CN111359554A - Large-particle-size polyurethane phase change microcapsule and preparation method thereof - Google Patents
Large-particle-size polyurethane phase change microcapsule and preparation method thereof Download PDFInfo
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 71
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 230000008859 change Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- 239000012782 phase change material Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
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- 238000000967 suction filtration Methods 0.000 claims abstract description 7
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- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
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- 150000003077 polyols Chemical class 0.000 claims description 3
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- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 5
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- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920002396 Polyurea Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000383 hazardous chemical Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003226 polyurethane urea Polymers 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 231100000206 health hazard Toxicity 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000162 poly(ureaurethane) Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 238000010792 warming Methods 0.000 description 1
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- 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
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- 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
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a large-particle-size polyurethane phase change microcapsule and a preparation method thereof. The method comprises the steps of firstly, reacting diisocyanate with dihydric alcohol to prepare a polyurethane prepolymer, then adding a phase-change material and uniformly stirring to obtain an oil phase; preparing nano titanium dioxide aqueous dispersion, and adding water-soluble polyhydric alcohol to obtain a water phase; and finally, dropwise adding the prepared oil phase into the water phase under the stirring action to form Pickering emulsion, carrying out condensation polymerization reaction at the interface of the Pickering emulsion to form the polyurethane phase-change microcapsule, and after the reaction is finished, carrying out suction filtration, washing with distilled water and drying to obtain the polyurethane phase-change microcapsule solid powder. The preparation method of the invention does not need high-speed shearing emulsification, does not need emulsifier, has controllable reaction rate, and the prepared phase-change microcapsule has the average grain diameter of more than 100 mu m, good thermal stability, good compactness, good mechanical strength and higher enthalpy.
Description
Technical Field
The invention belongs to the field of phase change microcapsules, and particularly relates to a large-particle-size polyurethane phase change microcapsule and a preparation method thereof.
Background
In recent years, environmental problems such as haze, global warming, and ocean acidification have become increasingly serious due to the continuous consumption of fossil fuels. Even more alarming is that fossil fuel resources are limited and non-renewable. Therefore, researchers have been working on the efficient use of clean and sustainable energy. In particular, to overcome the intermittent nature of most renewable energy sources, energy storage techniques have received great attention, such as the successful implementation of thermal energy storage using phase change materials as working media.
Phase change materials are a new type of energy storage material that have the ability to absorb or release large amounts of latent heat in the vicinity of its melting point as the ambient temperature increases or decreases, and therefore are receiving increasing attention. However, in practical applications, if pure phase change materials are directly used, there are defects such as loss and corrosion of the phase change materials, and poor compatibility of the phase change materials with the matrix materials, which greatly limits the application of the phase change materials. Especially when phase change occurs, handling of the liquid phase change material is also difficult. In order to expand the application field of phase change materials, a microencapsulated phase change material technology has been established and developed, which can separate the phase change material in a flowing state or a solid state from the surrounding environment.
Most of wall materials for preparing the phase-change microcapsule at present are melamine-formaldehyde resin, urea resin, polymethyl methacrylate and polyurea. However, because the melamine-formaldehyde resin and the urea-formaldehyde resin contain free formaldehyde, and the polymethyl methacrylate contains unreacted acrylate monomers, the existence of the substances can bring about the problems of environmental and health hazards and the like, and the application of the substances is greatly limited. The phase-change microcapsule taking polyurea and polyurethane-urea as wall materials does not have the problem of free formaldehyde, and the environmental protection property of the phase-change microcapsule is paid more and more attention.
Chinese patent application CN107903877A discloses a preparation method of polyurea resin phase change microcapsules, wherein an interfacial polymerization method is adopted to prepare the polyurea phase change microcapsules, and the thermal stability of the prepared microcapsules is improved.
Chinese patent application CN110215885A discloses a "preparation method of kaolinite polyurea phase-change microcapsule", which uses kaolinite as a stabilizer of Pickering emulsion, and utilizes the condensation polymerization reaction of IPDI and water at the interface of Pickering emulsion to coat paraffin to obtain a kaolinite polyurea phase-change microcapsule, but the prepared microcapsule can only bear the centrifugal washing at 4000 rpm, and the mechanical strength is poor.
Chinese patent application CN109126653A discloses a method for preparing a phase-change microcapsule with polyurethane as a wall material, which adopts a self-emulsifying method to coat a phase-change material with polyurethaneurea as a wall material, so as to prepare an ionic polyurethaneurea phase-change microcapsule with relatively high enthalpy, but the wall material is ionic polyurethane.
