensate depression phase-change material micro-capsule, its microcapsule are comprised of capsule-core and cyst wall two portions, count by weight percentage, and described capsule-core and cyst wall are respectively 30-85% and 15-70%, wherein:
The moiety of capsule-core and weight percentage thereof are: organic phase change material 83-99.7%, the cold inhibitor 0.1-16% of mistake, initiator 0.1-0.5%;
The moiety of cyst wall is: the multipolymer of alkyl methacrylate/aryl ester 80-95% and allyl ester class linking agent 5-20%.
Described organic phase change material refers to general formula C
nH
2n+2(n=12-32) the normal paraffin compounds of expression is with general formula C
nH
2n+2The halo normal paraffin compounds of X (n=12-32) expression and with general formula C
mH
2m+1COOCH
2C
pH
2p+1(n=12-32, m=10-20, p=4-10) expression fatty acid ester in any 1～3 kind;
The cold inhibitor of described mistake refers to polypyrrole;
Described initiator refers to Diisopropyl azodicarboxylate;
Described oxygenant refers to benzoyl peroxide;
Described alkyl methacrylate/aryl ester refers to general formula:
Described allyl ester class linking agent refers to 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, at least a in 6-hexylene glycol ester, trihydroxy methyl propane trimethyl acrylate, neopentyl glycol dimethacrylate, the ethoxylation bisphenol a dimethacrylate.
A kind of preparation method of low condensate depression phase-change material micro-capsule comprises following steps:
(1) preparation of oil mixture:
With organic phase change material, cross cold inhibitor monomer, initiator, oxygenant, alkyl methacrylate/aryl ester, allyl ester class linking agent and mix, be heated to above melt temperature 10-20 ℃ of scope of organic phase change material in ratio claimed in claim 2, stirring makes it to dissolve fully and presents water white mixed solution;
(2) preparation of aqueous mixture:
Emulsifying agent and assistant for emulsifying agent are dispersed in water as water, and wherein the emulsifying agent solid content is 0.5-4%, and assistant for emulsifying agent accounts for 0.1-2% with the total weight of water;
(3) preparation of emulsion:
Shear with refiner, make oil phase be dispersed in aqueous phase and form the O/W emulsion, velocity of shear is 3000-8000 rev/min;
(4) preparation of microcapsule:
The O/W emulsion that step (3) obtains is transferred in the reactor, adopted the oar formula to stir, stirring velocity is 30-500 rev/min, and heating in water bath namely obtains phase-change material micro-capsule after reacting 3-4 hour under the 60-68 ℃ of temperature;
(5) preparation of low cold phase-change material micro-capsule:
Step (4) is obtained phase-change material micro-capsule continue to be warmed up to 75-85 ℃ of reaction after 1-2 hour, naturally cooling namely obtains low cold phase-change material micro-capsule.
The described emulsifying agent of step (2) is styrene-maleic anhydride copolymer, and described assistant for emulsifying agent is n-Octanol.
The described oil mixture of step (1) accounts for the 10-30% of the described emulsion gross weight of step (3).
Compared with prior art, beneficial effect of the present invention is:
Technical scheme of the present invention has added in the preparation of microcapsule crosses cold inhibitor monomer, in preparation process because the existence of oxygenant, original position has generated the cold inhibitor particle of the small mistake that is dispersed in the phase change material, so that the crystallization of phase change material is carried out towards the direction of heterogeneous nucleation, suppressed the serious cold crystallization of crossing.Be that original position generates after microcapsule form owing to cross cold inhibitor, avoided adding the problems such as the encapsulated productive rate that cold inhibitor brings is low, particle adhesion.Operating process is simple, does not lump, and uses the microcapsule that obtain behind the allyl ester class linking agent to have more pliable and tougher shell, and the surface has and subsides and gauffer, and the volume change in the time of can alleviating phase change material and undergo phase transition is to the pressure of shell material.Except adding the cold inhibitor monomer of a small amount of mistake, do not mix other materials in the microcapsule preparation, therefore can obviously not reduce the heat storage capacity of microcapsule.
