CN102198386A - Preparation method of polyurethane (PU) nano-encapsulated phase-change material (NEPCM) - Google Patents
Preparation method of polyurethane (PU) nano-encapsulated phase-change material (NEPCM) Download PDFInfo
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- CN102198386A CN102198386A CN2010101378122A CN201010137812A CN102198386A CN 102198386 A CN102198386 A CN 102198386A CN 2010101378122 A CN2010101378122 A CN 2010101378122A CN 201010137812 A CN201010137812 A CN 201010137812A CN 102198386 A CN102198386 A CN 102198386A
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- polyurethane
- change material
- vinyl monomer
- amphipathic
- emulsion
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 65
- 239000012782 phase change material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 19
- 229920002635 polyurethane Polymers 0.000 claims abstract description 60
- 239000002088 nanocapsule Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 206010011732 Cyst Diseases 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 208000031513 cyst Diseases 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 150000003254 radicals Chemical class 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010382 chemical cross-linking Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 16
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000002775 capsule Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000011162 core material Substances 0.000 abstract 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract 1
- 230000028016 temperature homeostasis Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000012188 paraffin wax Substances 0.000 description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NQOGBCBPDVTBFM-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(C)COC(C)CO NQOGBCBPDVTBFM-UHFFFAOYSA-N 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 4
- LNDKRVOOYMEYTC-UHFFFAOYSA-N buta-1,3-dien-1-ol Chemical compound OC=CC=C LNDKRVOOYMEYTC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003094 microcapsule Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Abstract
The invention relates to a method for preparing nano-encapsulated phase-change material (NEPCM) by taking amphiphilic polyurethane (PU) or a composite amphiphilic PU material as a capsule wall without adding an emulsifier. The method comprises the following steps: dispersing PCM and a small quantity of vinyl monomers by utilizing the amphiphilic PU; and then chemically cross-linking the PU capsule wall through emulsion polymerization initiated by free radicals to finally obtain the NEPCM. By utilizing the novel method for preparing the NEPCM provided by the invention, the obtained nano-capsules have good dispersion stability and good re-dispersibility and average particle size of 50nm-800nm, wherein a core material accounts for 1%-80% of the weight of one capsule. In addition, the NEPCM can be used in latent functionally thermal fluid in the form of suspension, and can be compounded with other materials in the form of powder so as to achieve a thermoregulation function.
Description
Technical field
The present invention relates to be a kind of be the preparation method of the nano capsule phase change material of cyst wall with amphipathic polyurethane and composite thereof, its suspension can use as the functional form hot fluid, powder can make it have temperature adjustment function with other material is compound.
Background technology
The microcapsules of coating phase-change materials and Nano capsule are called nano capsule phase change material and microencapsulated phase change material, the particle diameter of microcapsules usually between 1～1000 μ m, less than the capsule of 1 μ m Nano capsule.The shell of nano capsule phase change material and microencapsulated phase change material mostly is macromolecular material, as Lauxite, melamine formaldehyde resin, polyureas, polyurethane, polystyrene, polymethacrylates etc.It can be used with the emulsion of water or silicone oil or the form of suspension, as: potential heat functional thermal fluid; Also can use with form of powder, as: carry out compound with fiber, foamed plastics, coating, construction material and biomaterial etc.
The microencapsulated phase change material of big particle diameter is free settling but also easier fragmentation during by pipeline and pump not only, and particle diameter is at the nano phase change capsule of tens nanometers to the hundreds of nanometer, and its suspension shows higher heat conduction speed, better stability and lower breakage rate.
In-situ polymerization, interfacial polymerization combine with miniemulsion or high speed shear technology can obtain Nano capsule, the part but these preparation methods come with some shortcomings, and all need to add emulsifying agent ability stable dispersion in water, dilution stability and heavy dispersed relatively poor, small-molecular emulsifier also can cause certain interference to the suspension flow sex change.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method for preparing nano capsule phase change material is provided, need not to add the nano capsule phase change material that emulsifying agent just can obtain stably dispersing.
The cyst wall of nano capsule phase change material of the present invention is the composite of amphipathic polyurethane material or amphipathic polyurethane and other alkene monomer polymer, core is an organic phase change material, at first use amphipathic polyurethane and phase-change material in the preparation process, a small amount of vinyl monomer mixes, under high speed shear, add deionized water then, obtain the emulsion of polyurethane coating phase-change materials and vinyl monomer after the several minutes of high speed dispersion, in the gained emulsion, add the radical type initator, carry out emulsion polymerisation at a certain temperature, make cyst wall generation chemical crosslinking, obtain Nano capsule.
Have hydrophilic radical, oleophylic segment and unsaturated double-bond on the molecular structure of amphipathic polyurethane simultaneously, hydrophilic radical can be that ionic also can be a nonionic.
