CN111253915A - Phase-change microcapsule and preparation method and application thereof - Google Patents
Phase-change microcapsule and preparation method and application thereof Download PDFInfo
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 30
- 239000012782 phase change material Substances 0.000 claims abstract description 24
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 19
- 239000000661 sodium alginate Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000001110 calcium chloride Substances 0.000 claims abstract description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000005684 electric field Effects 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 8
- 239000004566 building material Substances 0.000 claims abstract description 5
- 230000008859 change Effects 0.000 claims description 22
- 239000011258 core-shell material Substances 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- ZYURHZPYMFLWSH-UHFFFAOYSA-N octacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC ZYURHZPYMFLWSH-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 claims description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- JXTPJDDICSTXJX-UHFFFAOYSA-N triacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000012164 animal wax Substances 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000012180 soy wax Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 27
- 239000012792 core layer Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000005338 heat storage Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 230000006872 improvement Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/043—Drying and spraying
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the technical field of microcapsule preparation, and discloses a preparation method of a phase-change microcapsule, which takes a phase-change material as a core layer and sodium alginate as a shell layer, adopts a coaxial electrospray technique, and charged liquid drops are split into countless micro-nano-sized globules under the action of electric field force and are further mixed with CaCl2And (4) crosslinking to form the structurally-shaped phase-change microcapsule. The shell layer wraps the phase change material in the inner part, so that packaging is realized, and the problem of leakage is solved. The preparation method is simple, strong in operability, wide in raw material source, low in production cost and good in repeatability. The phase-change microcapsule prepared by the preparation method is controllable in size and uniform in size, can be used in the fields of energy-saving building materials, phase-change heat storage systems, functional fabrics and the like, and provides a new idea for development of phase-change heat storage materials.
Description
Technical Field
The invention belongs to the technical field of microcapsule preparation, and particularly relates to a phase change microcapsule as well as a preparation method and application thereof.
Background
The phase change material is a material with a heat storage function, absorbs or releases a large amount of heat through the change of a phase state, and the temperature of the phase change material is almost unchanged, so that the storage and the release of energy are realized, and the phase change material can be recycled. However, such materials have fluidity during phase transition and are prone to leakage, thus greatly limiting practical applications.
The microcapsule technology is a technology for encapsulating a core layer by using a shell layer to form particles with certain strength. The microcapsule size is usually 1-1000 μm, and in order to obtain the core-shell structure microcapsule, a proper core material and wall material need to be found. Microencapsulation techniques may encapsulate a phase change material as a core layer within a shell layer. Firstly, the wall material of the shell layer protects the phase-change material of the core layer, and the stability and the reusability of the phase-change material can be improved. Secondly, the wall material wraps the phase-change material, and the problem that the phase-change material is easy to leak is well solved. The phase-change microcapsule is applied to the fabric, so that the fabric can be endowed with the functions of energy storage and temperature regulation. In the 80 s of the 20 th century, the American aerospace agency finished phase-change microcapsules on fabric to prepare space suits, and the clothes can reduce the risk of astronauts in extremely cold environments.
However, in the preparation method of the phase-change microcapsule in the prior art, instruments and operation steps are complicated, and the size and the wrapping rate of the prepared phase-change microcapsule are uncontrollable, different in size, poor in repeatability and high in production cost.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the first purpose of the invention is to provide a preparation method of phase-change microcapsules, which takes phase-change materials as a core layer and sodium alginate as a shell layer, adopts a coaxial electrospray technique, and charged liquid drops are split into countless micro-nano-sized small balls under the action of electric field force and are further mixed with CaCl2And (4) crosslinking to form the structurally-shaped phase-change microcapsule.
The second purpose of the invention is to provide the phase change microcapsule with the core-shell structure prepared by the preparation method, wherein the latent heat value is 10-300J/g, and the coating rate is 10-70%.