However, the current methods have the following disadvantages:
(1) when polyurea/polyurethane urea is used as a wall material to prepare the microcapsule, the reaction rate of diamine monomer and isocyanate group is extremely fast and is not easy to control, the obtained microcapsule has poor compactness, and the core material is easy to leak; the polyurea microcapsule has brittle wall material and poor mechanical strength.
(2) When the ionic polyurethane is used as a wall material, although no emulsifier is used in the preparation process, hydrophilic anionic or cationic groups exist in a molecular chain, so that the washing and purification of the microcapsule are difficult, and the prepared microcapsule has poor acid-base resistance and electrolyte resistance.
(3) The phase-change microcapsules prepared by the patent application have the advantages that the particle size is smaller than 100 mu m, the microcapsule wall is thin, and the thermal stability and the compactness are poor.
It was found that during the expansion/contraction process of the phase change cycle, the core material loss of microcapsules of smaller particle size (particle size <100 μm) is more severe at high temperature than that of microcapsules of larger particle size. However, conventional interfacial polymerization techniques have certain limitations in increasing microcapsule wall thickness and diameter due to emulsion instability, but these limitations depend on the preparation conditions.
Disclosure of Invention
The invention aims to provide a polyurethane phase change microcapsule with large particle size and a preparation method thereof aiming at the defects of the prior art. And (3) combining prepolymerization with Pickering emulsion polymerization to prepare the large-particle-size polyurethane phase-change microcapsule with the average particle size of more than 100 mu m. The preparation method is simple, the conditions are mild, the obtained large-particle-size polyurethane phase-change microcapsule is environment-friendly, and the mechanical strength of the product is excellent.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a large-particle-size polyurethane phase change microcapsule comprises the following steps:
(1) synthesizing a polyurethane prepolymer by using diisocyanate and dihydric alcohol as raw materials, adding a phase-change material, and uniformly stirring to obtain an oil phase;
(2) preparing aqueous dispersion containing nano titanium dioxide, and adding water-soluble polyhydric alcohol to obtain a water phase;
(3) dropwise adding the oil phase prepared in the step (1) into the water phase prepared in the step (2) under stirring to form Pickering emulsion, and carrying out condensation polymerization reaction at the interface of the Pickering emulsion to obtain a polyurethane phase-change microcapsule;
(4) and after the reaction is finished, carrying out suction filtration, washing and drying to obtain polyurethane phase change microcapsule solid powder.
Preferably, the dihydric alcohol is one or a mixture of more than two of polyethylene glycol, polytetrahydrofuran and polypropylene glycol.
More preferably, the molecular weight of the polyethylene glycol is 400-1000; the molecular weight of the polytetrahydrofuran is 650-1000; the molecular weight of the polypropylene glycol is 400-1000.
Preferably, the amount of the diol is 11 to 22 percent of the molar amount of the diisocyanate.
Preferably, the water-soluble polyhydric alcohol is one or a mixture of more than two of trimethylolpropane, glycerol, pentaerythritol and triethanolamine.
Preferably, the aqueous dispersion containing nano titanium dioxide is one of rutile type nano titanium dioxide, anatase type nano titanium dioxide and nano titanium dioxide aqueous dispersion.
Preferably, in the water phase in the step (2), the mass ratio of the water, the water-soluble polyol and the nano titanium dioxide is 100:0.5-5: 0.06-10.
Preferably, the stirring rate in step (3) is 250-400 rpm.
Preferably, the condensation polymerization reaction in the step (3) is carried out at the temperature of 50-70 ℃ for 2-4 h.
The polyurethane phase change microcapsule with large particle size prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phase-change microcapsule prepared by the invention has large grain diameter, and the average grain diameter is more than 100 mu m.
(2) The phase-change microcapsule prepared by the invention adopts the interfacial polymerization coating phase-change material between the polyurethane prepolymer and the water-soluble polyol, the content of the isocyanic acid radical of the prepolymer is lower than that of an isocyanate monomer, the reaction intensity is greatly reduced, and the side reaction between the isocyanic acid radical and water is also reduced, so that the wall material structure of the generated microcapsule is more ordered and more compact, and the preparation of the phase-change microcapsule with better thermal stability is facilitated.