Description of drawings
Fig. 1. for the present invention low the electron scanning micrograph figure of cold phase-change material micro-capsule embodiment 1;
Fig. 2. for the present invention low the DSC figure of cold phase-change material micro-capsule embodiment 3-6, wherein: a-pyrroles 0%; B-pyrroles 4%; C-pyrroles 8%; D-pyrroles 12%; The e-pure phase becomes material (experiment condition: N
2Atmosphere, 10 ℃/minutes of sweep velocitys).
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is described in more detail.
Embodiment 1
Microcapsule mass percent composition is designed to:
Capsule-core 128g, wherein organic phase change material Octadecane 120g crosses cold inhibitor polypyrrole 5g, initiator Diisopropyl azodicarboxylate (AIBN) 1.5g, oxygenant benzoyl peroxide (BPO) 1.5g; Cyst wall 110g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 10g.
The preparation method of microcapsule is:
(1) preparation of oil mixture: under 45 ℃ the temperature and under 300 rev/mins the stirring velocity, organic phase change material, the cold inhibitor monomer of mistake, initiator, oxygenant, alkyl methacrylate/aryl ester, the allyl ester class linking agent of described quality are mixed in proportion and stir, make oil mixture;
(2) preparation of aqueous mixture: take by weighing 2000g water, 100gTA (19% styrene-maleic anhydride copolymer sodium-salt aqueous solution, be purchased from Shanghai Leather Chemical Plant) and the 10g n-Octanol in 5L glass reaction still, stir and heating in water bath to 45 ℃, make aqueous mixture; To account for emulsion gross weight mark be 10.1% to oil mixture in the present embodiment;
(3) preparation of emulsion: the refiner cutting head is placed aqueous mixture, and regulating velocity of shear is 3000 rev/mins, and emulsification times formed evenly in 10 minutes;
(4) preparation of microcapsule: the temperature of O/W emulsion emulsion is risen to 68 ℃, and opening blade stirring adjusting stirring velocity is 300 rev/mins, reacts and finishes in 3 hours, makes phase-change material micro-capsule;
(5) preparation of low cold phase-change material micro-capsule: will obtain phase-change material micro-capsule and continue to be warmed up to 78 ℃ and kept 1 hour, and observe microcapsule suspensions and become gradually grey black, naturally cooling namely obtains low cold phase-change material micro-capsule.Stop to stir, cooling water circulation is to room temperature, and filtering separation behind the deionized water rinsing product of quality 1000g 3 times, is dried to constant weight in 50 ℃ of vacuum drying ovens, namely obtain phase-change material micro-capsule dry powder.
After testing, the median size of gained phase-change material micro-capsule is 15.2 μ m, 28.1 ℃ of endothermic temperatures (Tm), melting enthalpy (Δ Hm) 118.3J/g, 22.8 ℃ of exothermic temperatures (Tc3), crystallization heat content (Δ Hc3) 28.3J/g, 17.6 ℃ of exothermic temperatures (Tc2), crystallization heat content (Δ Hc2) 4.8J/g, 11.7 ℃ of exothermic temperatures (Tc1), crystallization heat content (Δ Hc1) 3.3J/g; 227 ℃ of heat decomposition temperatures (Td) (data of thermal weight loss 5%).
Embodiment 2
Microcapsule mass percent composition is designed to:
Capsule-core 263g, wherein organic phase change material 1-bromo eicosane 240g crosses cold inhibitor polypyrrole 15g, initiator Diisopropyl azodicarboxylate (AIBN) 1g, oxygenant benzoyl peroxide (BPO) 1g; Cyst wall 320g, wherein methacrylic acid phenylester and linking agent dimethacrylate TEG ester are respectively 300g and 20g.