The third purpose of the invention is to provide the application of the phase change microcapsule with the core-shell structure in the fields of energy-saving building materials, functional fabrics and the like.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of the phase-change microcapsule comprises the following steps:
1) taking a liquid phase-change material or a phase-change material dissolved by a first solvent as a nuclear layer solution, wherein the mass concentration of the phase-change material in the nuclear layer solution is 10-100%;
2) taking sodium alginate dissolved by the second solvent as a shell solution, wherein the mass volume concentration of the sodium alginate in the shell solution is 0.1-5 g/L;
3) with CaCl2The solution is used as a receiving substrate, the core layer solution obtained in the step 1) is connected with an inner layer solution channel of a coaxial electric spraying device by adopting a coaxial electric spraying technology, the shell layer solution obtained in the step 2) is connected with an outer layer solution channel of the coaxial electric spraying device, parameters are adjusted, coaxial electric spraying is carried out by utilizing high pressure, charged liquid drops are sprayed under the action of electric field force to form countless small drops which are deposited on CaCl2Drying the solution to obtain phase change microcapsules;
wherein, the parameters of the coaxial electrospray are as follows: the voltage is 5-30kV, the receiving distance is 5-25cm, the pushing speed of the nuclear layer solution is 0.01-5mL/h, and the pushing speed of the shell layer solution is 0.01-5 mL/h.
Coaxial electrospray is a novel nano packaging technology, and a method for preparing micro-nano particles or fibers by utilizing a charged hydrodynamic jet technology. The coaxial electric spraying device used in the technology mainly comprises a high-voltage power supply, a needle head and a receiving device. The nuclear layer solution and the shell layer solution are respectively filled into an injector, and flow out through a needle head at a certain speed under the driving of a micro-injection pump, and meet at a coaxial needle head nozzle. The pinhead is connected with the positive pole of a high-voltage power supply, the receiving device is connected with the negative pole, and a high-voltage electric field is formed between the pinhead and the receiving device, so that charged liquid drops are gradually stretched under the action of the electric field, the taylor cone is formed by stretching the balls at the pinhead, when electrostatic force is enough to overcome the surface tension of the liquid drops, the liquid drops are sprayed out to form small balls with micro-nano sizes, and finally, the small balls are solidified and deposited after treatment.
Meanwhile, sodium alginate is a natural linear anionic polysaccharide, and is formed by bonding β -D-mannuronic acid (M) and α -L-guluronic acid (G) through 1-4 glycosidic bonds.
As a further improvement of the above scheme, the phase change material is selected from one of paraffin, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane, n-tetracosane, n-hexacosane, n-octacosane, n-triacontane, polyethylene glycol monomethyl ether, stearic acid, oleic acid, lauric acid, oxalic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, octanol, lauryl alcohol, tetradecanol, cetyl alcohol, octadecanol, butanediol, hexanediol, glycerol, pentaerythritol, n-hexane, soy wax, vegetable oil or animal wax.
Further preferably, the phase-change material is paraffin, and has the advantages of low price, no toxicity, high enthalpy value, no supercooling phenomenon and adjustable phase-change temperature.
As a further improvement of the above, the CaCl is2The mass concentration of the solution is 10-60%.
As a further improvement of the scheme, the first solvent is one or two of kerosene, toluene, xylene, petroleum ether, carbon tetrachloride, chloroform, dichloromethane, tetrahydrofuran, n-pentane, n-hexane, n-octane, water and ethanol. Preferably kerosene, which has low price, no toxicity, easy obtainment and better solubility to paraffin.
A phase change microcapsule prepared according to the preparation method of any one of the above.
As a further improvement of the scheme, the phase change microcapsule is a paraffin @ sodium alginate core-shell structure phase change microcapsule.
As a further improvement of the scheme, the latent heat value of the phase-change microcapsule is 10-300J/g.
As a further improvement of the scheme, the particle size of the phase-change microcapsule is 0.1-100 μm.
As a further improvement of the scheme, the encapsulation rate of the phase change microcapsule is 10-70%. Preferably 30 to 70 percent.
Use of a phase change microcapsule according to any of the above in energy saving building materials and functional fabrics.
