CN112742316B - Preparation method of phase-change microcapsule material - Google Patents
Preparation method of phase-change microcapsule material Download PDFInfo
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- CN112742316B CN112742316B CN201911048921.4A CN201911048921A CN112742316B CN 112742316 B CN112742316 B CN 112742316B CN 201911048921 A CN201911048921 A CN 201911048921A CN 112742316 B CN112742316 B CN 112742316B
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 39
- 239000012071 phase Substances 0.000 claims abstract description 31
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019441 ethanol Nutrition 0.000 claims abstract description 25
- 239000012188 paraffin wax Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000005507 spraying Methods 0.000 claims abstract description 15
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000000084 colloidal system Substances 0.000 claims description 11
- -1 ethylene glycol dimethyl propylene ester Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000002775 capsule Substances 0.000 abstract description 15
- 239000003921 oil Substances 0.000 abstract description 10
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000012782 phase change material Substances 0.000 description 14
- 239000011162 core material Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 238000005338 heat storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- JAVJHSMUVDYTBF-UHFFFAOYSA-N [Si](=O)=O.C=CC1=CC=CC=C1 Chemical compound [Si](=O)=O.C=CC1=CC=CC=C1 JAVJHSMUVDYTBF-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Abstract
A preparation method of a phase-change microcapsule material comprises the following steps: (1) Dropwise adding ammonia water into an ethanol solution of tetraethoxysilane for reaction, and then dropwise adding gamma-methacryloxypropyl trimethoxysilane to obtain silica sol; mixing styrene, paraffin, methyl methacrylate, azodiisoheptanenitrile and ethylene glycol dimethacrylate to prepare an oil phase, dissolving an emulsifier in water to prepare an aqueous phase solution, mixing the two phases to obtain an emulsion, spraying silica sol into the emulsion, adding NaCl solution and absolute ethyl alcohol to demulsify, and washing to obtain the phase-change microcapsule material. The invention uses the silicon dioxide-polystyrene capsule wall material, improves the compressive strength and the flexural strength of the phase-change microcapsule, has higher phase-change latent heat, and has regular shape, good coating and high yield.
Description
Technical Field
The invention relates to a phase-change microcapsule material, in particular to a phase-change microcapsule taking paraffin as a phase-change material and silicon dioxide-styrene as a capsule wall, belonging to the field of building energy-saving materials.
Background
The phase change material has the heat storage function, can change phase along with the change of the ambient temperature, absorbs or releases heat in the phase change process, has the advantages of high heat storage density, large heat storage capacity, strong chemical stability, low cost and the like, can be used for improving the energy utilization efficiency and developing renewable energy sources, is widely applied in the fields of building energy conservation, industrial heat recovery, aerospace, solar energy utilization and the like, and is also widely paid attention to the fields of energy sources and material science. Phase change materials can change phase during phase change, particularly in liquid state, and are easy to flow and leak, so that the phase change materials are greatly limited in practical application process.
The phase change microcapsule is prepared by coating a phase change material by a film forming technology to prepare micron-sized solid small particles with a core-shell structure, the phase change material coated in the microcapsule is subjected to phase transition near the phase change temperature to generate a thermal effect, so that the effect of absorbing, storing or releasing heat is realized, after the phase change microcapsule is encapsulated, the capsule wall can isolate the external environment from the phase change material, the phase change material is effectively protected from being damaged, and the phase change microcapsule has the advantages of convenience in use, storage and transportation.
The phase-change microcapsule consists of two parts, namely a capsule wall and a capsule core, wherein the capsule core is made of a phase-change material, and common solid-liquid phase-change materials comprise straight-chain alkane, polyethylene glycol, crystalline hydrated salt, eutectic hydrated salt, paraffin, fatty acid and the like. The capsule wall is generally a high molecular polymer, and common polyamide, polyurea, urea-formaldehyde resin, melamine-formaldehyde resin, polyurethane or a composite system thereof are often selected. The phase change microcapsule is prepared through in-situ polymerization, interfacial polymerization, suspension polymerization, sulfurizing spraying, etc.