(3) The dihydric alcohol adopted by the invention has larger molecular weight, and the phase change microcapsule with certain elasticity and excellent mechanical strength of the shell material can be prepared; the phase-change microcapsule prepared by the invention does not need high-speed shearing emulsification, and the preparation process of the phase-change microcapsule is optimized.
(4) The phase change microcapsule prepared by the invention does not contain free formaldehyde, and does not have environmental and health hazards. In addition, the invention does not need emulsifier, thus being more environment-friendly; the nanometer titanium dioxide is used as a stabilizer to prepare the nanometer titanium dioxide-polyurethane composite wall material microcapsule, and the prepared phase change microcapsule has organic-inorganic characteristics, so that the wall material of the microcapsule has better heat conductivity and is beneficial to heat exchange.
Drawings
FIG. 1 is an optical microscope photograph of the phase-change polyurethane microcapsule with large particle size obtained in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the polyurethane phase change microcapsule with large particle size obtained in example 1.
FIG. 3 is a distribution diagram of the particle size of the polyurethane phase-change microcapsules with large particle size obtained in example 1.
FIG. 4 is a thermogravimetric plot of the large-particle-size polyurethane phase-change microcapsules and phase-change materials obtained in example 1.
Detailed Description
The following further describes embodiments of the present invention with reference to the examples and the drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a large-particle-size polyurethane phase change microcapsule comprises the following steps:
(1) 25.00g of isophorone diisocyanate and 5.00g of polyethylene glycol (molecular weight 400) were dissolved in 25.00g of ethyl acetate, 0.4 mL of dibutyltin dilaurate was added dropwise, reaction was carried out at 50 ℃ for 1 hour under nitrogen protection, and 110.40 g of methyl laurate was added to obtain an oil phase.
(2) Adding 3 g of 20wt% nano titanium dioxide aqueous dispersion into 997 g of water to obtain 1000 g of 0.06 wt% nano titanium dioxide aqueous dispersion, adding 5.00g of pentaerythritol, and uniformly stirring.
(3) Slowly adding the oil phase prepared in the step (1) into the dispersion prepared in the step (2) under the stirring action of 300 rpm, continuously stirring, and heating to 60 ℃ for reaction for 2.5 hours.
(4) After the reaction is finished, obtaining polyurethane phase change microcapsule solid powder (see figure 1 and figure 2) through suction filtration, distilled water washing and drying, wherein the average particle size of the polyurethane phase change microcapsule solid powder is 225 microns (see figure 3), the polyurethane phase change microcapsule solid powder can withstand 8000 rpm centrifugal washing, the mechanical strength is good, and the complete weight loss temperature of the phase change material is increased from 141 ℃ to 223 ℃ (see figure 4).
Example 2
A preparation method of a large-particle-size polyurethane phase change microcapsule comprises the following steps:
(1) 11.00 g of 2, 4-tolylene diisocyanate and 14.00 g of polytetrahydrofuran (molecular weight 1000) were dissolved in 25.00g of toluene, 0.2 mL of dibutyltin dilaurate was added dropwise, and the mixture was reacted at 50 ℃ for 1 hour under nitrogen protection, followed by addition of 128.80 g of n-octadecane to obtain an oil phase.
(2) 50.00 g of rutile type nano titanium dioxide is added into 1000.00 g of water, and then 27.50 g of glycerol is added, and the mixture is stirred uniformly.
(3) Slowly adding the oil phase prepared in the step (1) into the dispersion prepared in the step (2) under the stirring action of 400rpm, continuously stirring, and heating to 50 ℃ for reaction for 4 hours.
(4) After the reaction is finished, carrying out suction filtration, washing with distilled water, and drying to obtain polyurethane phase change microcapsule solid powder, wherein the average particle size of the polyurethane phase change microcapsule solid powder is 103 microns, the polyurethane phase change microcapsule solid powder can withstand 8000 rpm centrifugal washing, and the complete weight loss temperature of the phase change material with good mechanical strength is increased to 215 ℃ from 162 ℃.
Example 3
A preparation method of a large-particle-size polyurethane phase change microcapsule comprises the following steps:
(1) 18.90 g of hexamethylene diisocyanate, 28.14 g of diphenylmethane diisocyanate and 50.00 g of polypropylene glycol (molecular weight 1000) were dissolved in 48.53 g of ethyl acetate, 0.3 mL of dibutyltin dilaurate was added dropwise thereto, and the mixture was reacted at 50 ℃ for 1 hour under nitrogen protection, followed by addition of 147.2 g of butyl stearate to obtain an oil phase.