The invention has the beneficial effects that:
the invention takes phase-change material as a core layer, takes sodium alginate solution as a shell layer, adopts a coaxial electric spraying technology, charged liquid drops are split into countless micro-nano-sized globules under the action of electric field force, and the sodium alginate solution of the shell layer is further mixed with CaCl2Crosslinking to form the phase-change microcapsule with fixed structure, wherein α -L-guluronic acid (G) in the sodium alginate solution can react with Ca2+Bonding and gelating, wherein adjacent sodium alginate molecular chains are changed into an ordered belt structure from natural irregular curling to form the gel with the three-dimensional network structure. Ca2+And the cross-linking is carried out with the sodium alginate, which provides possibility for the sodium alginate as a wall material to wrap the phase-change material. Therefore, the shell layer wraps the phase change material inside, and the problem of leakage of the phase change material is solved. The preparation method is simple, strong in operability, wide in raw material source, low in production cost and good in repeatability.
The invention also provides the phase-change microcapsule prepared by the preparation method, the phase-change microcapsule has controllable size and uniform size, can be used in the fields of energy-saving building materials, functional fabrics and the like, and provides a new idea for the development of phase-change heat storage materials.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
Preparation of phase change microcapsule with paraffin @ sodium alginate core-shell structure
Adding paraffin into kerosene for dissolving to obtain a nuclear layer solution, wherein the mass concentration of the paraffin is 60%; dissolving sodium alginate in deionized water to obtain a shell solution, wherein the mass volume concentration of the sodium alginate is 1 g/L;
with CaCl2The solution is used as a receiving substrate, a coaxial electric spraying technology is adopted, the pushing speed of the nuclear layer solution is adjusted to be 0.05mL/h, the pushing speed of the shell layer solution is 0.1mL/h, the receiving distance is 15cm, the voltage is 10kV, high-voltage coaxial electric spraying is utilized, charged liquid drops are sprayed under the action of electric field force to form countless small liquid drops which are deposited on CaCl2And drying the solution to obtain the paraffin @ sodium alginate core-shell structure phase change microcapsule. The wrapping rate of the paraffin @ sodium alginate core-shell structure phase change microcapsule is 50%.
Example 2
Preparation of phase change microcapsule with paraffin @ sodium alginate core-shell structure
Adding paraffin into kerosene for dissolving to obtain a nuclear layer solution, wherein the mass concentration of the paraffin is 60%; dissolving sodium alginate in deionized water to obtain a shell solution, wherein the mass volume concentration of the sodium alginate is 1 g/L;
with CaCl2The solution is used as a receiving substrate, a coaxial electric spraying technology is adopted, the pushing speed of the nuclear layer solution is adjusted to be 0.5mL/h, the pushing speed of the shell layer solution is 2mL/h, the receiving distance is 15cm, the voltage is 15kV, high-voltage coaxial electric spraying is utilized, charged liquid drops are sprayed under the action of electric field force to form countless small drops which are deposited on CaCl2And drying the solution to obtain the paraffin @ sodium alginate core-shell structure phase change microcapsule. The wrapping rate of the paraffin @ sodium alginate core-shell structure phase change microcapsule is 30%.
Example 3
Preparation of phase change microcapsule with paraffin @ sodium alginate core-shell structure
Adding paraffin into kerosene for dissolving to obtain a nuclear layer solution, wherein the mass concentration of the paraffin is 60%; dissolving sodium alginate in deionized water to obtain a shell solution, wherein the mass volume concentration of the sodium alginate is 1 g/L;
with CaCl2The solution is used as a receiving substrate, a coaxial electric spraying technology is adopted, the pushing speed of the nuclear layer solution is adjusted to be 1mL/h, the pushing speed of the shell layer solution is adjusted to be 1.5mL/h, the receiving distance is 15cm, the voltage is 15kV, and high-voltage coaxial electric spraying is utilizedThe charged liquid drops are sprayed under the action of electric field force to form countless small liquid drops which are deposited on CaCl2And drying the solution to obtain the paraffin @ sodium alginate core-shell structure phase change microcapsule. The wrapping rate of the paraffin @ sodium alginate core-shell structure phase change microcapsule is 60%.