Patent CN1513938A discloses a microcapsule coated with phase-change material and a preparation method thereof, wherein the method uses direct-connection alkane, fatty alcohol and organic ester compound as core materials, and melamine-formaldehyde resin as wall materials to prepare the phase-change microcapsule material; patent CN101045857A discloses a phase-change energy-storage microcapsule material and a preparation method thereof, wherein paraffin is used as a core material, toluene diisocyanate and urea-formaldehyde resin are used as capsule wall materials, and an interfacial polymerization method and an in-situ polymerization method are adopted to prepare a double-layer microcapsule-encapsulated paraffin phase-change material; patent CN102827586a discloses a double-layer aromatic organic phase-change material microcapsule and a preparation method thereof, wherein n-hexane, n-hexadecane, n-octadecane or liquid paraffin is used as a core material, and urea-formaldehyde resin and beta-cyclodextrin are used as wall materials to prepare the phase-change microcapsule; in most of the reported methods, melamine resin, urea resin and phenolic resin are used as wall materials, and the residual formaldehyde in the capsule wall becomes necessary due to the influence of the materials, so that the problem of environmental pollution can be generated; in addition, the cost of the resin organic capsule wall material is high, the preparation process is complex, and the application in the building field is greatly limited.
According to data, when the phase-change microcapsule prepared by singly using the inorganic silica wall material is applied to building energy storage materials such as gypsum boards, wallboards and the like, the phase-change microcapsule is easy to break under the condition of large temperature change due to the fact that the simple silica wall material is brittle and the material is porous, poor in elasticity and toughness, the strength of the gypsum boards is also reduced, the using effect is influenced, and the application of the phase-change microcapsule is limited.
Disclosure of Invention
Aiming at the problems of high cost, easy breakage, complex preparation process, environmental pollution, low enthalpy saturation rate of products and the like of capsule wall materials in the production of phase-change microcapsules in the prior art, the invention provides a preparation method of the phase-change microcapsules, which takes paraffin as a phase-change material and silicon dioxide-styrene as a capsule wall material and adopts a chemical deposition method to prepare the phase-change microcapsules.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a phase-change microcapsule material comprises the following steps:
(1) Preparation of silica sol: dropwise adding ammonia water into an ethanol solution of tetraethoxysilane, reacting, dropwise adding gamma-methacryloxypropyl trimethoxysilane, continuously reacting, and cooling;
(2) Emulsion preparation: mixing styrene, paraffin, methyl methacrylate, azodiisoheptonitrile and ethylene glycol dimethyl propylene ester to prepare an oil phase, dissolving an emulsifier in water to prepare an aqueous solution, mixing the two solutions, and fully emulsifying to obtain an emulsion;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the emulsion prepared in the step (2) to replace air, controlling the refrigerating reflux condition, spraying the silica sol prepared in the step (1) to react, and then cooling;
(4) Post-treatment: adding NaCl solution and absolute ethyl alcohol into the product of the step (3) to demulsify, washing for a plurality of times, removing the paraffin which is not wrapped, and obtaining the phase-change microcapsule material after suction filtration and drying.
Further, in the ethanol solution of the ethyl orthosilicate in the step (1), the mass percentage concentration of the ethyl orthosilicate is 25% -40%;
further, the mass concentration of the ammonia water in the step (1) is 25% -28%, the dropping amount of the ammonia water is 1% -3% of the ethanol solution of the ethyl orthosilicate by mass, the reaction time of the ethanol solution of the ethyl orthosilicate and the ammonia water is 20-60 min, the reaction temperature is 50-70 ℃, and the stirring revolution of the solution in the dropping process is 200-300 r/min;
further, in the step (1), the dropping amount of the gamma-methacryloxypropyl trimethoxysilane is 0.2-0.5% of the ethanol solution of the tetraethoxysilane by mass, the continuous reaction time is 3-6 hours, the reaction temperature is 50-70 ℃, and the stirring revolution is 200-300 r/min.