(2) Adding 20.00 g of anatase type nano titanium dioxide into 1000.00 g of water, then adding 50.00 g of trimethylolpropane, and uniformly stirring.
(3) And (3) slowly adding the oil phase prepared in the step (1) into the dispersion prepared in the step (2) under the stirring action of 250 rpm, continuously stirring, and heating to 70 ℃ for reaction for 2 hours.
(4) After the reaction is finished, carrying out suction filtration, washing with distilled water and drying to obtain polyurethane phase change microcapsule solid powder, wherein the average particle size of the polyurethane phase change microcapsule solid powder is 439 mu m, the polyurethane phase change microcapsule solid powder can withstand centrifugal washing at 8000 rpm, and the complete weight loss temperature of the phase change material with good mechanical strength is increased to 230 ℃ from 136 ℃.
Example 4
A preparation method of a large-particle-size polyurethane phase change microcapsule comprises the following steps:
(1) 25.00g of isophorone diisocyanate and 11.30 g of polytetrahydrofuran (molecular weight 650) were dissolved in 25.00g of toluene, 0.4 mL of dibutyltin dilaurate was added dropwise under nitrogen protection, and the mixture was reacted at 50 ℃ for 1 hour, followed by addition of 168.9 g of liquid paraffin to obtain an oil phase.
(2) 500 g of 20wt% nano titanium dioxide aqueous dispersion is added into 500 g of water to obtain 1000 g of 10.00 wt% nano titanium dioxide aqueous dispersion, and then 20.00 g of triethanolamine is added and stirred uniformly.
(3) Adding the oil phase prepared in the step (1) into the dispersion prepared in the step (2) under the stirring action of 400rpm, continuously stirring, and heating to 60 ℃ for reaction for 3 hours.
(4) After the reaction is finished, carrying out suction filtration, washing with distilled water, and drying to obtain polyurethane phase change microcapsule solid powder, wherein the average particle size of the polyurethane phase change microcapsule solid powder is 118 microns, the polyurethane phase change microcapsule solid powder can withstand centrifugal washing at 8000 rpm, the mechanical strength is good, and the complete weight loss temperature of the phase change material is increased from 139 ℃ to 226 ℃.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (10)
1. A preparation method of a large-particle-size polyurethane phase change microcapsule is characterized by comprising the following steps of:
(1) synthesizing a polyurethane prepolymer by using diisocyanate and dihydric alcohol as raw materials, adding a phase-change material, and uniformly stirring to obtain an oil phase;
(2) preparing aqueous dispersion containing nano titanium dioxide, and adding water-soluble polyhydric alcohol to obtain a water phase;
(3) dropwise adding the oil phase prepared in the step (1) into the water phase prepared in the step (2) under stirring to form Pickering emulsion, and carrying out condensation polymerization reaction at the interface of the Pickering emulsion to obtain a polyurethane phase-change microcapsule;
(4) and after the reaction is finished, carrying out suction filtration, washing and drying to obtain polyurethane phase change microcapsule solid powder.
2. The method according to claim 1, wherein the diol is one or a mixture of two or more of polyethylene glycol, polytetrahydrofuran, and polypropylene glycol.
3. The preparation method according to claim 2, wherein the molecular weight of the polyethylene glycol is 400 to 1000; the molecular weight of the polytetrahydrofuran is 650-1000; the molecular weight of the polypropylene glycol is 400-1000.
4. The method according to claim 1, wherein the diol is used in an amount of 11 to 22 mole% based on the diisocyanate.
5. The method according to claim 1, wherein the water-soluble polyhydric alcohol is one or a mixture of two or more of trimethylolpropane, glycerol, pentaerythritol, and triethanolamine.
6. The method according to claim 1, wherein the aqueous dispersion of nano-titania is one of rutile nano-titania, anatase nano-titania, and an aqueous dispersion of nano-titania.
7. The preparation method according to claim 1, wherein in the aqueous phase in the step (2), the mass ratio of the water, the water-soluble polyol and the nano titanium dioxide is 100:0.5-5: 0.06-10.
8. The method as claimed in claim 1, wherein the stirring rate in step (3) is 400rpm, 250 ℃.
9. The method according to claim 1, wherein the condensation polymerization in step (3) is carried out at a temperature of 50 to 70 ℃ for 2 to 4 hours.
10. A large-particle-size polyurethane phase-change microcapsule prepared by the preparation method according to any one of claims 1 to 9.
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