The coaxial electrospray device in the embodiments of the present invention was purchased from Beijing, New Rui Bai Nakou technology, Inc.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (10)
1. A preparation method of a phase-change microcapsule is characterized by comprising the following steps:
1) taking a liquid phase-change material or a phase-change material dissolved by a first solvent as a nuclear layer solution, wherein the mass concentration of the phase-change material in the nuclear layer solution is 10-100%;
2) taking sodium alginate dissolved by water as a shell solution, wherein the mass volume concentration of the sodium alginate in the shell solution is 0.1-5 g/L;
3) with CaCl2The solution is used as a receiving substrate, a coaxial electric spraying technology is adopted, parameters are adjusted, coaxial electric spraying is carried out by utilizing high pressure, charged liquid drops are sprayed under the action of electric field force to form countless small drops which are deposited on CaCl2Drying the solution to obtain phase change microcapsules;
wherein, the parameters of the coaxial electrospray are as follows: the voltage is 5-30kV, the receiving distance is 5-25cm, the pushing speed of the nuclear layer solution is 0.01-5mL/h, and the pushing speed of the shell layer solution is 0.01-5 mL/h.
2. The method according to claim 1, wherein the phase change material is one selected from paraffin, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane, n-tetracosane, n-hexacosane, n-octacosane, n-triacontane, polyethylene glycol monomethyl ether, stearic acid, oleic acid, lauric acid, oxalic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, octanol, lauryl alcohol, tetradecanol, hexadecanol, octadecanol, butanediol, hexanediol, glycerol, pentaerythritol, n-hexane, soy wax, vegetable oil, and animal wax.
3. The method of claim 1, wherein the CaCl is2The mass concentration of the solution is 10-60%.
4. The method according to claim 1, wherein the first solvent is one or two selected from kerosene, toluene, xylene, petroleum ether, carbon tetrachloride, chloroform, methylene chloride, tetrahydrofuran, n-pentane, n-hexane, n-octane, water, and ethanol.
5. A phase change microcapsule prepared by the process according to any of claims 1 to 4.
6. The phase-change microcapsule according to claim 5, wherein said phase-change microcapsule is a paraffin @ sodium alginate core-shell structure phase-change microcapsule.
7. The phase-change microcapsule according to claim 5, wherein said phase-change microcapsule has a latent heat value of 10 to 300J/g.
8. The phase-change microcapsule according to claim 5, wherein said phase-change microcapsule has a particle size of 0.1 μm to 100 μm.
9. The phase-change microcapsule according to claim 5, wherein said phase-change microcapsule has an encapsulation rate of 10% to 70%.
10. Use of the phase change microcapsules according to any of claims 5 to 9 in energy saving building materials or functional fabrics.
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| CN111839887A (en) * | 2020-08-19 | 2020-10-30 | 福建恒安集团有限公司 | Fragrant warm plaster |
| CN111887484A (en) * | 2020-08-05 | 2020-11-06 | 福建中烟工业有限责任公司 | Aerosol cooling element and application thereof |
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| CN102407088A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院化学研究所 | Preparation method for phase-change energy-storage microcapsule and phase-change energy-storage microcapsule |
| CN108570766A (en) * | 2018-03-16 | 2018-09-25 | 中国科学院广州能源研究所 | A method of preparing the phase-change thermal storage tunica fibrosa of nucleocapsid using coaxial electrostatic spinning technology |
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| CN102070895A (en) * | 2010-11-17 | 2011-05-25 | 无锡中科光远生物材料有限公司 | Core-shell microcapsule and preparation method thereof |
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| CN111887484A (en) * | 2020-08-05 | 2020-11-06 | 福建中烟工业有限责任公司 | Aerosol cooling element and application thereof |
| CN111887484B (en) * | 2020-08-05 | 2023-10-20 | 福建中烟工业有限责任公司 | Aerosol cooling element and application thereof |
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