Further, the emulsifier in the step (2) is a mixture of sodium dodecyl sulfate and octyl phenol polyoxyethylene ether, the dosage of the emulsifier is 1-3% of the total weight of the emulsion, and the dosage ratio of the two emulsifiers is 1:1-1:3 by weight.
Further, the addition amount of the paraffin wax in the step (2) is 10% -15% of the total weight of the emulsion; the addition amount of the styrene is 10% -15% of the total weight of the emulsion; the adding amount of the methyl methacrylate is 0.5-1% of the total weight of the emulsion; the addition amount of the azodiisoheptonitrile is 0.05-0.1% of the total weight of the emulsion; the addition amount of the ethylene glycol dimethyl propylene ester is 0.05-0.1% of the total weight of the emulsion.
Further, the temperature of the water phase solution prepared in the step (2) is 35-55 ℃, and the temperature of the oil phase solution prepared is 5-20 ℃ higher than the melting temperature of paraffin.
Further, the emulsification in the step (2) is performed in a colloid mill, wherein the diameter of a millstone of the colloid mill is 50-80 mm, the emulsification fineness is 2-40 mu m, and the revolution is 1700-3500 r/min.
Further, the nitrogen gas is introduced in the step (3) for 15-30 min.
Further, the spraying amount of the silica sol in the step (3) is 1% -5% of the total mass of the emulsion; the silica sol is sprayed and added by an atomizing nozzle, and atomized liquid drops fall into a circular surface formed by the emulsion to have the diameter of 3-6 cm.
Further, the reaction temperature after spraying the silica sol in the step (3) is 40-60 ℃, the stirring revolution is 250-350 r/min, and the reaction time is 4-6 h;
further, in the step (4), the mass concentration of the NaCl solution is 10-15%, and the dosage is 10-15% of the total product; the ethanol consumption is 10% -15% of the total product;
further, the solution used in the washing in the step (4) is petroleum ether and water, the washing temperature is 30-40 ℃, and the washing times are 3-5 times;
further, the temperature of the drying in the step (4) is 40-60 ℃ and the time is 40-50 hours.
Compared with the prior art, the invention has the following advantages:
(1) The silica-polystyrene capsule wall material is used, so that the combination capability of the phase-change microcapsule and the building material is improved, the elasticity and toughness of the capsule wall are enhanced, and the mechanical strength of the building material is improved; by using proper emulsifying agent and proportion thereof, the core paraffin can be better dispersed in the water phase to form stable oil-in-water emulsion, so that the product has higher phase change enthalpy value, and the enthalpy value saturation rate of the product is improved.
(2) The emulsion is carried out by using a colloid mill, so that the oil-in-water emulsion has more uniform drop size and better dispersion; the atomizing nozzle is used for spraying and adding the silica sol, the silica sol is dispersed into tiny liquid drops in advance, and then the tiny liquid drops are dripped into the position where turbulent flow is the most rapid contact in the emulsion, so that the silica sol can be more uniformly and firmly adsorbed on the surface of the oil liquid drop in water to carry out chemical reaction, a uniform capsule wall structure is formed, the microcapsule wall is not easy to break, and the product yield is higher.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an electron microscope scan of the phase change microcapsules prepared in example 2;
fig. 2 is a graph showing the experimental results of water contact angle of the phase-change microcapsules prepared in example 2.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless otherwise specified, the following examples and comparative examples are given in% by mass. The core paraffin is No. 25 paraffin, provided by Dalian petrochemical institute, the phase transition temperature is 25 ℃, and the phase transition enthalpy value is 148KJ/kg.
Example 1
Preparation of phase-change microcapsules:
(1) Preparation of silica sol: 100g of ethyl orthosilicate is dissolved in 300mL of ethanol solution, 27g of ammonia water with the mass concentration of 26% is weighed and added into the ethanol solution of the ethyl orthosilicate for reaction for 30min, the reaction temperature is 50 ℃, and the stirring revolution is 200r/min; after the reaction, 1.4g of gamma-methacryloxypropyl trimethoxy silane was added, the reaction was continued for 3 hours at 60℃and the stirring speed was 250r/min, and the mixture was cooled for use.