The preparation method of microcapsule is:
(1) preparation of oil mixture: under 55 ℃ the temperature and under 500 rev/mins the stirring velocity, organic phase change material, the cold inhibitor monomer of mistake, initiator, oxygenant, alkyl methacrylate/aryl ester, the allyl ester class linking agent of described quality are mixed in proportion and stir, make oil mixture;
(2) preparation of aqueous mixture: take by weighing 1800g water, 150gTA (19% styrene-maleic anhydride copolymer sodium-salt aqueous solution, be purchased from Shanghai Leather Chemical Plant) and the 10g n-Octanol in 5L glass reaction still, stir and heating in water bath to 55 ℃, make aqueous mixture;
(3) preparation of emulsion: the refiner cutting head is placed aqueous mixture, and regulating velocity of shear is 8000 rev/mins, and emulsification times formed evenly in 10 minutes; To account for emulsion gross weight mark be 23% to oil mixture in the present embodiment;
(4) preparation of microcapsule: the temperature of O/W emulsion emulsion is risen to 65 ℃, and opening blade stirring adjusting stirring velocity is 400 rev/mins, reacts and finishes in 4 hours, makes phase-change material micro-capsule;
(5) preparation of low cold phase-change material micro-capsule: will obtain phase-change material micro-capsule and continue to be warmed up to 75 ℃ and kept 2 hours, and observe microcapsule suspensions and become gradually grey black, naturally cooling namely obtains low cold phase-change material micro-capsule.Stop to stir, cooling water circulation is to room temperature, and filtering separation behind the deionized water rinsing product of quality 1000g 3 times, is dried to constant weight in 50 ℃ of vacuum drying ovens, namely obtain phase-change material micro-capsule dry powder.
After testing, the median size of gained phase-change material micro-capsule is 3.2 μ m, 34.1 ℃ of endothermic temperatures (Tm), melting enthalpy (Δ Hm) 115J/g, 25.2 ℃ of exothermic temperatures (Tc3), crystallization heat content (Δ Hc3) 21.8J/g, 19.6 ℃ of exothermic temperatures (Tc2), crystallization heat content (Δ Hc2) 3.6J/g, 13.5 ℃ of exothermic temperatures (Tc1), crystallization heat content (Δ Hc1) 2.8J/g; 237 ℃ of heat decomposition temperatures (Td) (data of thermal weight loss 5%).
Adopt the processing condition identical with embodiment 1, only change pyrroles's content, obtain different low the cold phase-change material micro-capsule of polypyrrole content, its performance is as shown in table 1.The composition of embodiment 3～7 microcapsule is respectively:
Capsule-core 295.2g, wherein organic phase change material 280g crosses cold inhibitor 0g, initiator 1.2g, oxygenant 1.0g; Cyst wall 115g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 15g; To account for emulsion gross weight mark be 16% to oil mixture in the present embodiment;
Capsule-core 377.2g, wherein organic phase change material 360g crosses cold inhibitor 15g, initiator 1.2g, oxygenant 1.0g; Cyst wall 115g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 100g and 15g; To account for emulsion gross weight mark be 19% to oil mixture in the present embodiment;
Embodiment 5
Capsule-core 395.2g, wherein organic phase change material 360g crosses cold inhibitor 32g, initiator 1.2g, oxygenant 1.0g; Cyst wall 240g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 220g and 20g; To account for emulsion gross weight mark be 23.2% to oil mixture in the present embodiment;
Embodiment 6
Capsule-core 412.2g, wherein organic phase change material 360g crosses cold inhibitor 50g, initiator 1.2g, oxygenant 1.0g; Cyst wall 320g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 290g and 30g; To account for emulsion gross weight mark be 25.8% to oil mixture in the present embodiment;
Embodiment 7
Capsule-core 432.2g, wherein organic phase change material 400g crosses cold inhibitor 77g, initiator 1.2g, oxygenant 1.0g; Cyst wall 330g, wherein methyl methacrylate and linking agent allyl methacrylate(AMA) are respectively 300g and 30g; To account for emulsion gross weight mark be 27.7% to oil mixture in the present embodiment;
The different performance tables of crossing cold inhibitor polypyrrole phase-change material micro-capsule of table 1
Data can be found out from table 1, and along with the increase of crossing cold inhibitor, Δ Hc1, Δ Hc2 are reducing, and Δ Hc3 increases, but when crossing cold inhibitor and surpassing 10%, Δ Hc1, Δ Hc2 increase again gradually, and Δ Hc3 reduces; Along with the increase that oil mixture accounts for emulsion gross weight mark, can occur reuniting and caking phenomenon.