The vinyl monomer compound with polyurethane is esters of acrylic acid reactive diluents such as styrene, methyl methacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, neopentylglycol diacrylate.The purpose that adds a small amount of vinyl monomer is to increase crosslink density, to a certain degree improves the intensity of cyst wall, and the cyst wall main component remains polyurethane, and the quality of vinyl monomer is no more than 50% of polyurethane.It is as follows that polyurethane disperses the prescription of phase-change material and vinyl monomer to form mass fraction:
Organic phase change material 1～80
Vinyl monomer 1～25
The initator can produce free radical is adopted in emulsion polymerisation, Ammonium Persulfate 98.5, potassium peroxydisulfate, azo-bis-isobutyl cyanide etc., and under the emulsion polymerisation temperature of routine, initator discharges free radical makes cyst wall generation cross-linking reaction.
Operation principle of the present invention is as follows:
Amphipathic polyurethane not only has good self-emulsifying ability in water, but also has the ability of other compound of dispersion and emulsion, and the size of its suspended particles is then in the scope of tens nanometers to the hundreds of nanometer.This specific character makes with amphipathic polyurethane dispersion and emulsion phase-change material, does not need to add the Nano capsule that emulsifying agent just can access small particle diameter.
Be used to prepare the amphipathic polyurethane of Nano capsule, in its molecular structure: long-chain is given PU certain pliability for hydrophobic soft section, makes capsule can bear the Volume Changes that phase transformation causes; Hard section is given PU certain mechanical strength; Hydrophilic radical makes PU phase-change materials such as paraffin class, stearate class, PTMG can be emulsified in the water, and unsaturated double-bond can make the cyst wall polymer carry out chemical crosslinking.
Emulsion polymerisation makes and polyurethane cyst wall generation chemical crosslinking obtains hot property, mechanical performance and good sealing performance Nano capsule, if there is vinyl monomer to participate in cross-linking reaction, then the crosslink density of cyst wall increases, and sealing and mechanical performance can increase.The content by regulating the polyurethane internal double bond and the amount of vinyl monomer can obtain the cyst wall of different crosslink densities, and the performance of its Nano capsule is also different.
The present invention has following advantage and effect with respect to the technology of existing preparation nano capsule phase change material:
(1) need not to add emulsifying agent and just can obtain Nano capsule, eliminate emulsifying agent capsule and suspension Effect on Performance.
(2) disperse the back emulsion only to contain polyurethane, vinyl monomer, phase-change material and water, composition is simple, and preparation technology is also simple relatively.
(3) gained Nano capsule stability of suspension is good, and has heavy preferably dispersed.
(4) polyurethane is the adjustable polymer of a kind of structure, can have better elastic and mechanical strength simultaneously, and the polyurethane cyst wall can provide enough volume extendable rooms for phase transformation, avoids damaged.
Description of drawings
The transmission electron microscope picture of Fig. 1 polyurethane nano capsule phase change material,
The particle diameter distribution map of Fig. 2 polyurethane nano capsule phase change material.
The specific embodiment
Embodiment 1
One, the preparation of amphipathic polyurethane.
A certain amount of toluene di-isocyanate(TDI), polytetrahydrofuran diol and organotin catalysts dibutyl tin laurate are mixed, after reacting a period of time at a certain temperature, add dihydromethyl propionic acid, add the Jia Jibingxisuanβ-Qiang Yizhi end-blocking at last, obtain amphipathic polyurethane.Be reflected in the nitrogen atmosphere and carry out, it is as follows that the raw material of amphipathic polyurethane is formed mass fraction:
Toluene di-isocyanate(TDI) 100
Polytetrahydrofuran diol 77
Dihydromethyl propionic acid 44
Jia Jibingxisuanβ-Qiang Yizhi 58
Dibutyl tin laurate 0.4
Two, the preparation of emulsion.
Get a certain amount of amphipathic polyurethane, add a certain amount of phase-change material PolyTHF (molecular weight is greater than 2000) in proportion, deionized water.Adopt high-shearing dispersion emulsifying machine 10000r/min emulsification to obtain even pre-emulsion, the composition mass fraction of emulsion is as follows:
Amphipathic polyurethane 10.5
PolyTHF 19.5
Deionized water 70
Three, emulsion polymerisation.
Above-mentioned emulsion is warmed up to 70 ℃, adds initiator ammonium persulfate, the reaction certain hour makes Nano capsule.
The gained emulsion is uniform and stable, average grain diameter 379nm.Emulsion is through behind the decompress filter, and low-temperature freeze-dry is removed moisture and solvent, and the gained dried particle carries out dsc analysis, and its enthalpy of phase change is reached for pure phase and becomes 65% of material, and TGA the analysis showed that its maximum weight loss rate peak about 410～420 ℃, Heat stability is good.
Embodiment 2
One, the preparation of amphipathic polyurethane.