(2) Emulsion preparation: 34g of styrene, 50g of paraffin, 3g of methyl methacrylate, 0.3g of azobisisoheptonitrile and 0.2g of ethylene glycol dimethyl propylene ester are mixed at 50 ℃ to prepare an oil phase, 2.5g of sodium dodecyl sulfate and 3.0g of octyl phenol polyoxyethylene ether are dissolved in 300mL of water to prepare an aqueous phase solution, the temperature is raised to 45 ℃, the two solutions are mixed, and the two solutions are fully emulsified for 2 minutes by using a colloid mill to obtain an emulsion and are put into a reactor;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the reactor for 20min, controlling cold reflux conditions, spraying and adding the silica sol prepared in the step (1) into the reactor for reaction, wherein the reaction temperature is 45 ℃, the stirring revolution is 300r/min, the reaction time is 6h, and then cooling;
(4) Post-treatment: adding 100g of NaCl solution with 15% concentration and 80g of absolute ethyl alcohol into a reactor, stirring, filtering, respectively washing with petroleum ether and deionized water for 3 times, wherein the washing temperature is 35 ℃, and drying for 50 hours at 45 ℃ after suction filtration to obtain the phase-change microcapsule material.
Example 2
Preparation of phase-change microcapsules:
(1) Preparation of silica sol: dissolving 110g of ethyl orthosilicate in 300mL of ethanol solution, weighing 30g of ammonia water with the mass concentration of 26% and dropwise adding the ammonia water into the ethanol solution of the ethyl orthosilicate for reaction for 30min at the temperature of 45 ℃ and stirring for 200r/min; after the reaction, 1.2g of gamma-methacryloxypropyl trimethoxy silane was added, the reaction was continued for 4 hours at 60℃with stirring at 250r/min and cooled for use.
(2) Emulsion preparation: mixing 35g of styrene, 55g of paraffin, 3g of methyl methacrylate, 0.3g of azodiisoheptanenitrile and 0.15g of ethylene glycol dimethyl propylene ester at 50 ℃ to prepare an oil phase, dissolving 2.8g of sodium dodecyl sulfate and 3.2g of octyl phenol polyoxyethylene ether in 300mL of water to prepare an aqueous phase solution, heating to 45 ℃, mixing the two solutions, fully emulsifying for 1 minute by using a colloid mill to obtain an emulsion, and putting the emulsion into a reactor;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the reactor for 20min, controlling cold reflux conditions, spraying and adding the silica sol prepared in the step (1) into the reactor for reaction, wherein the reaction temperature is 45 ℃, the stirring revolution is 300r/min, the reaction time is 5h, and then cooling;
(4) Post-treatment: adding 100g of NaCl solution with 15% concentration and 80g of absolute ethyl alcohol into a reactor, stirring, filtering, respectively washing with petroleum ether and deionized water for 3 times, wherein the washing temperature is 35 ℃, and drying for 50 hours at 45 ℃ after suction filtration to obtain the phase-change microcapsule material.
And scanning the prepared phase-change microcapsule by an electron microscope, and the result shows that the prepared phase-change microcapsule is well-packed, complete in appearance and free from breakage, as shown in figure 1.
And carrying out contact angle experiments on the prepared phase-change microcapsule: the dried phase-change microcapsule powder is pressed into tablets and tested on an SDC-100 type water contact angle measuring instrument, the smaller the contact angle is, the better the wettability is, the better the affinity with water is, and the test result shows that the contact angle is 20.9 degrees and 21.1 degrees, and the phase-change microcapsule has better hydrophilic performance, and the result is shown in figure 2.