Embodiment 8
Capsule-core 263g, wherein organic phase change material n-butyl stearate 300g crosses cold inhibitor polypyrrole 15g, initiator Diisopropyl azodicarboxylate (AIBN) 1g, oxygenant benzoyl peroxide (BPO) 1g; Cyst wall 200g, wherein methacrylic acid butyl ester and linking agent dimethacrylate BDO ester are respectively 300g and 20g.
The preparation method of microcapsule is:
(1) preparation of oil mixture: under 40 ℃ the temperature and under 500 rev/mins the stirring velocity, organic phase change material, the cold inhibitor monomer of mistake, initiator, oxygenant, alkyl methacrylate/aryl ester, the allyl ester class linking agent of described quality are mixed in proportion and stir, make oil mixture;
(2) preparation of aqueous mixture: take by weighing 1800g water, 150gTA (19% styrene-maleic anhydride copolymer sodium-salt aqueous solution, Shanghai Leather Chemical Plant) and the 5g n-Octanol in 5L glass reaction still, stir and heating in water bath to 40 ℃, make aqueous mixture;
(3) preparation of emulsion: the refiner cutting head is placed aqueous mixture, and regulating velocity of shear is 5000 rev/mins, and emulsification times formed evenly in 20 minutes; To account for emulsion gross weight mark be 23% to oil mixture in the present embodiment;
(4) preparation of microcapsule: the temperature of O/W emulsion emulsion is risen to 66 ℃, and opening blade stirring adjusting stirring velocity is 300 rev/mins, reacts and finishes in 3.5 hours, makes phase-change material micro-capsule;
(5) preparation of low cold phase-change material micro-capsule: will obtain phase-change material micro-capsule and continue to be warmed up to 85 ℃ and kept 1 hour, and observe microcapsule suspensions and become gradually grey black, naturally cooling namely obtains low cold phase-change material micro-capsule.Stop to stir, cooling water circulation is to room temperature, and filtering separation behind the deionized water rinsing product of quality 1000g 3 times, is dried to constant weight in 50 ℃ of vacuum drying ovens.
After testing, the median size of gained phase-change material micro-capsule is 5.8 μ m, 23.1 ℃ of endothermic temperatures (Tm), melting enthalpy (Δ Hm) 69J/g, 13.1 ℃ of exothermic temperatures (Tc3), crystallization heat content (Δ Hc3) 34.8J/g, 8.9 ℃ of exothermic temperatures (Tc2), crystallization heat content (Δ Hc2) 4.6J/g, 3.5 ℃ of exothermic temperatures (Tc1), crystallization heat content (Δ Hc1) 29.8J/g; 227 ℃ of heat decomposition temperatures (Td) (data of thermal weight loss 5%).
The above; only be the better embodiment of the present invention; protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, the simple change of the technical scheme that can obtain apparently or equivalence are replaced and are all fallen within the scope of protection of the present invention.