Example 3
Preparation of phase-change microcapsules:
(1) Preparation of silica sol: 100g of ethyl orthosilicate is dissolved in 300mL of ethanol solution, 30g of ammonia water with the mass concentration of 25% is weighed and added into the ethanol solution of the ethyl orthosilicate for reaction for 30min, the reaction temperature is 50 ℃, and the stirring revolution is 250r/min; after the reaction, 1.1g of gamma-methacryloxypropyl trimethoxy silane was added, the reaction was continued for 3 hours at 60℃and the stirring speed was 250r/min, and the mixture was cooled for use.
(2) Emulsion preparation: 30g of styrene, 58g of paraffin, 3g of methyl methacrylate, 0.33g of azobisisoheptonitrile and 0.24g of ethylene glycol dimethyl propylene ester are mixed at 50 ℃ to prepare an oil phase, 2.5g of sodium dodecyl sulfate and 3.5g of octyl phenol polyoxyethylene ether are dissolved in 300mL of water to prepare an aqueous phase solution, the temperature is raised to 45 ℃, the two solutions are mixed, and the two solutions are fully emulsified for 2 minutes by using a colloid mill to obtain an emulsion and are put into a reactor;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the reactor for 20min, controlling cold reflux conditions, spraying and adding the silica sol prepared in the step (1) into the reactor for reaction, wherein the reaction temperature is 50 ℃, the stirring revolution is 300r/min, the reaction time is 6h, and then cooling;
(4) Post-treatment: adding 100g of NaCl solution with 15% concentration and 80g of absolute ethyl alcohol into a reactor, stirring, filtering, respectively washing with petroleum ether and deionized water for 3 times, wherein the washing temperature is 35 ℃, and drying for 50 hours at 45 ℃ after suction filtration to obtain the phase-change microcapsule material.
Example 4
Preparation of phase-change microcapsules:
(1) Preparation of silica sol: dissolving 110g of ethyl orthosilicate in 300mL of ethanol solution, weighing 27g of 28% ammonia water by mass concentration, dropwise adding the ammonia water into the ethanol solution of the ethyl orthosilicate for reaction for 30min at 50 ℃ with stirring revolution of 200r/min; after the reaction, 1.5g of gamma-methacryloxypropyl trimethoxy silane was added, the reaction was continued for 3 hours at 60℃and the stirring speed was 250r/min, and the mixture was cooled for use.
(2) Emulsion preparation: 34g of styrene, 50g of paraffin, 3g of methyl methacrylate, 0.3g of azobisisoheptonitrile and 0.2g of ethylene glycol dimethyl propylene ester are mixed at 50 ℃ to prepare an oil phase, 2.5g of sodium dodecyl sulfate and 3.0g of octyl phenol polyoxyethylene ether are dissolved in 300mL of water to prepare an aqueous phase solution, the temperature is raised to 45 ℃, the two solutions are mixed, and the two solutions are fully emulsified for 2 minutes by using a colloid mill to obtain an emulsion and are put into a reactor;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the reactor for 20min, controlling cold reflux conditions, spraying and adding the silica sol prepared in the step (1) into the reactor for reaction, wherein the reaction temperature is 50 ℃, the stirring revolution is 300r/min, the reaction time is 6h, and then cooling;
(4) Post-treatment: adding 100g of NaCl solution with 15% concentration and 80g of absolute ethyl alcohol into a reactor, stirring, filtering, respectively washing with petroleum ether and deionized water for 3 times, wherein the washing temperature is 35 ℃, and drying for 50 hours at 45 ℃ after suction filtration to obtain the phase-change microcapsule material.
Example 5
Preparation of phase-change microcapsules:
(1) Preparation of silica sol: 100g of ethyl orthosilicate is dissolved in 300mL of ethanol solution, 27g of ammonia water with the mass concentration of 27% is weighed and added into the ethanol solution of the ethyl orthosilicate for reaction for 30min, the reaction temperature is 50 ℃, and the stirring revolution is 200r/min; after the reaction, 1.6g of gamma-methacryloxypropyl trimethoxy silane was added, the reaction was continued for 3 hours at 60℃and the stirring speed was 250r/min, and the mixture was cooled for use.