Claims (5)
1. one kind low condensate depression phase-change material micro-capsule is characterized in that, its microcapsule are comprised of capsule-core and cyst wall two portions, count by weight percentage, and described capsule-core and cyst wall are respectively 30-85% and 15-70%, wherein:
The moiety of capsule-core and weight percentage thereof are: organic phase change material 83-99.7%, the cold inhibitor 0.1-16% of mistake, initiator 0.1-0.5%;
The moiety of cyst wall is: 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 refers to general formula C
nH
2n+2(n=12-32) the normal paraffin compounds of expression is with general formula C
nH
2n+2The halo normal paraffin compounds of X (n=12-32) expression and with general formula C
mH
2m+1COOCH
2CpH
2p+1(n=12-32, m=10-20, p=4-10) expression fatty acid ester in any 1～3 kind;
The cold inhibitor of described mistake refers to polypyrrole;
Described initiator refers to Diisopropyl azodicarboxylate;
Described oxygenant refers to benzoyl peroxide;
Described alkyl methacrylate/aryl ester refers to general formula:
Described allyl ester class linking agent refers to 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, at least a in 6-hexylene glycol ester, trihydroxy methyl propane trimethyl acrylate, neopentyl glycol dimethacrylate, the ethoxylation bisphenol a dimethacrylate.
3. the preparation method of the described low condensate depression phase-change material micro-capsule of claim 1 is characterized in that, comprises following steps:
(1) preparation of oil mixture:
With organic phase change material, cross cold inhibitor monomer, initiator, oxygenant, alkyl methacrylate/aryl ester, allyl ester class linking agent and mix, be heated to above melt temperature 10-20 ℃ of scope of organic phase change material in ratio claimed in claim 2, stirring makes it to dissolve fully and presents water white mixed solution;
(2) preparation of aqueous mixture:
Emulsifying agent and assistant for emulsifying agent are dispersed in water as water, and wherein the emulsifying agent solid content is 0.5-4%, and assistant for emulsifying agent accounts for 0.1-2% with the total weight of water;
(3) preparation of emulsion:
Shear with refiner, make oil phase be dispersed in aqueous phase and form the O/W emulsion, velocity of shear is 3000-8000 rev/min;
(4) preparation of microcapsule:
The O/W emulsion that step (3) obtains is transferred in the reactor, adopted the oar formula to stir, stirring velocity is 30-500 rev/min, and heating in water bath namely obtains phase-change material micro-capsule after reacting 3-4 hour under the 60-68 ℃ of temperature;
(5) preparation of low cold phase-change material micro-capsule:
Step (4) is obtained phase-change material micro-capsule continue to be warmed up to 75-85 ℃ of reaction after 1-2 hour, naturally cooling namely obtains low cold phase-change material micro-capsule.
4. the preparation method of low condensate depression phase-change material micro-capsule according to claim 3 is characterized in that, the described emulsifying agent of step (2) is styrene-maleic anhydride copolymer, and described assistant for emulsifying agent is n-Octanol.
5. the preparation method of low condensate depression phase-change material micro-capsule according to claim 3 is characterized in that, the described oil mixture of step (1) accounts for the 10-30% of the described emulsion gross weight of step (3).
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| CN101701146A (en) * | 2009-10-22 | 2010-05-05 | 天津工业大学 | Phase-change material microcapsule and preparation method thereof |
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Patent Citations (1)
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| CN110746938B (en) * | 2019-10-17 | 2021-05-11 | 东华大学 | Cellulose/polypyrrole supported composite phase change heat storage material and preparation method thereof |
| CN110746938A (en) * | 2019-10-17 | 2020-02-04 | 东华大学 | Cellulose/polypyrrole supported composite phase change heat storage material and preparation method thereof |
| CN111072958A (en) * | 2019-12-03 | 2020-04-28 | 天津圣工科技有限公司 | Polypyrrole/melamine resin double-shell structure microcapsule and preparation method thereof |
| 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 |
| CN113355056A (en) * | 2021-06-22 | 2021-09-07 | 广西民族大学 | Preparation method of photo-thermal phase change energy storage micro-nano super-hydrophobic anti-freezing particle material |
| 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 |
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