(2) Emulsion preparation: 34g of styrene, 50g of paraffin, 3g of methyl methacrylate, 0.35g of azobisisoheptonitrile and 0.25g of ethylene glycol dimethyl propylene ester are mixed at 50 ℃ to prepare an oil phase, 3.0g of sodium dodecyl sulfate and 4.0g of octyl phenol polyoxyethylene ether are dissolved in 300mL of water to prepare an aqueous phase solution, the temperature is raised to 45 ℃, the two solutions are mixed, and the two solutions are fully emulsified for 3 minutes by using a colloid mill to obtain an emulsion and are put into a reactor;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the reactor for 20min, controlling cold reflux conditions, spraying and adding the silica sol prepared in the step (1) into the reactor for reaction, wherein the reaction temperature is 55 ℃, the stirring revolution is 300r/min, the reaction time is 5h, and then cooling;
(4) Post-treatment: adding 100g of NaCl solution with 15% concentration and 80g of absolute ethyl alcohol into a reactor, stirring, filtering, respectively washing with petroleum ether and deionized water for 3 times, wherein the washing temperature is 35 ℃, and drying for 50 hours at 45 ℃ after suction filtration to obtain the phase-change microcapsule material.
Example 6
Preparation of phase-change microcapsules:
(1) Preparation of silica sol: dissolving 110g of ethyl orthosilicate in 300mL of ethanol solution, weighing 27g of ammonia water with the mass concentration of 26% and dropwise adding the ammonia water into the ethanol solution of the ethyl orthosilicate for reaction for 30min at 50 ℃ with stirring revolution of 200r/min; after the reaction, 1.6g of gamma-methacryloxypropyl trimethoxy silane was added, the reaction was continued for 3 hours at 60℃and the stirring speed was 250r/min, and the mixture was cooled for use.
(2) Emulsion preparation: 34g of styrene, 50g of paraffin, 3g of methyl methacrylate, 0.3g of azobisisoheptonitrile and 0.2g of ethylene glycol dimethyl propylene ester are mixed at 50 ℃ to prepare an oil phase, 2.5g of sodium dodecyl sulfate and 3.0g of octyl phenol polyoxyethylene ether are dissolved in 300mL of water to prepare an aqueous phase solution, the temperature is raised to 45 ℃, the two solutions are mixed, and the two solutions are fully emulsified for 2 minutes by using a colloid mill to obtain an emulsion and are put into a reactor;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the reactor for 20min, controlling cold reflux conditions, spraying and adding the silica sol prepared in the step (1) into the reactor for reaction, wherein the reaction temperature is 55 ℃, the stirring revolution is 300r/min, the reaction time is 6h, and then cooling;
(4) Post-treatment: adding 100g of NaCl solution with 15% concentration and 80g of absolute ethyl alcohol into a reactor, stirring, filtering, respectively washing with petroleum ether and deionized water for 3 times, wherein the washing temperature is 35 ℃, and drying for 50 hours at 45 ℃ after suction filtration to obtain the phase-change microcapsule material.
Performance analysis of phase change microcapsules:
(1) Analyzing DSC enthalpy values of the phase-change microcapsules prepared in the examples 1-6, wherein the enthalpy values are tested on an HS-DSC-101 type differential scanning calorimeter by using a differential scanning calorimeter, and then calculating the enthalpy value saturation rate of the phase-change microcapsules, wherein the higher the enthalpy value saturation rate is, the better the heat preservation and constant temperature effects of the product are shown; the results are shown in Table 1.
(2) Mixing phase-change microcapsules with gypsum powder: weighing 300g of gypsum powder, dissolving 15g of phase-change microcapsule in 180g of water, dispersing for 3 minutes by microwave vibration, pouring into the gypsum powder, fully stirring and mixing for 50 seconds to obtain a blending material, testing the setting time of the blending material, drying the prepared gypsum board to constant weight at 45 ℃, and testing the compressive strength and the flexural strength of the gypsum board. In contrast to gypsum without phase change microcapsules. Wherein the water-paste ratio refers to the weight ratio of water to solid at which the product reached the same degree of flow, and the results are shown in Table 1.
TABLE 1
Enthalpy saturation = phase change microcapsule enthalpy/core paraffin enthalpy).
Claims (8)
1. A preparation method of a phase-change microcapsule material comprises the following steps:
(1) Preparation of silica sol: dropwise adding ammonia water into an ethanol solution of tetraethoxysilane, reacting, dropwise adding gamma-methacryloxypropyl trimethoxysilane, continuously reacting, and cooling;
(2) Emulsion preparation: mixing styrene, paraffin, methyl methacrylate, azodiisoheptonitrile and ethylene glycol dimethyl propylene ester to prepare an oil phase, dissolving an emulsifier in water to prepare an aqueous solution, mixing the two solutions, and fully emulsifying to obtain an emulsion; the emulsification is carried out in a colloid mill, the diameter of a millstone of the colloid mill is 50-80 mm, the emulsification fineness is 2-40 mu m, and the revolution is 1700-3500 r/min; the emulsifier is a mixture of sodium dodecyl sulfate and octyl phenol polyoxyethylene ether, wherein the weight ratio of the sodium dodecyl sulfate to the octyl phenol polyoxyethylene ether is 1:1-1:3, the weight of the emulsifier is 1-3% of the total weight of the emulsion, and the addition of the paraffin is 10-15% of the total weight of the emulsion; the addition amount of the styrene is 10% -15% of the total weight of the emulsion; the adding amount of the methyl methacrylate is 0.5-1% of the total weight of the emulsion; the addition amount of the azodiisoheptonitrile is 0.05-0.1% of the total weight of the emulsion; the addition amount of the ethylene glycol dimethyl propylene ester is 0.05-0.1% of the total weight of the emulsion; the temperature for preparing the aqueous phase solution is 35-55 ℃, and the temperature for preparing the oil phase solution is 5-20 ℃ higher than the melting temperature of paraffin;
(3) And (3) phase-change microcapsule forming: introducing nitrogen into the emulsion prepared in the step (2) to replace air, controlling the refrigerating reflux condition, spraying the silica sol prepared in the step (1) to react, and then cooling; the spraying amount of the silica sol is 1% -5% of the total mass of the emulsion; the silica sol is sprayed and added by an atomizing nozzle, and atomized liquid drops fall into a circular surface formed by the emulsion to have a diameter of 3-6 cm;
(4) Post-treatment: adding NaCl solution and absolute ethyl alcohol into the product of the step (3) to demulsify, washing for a plurality of times, removing the paraffin which is not wrapped, and obtaining the phase-change microcapsule material after suction filtration and drying.
2. The preparation method according to claim 1, wherein the ethyl orthosilicate in the ethanol solution of the ethyl orthosilicate in the step (1) has a mass percentage concentration of 25% -40%.
3. The method according to claim 1, wherein the ammonia water in the step (1) has a mass concentration of 25 to 28% and a dropping amount of 1 to 3% by mass of the ethyl orthosilicate in the ethanol solution.
4. The process according to claim 1, wherein the reaction time of the ethyl orthosilicate in the ethanol solution and the aqueous ammonia in the step (1) is 20 to 60 minutes and the reaction temperature is 50 to 70 ℃.
5. The method according to claim 1, wherein the amount of the gamma-methacryloxypropyl trimethoxysilane dropped in the step (1) is 0.2 to 0.5% by mass of the ethanol solution of ethyl orthosilicate.
6. The preparation method according to claim 1, wherein the reaction is continued for 3 to 6 hours after the gamma-methacryloxypropyl trimethoxysilane is added in step (1), and the reaction temperature is 50 to 70 ℃.
7. The process according to claim 1, wherein the reaction temperature after spraying the silica sol in step (3) is 40 to 60 ℃.
8. The preparation method according to claim 1, wherein the mass concentration of the NaCl solution in the step (4) is 10% -15%, and the dosage is 10% -15% of the total amount of the product; the ethanol consumption is 10% -15% of the total product.
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