A certain amount of toluene di-isocyanate(TDI), allylin and dibutyl tin laurate are mixed, after reacting a period of time at a certain temperature, add dimethylolpropionic acid/acetone soln, add 1-dodecanol end-blocking at last, reaction finishes the back steams except that acetone, obtains amphipathic polyurethane.Be reflected in the nitrogen atmosphere and carry out, it is as follows that the raw material of amphipathic polyurethane is formed mass fraction:
Toluene di-isocyanate(TDI) 100
Allylin 25
Dimethylolpropionic acid 52
1-dodecanol 58
Dibutyl tin laurate 0.3
Two, the preparation of emulsion.
Get a certain amount of amphipathic polyurethane, add a certain amount of solid paraffin and tripropylene glycol acrylate in proportion, heating mixes, and adds deionized water again.Adopt high-shearing dispersion emulsifying machine 10000r/min emulsification to obtain even pre-emulsion, the composition mass fraction of emulsion is as follows:
Amphipathic polyurethane 12
Solid paraffin 15
Tripropylene glycol acrylate 3
Deionized water 70
Three, emulsion polymerisation.
Above-mentioned emulsion is warmed up to 70 ℃, adds initiator ammonium persulfate, the reaction certain hour makes Nano capsule.
The gained emulsion is uniform and stable, average grain diameter 300nm.Emulsion is through behind the decompress filter, and low-temperature freeze-dry is removed moisture and solvent, and the gained dried particle carries out dsc analysis, and its enthalpy of phase change reaches 102J/g.Dry particle adds in the entry, stirs and can be suspended in the water again with glass bar.
Embodiment 3
One, the preparation of amphipathic polyurethane.
A certain amount of toluene di-isocyanate(TDI), allylin and dibutyl tin laurate are mixed, after reacting a period of time at a certain temperature, add dimethylolpropionic acid/acetone soln, add 1-dodecanol end-blocking at last, reaction finishes the back steams except that acetone, obtains amphipathic polyurethane.Be reflected in the nitrogen atmosphere and carry out, it is as follows that the raw material of amphipathic polyurethane is formed mass fraction:
Toluene di-isocyanate(TDI) 100
Allylin 23
Dimethylolpropionic acid 46
1-dodecanol 58
Dibutyl tin laurate 0.3
Two, the preparation of emulsion.
Get a certain amount of amphipathic polyurethane, add a certain amount of methyl stearate and tripropylene glycol acrylate in proportion, heating mixes, and adds deionized water again.Adopt high-shearing dispersion emulsifying machine 10000r/min emulsification to obtain even pre-emulsion, the composition mass fraction of emulsion is as follows:
Amphipathic polyurethane 12
Tripropylene glycol acrylate 3
Deionized water 70
Three, emulsion polymerisation.
Above-mentioned emulsion is warmed up to 70 ℃, adds initiator ammonium persulfate, the reaction certain hour makes Nano capsule.
The gained emulsion is uniform and stable, average grain diameter 277nm.Emulsion is through behind the decompress filter, and low-temperature freeze-dry is removed moisture and solvent, and the gained dried particle carries out dsc analysis, and its enthalpy of phase change reaches 75J/g.Dry particle adds in the entry, stirs and can be suspended in the water again with glass bar.
Embodiment 4
One, the preparation of amphipathic polyurethane.
A certain amount of toluene di-isocyanate(TDI), dimethylolpropionic acid/acetone soln and dibutyl tin laurate are mixed, after reacting a period of time at a certain temperature, add end hydroxy butadiene, add the methyl alcohol end-blocking at last, reaction finishes the back steams except that acetone, obtains amphipathic polyurethane.Be reflected in the nitrogen atmosphere and carry out, it is as follows that the raw material of amphipathic polyurethane is formed mass fraction:
End hydroxy butadiene 100
Toluene di-isocyanate(TDI) 60
Dimethylolpropionic acid 35
Methyl alcohol 3
Dibutyl tin laurate 0.3
Two, the preparation of emulsion.
Get a certain amount of amphipathic polyurethane, add a certain amount of paraffin and styrene in proportion, heating mixes, and adds deionized water again.Adopt high-shearing dispersion emulsifying machine 10000r/min emulsification to obtain even pre-emulsion, the composition mass fraction of emulsion is as follows:
Amphipathic polyurethane 12
Styrene 3
Deionized water 70
Three, emulsion polymerisation.
Above-mentioned emulsion is warmed up to 70 ℃, adds initiator ammonium persulfate, the reaction certain hour makes Nano capsule.
The gained emulsion is uniform and stable, average grain diameter 198nm.Emulsion is through behind the decompress filter, and low-temperature freeze-dry is removed moisture and solvent, and the gained dried particle carries out dsc analysis, and its enthalpy of phase change reaches 101J/g.Dry particle adds in the entry, stirs and can be suspended in the water again with glass bar.
One, the preparation of amphipathic polyurethane.
A certain amount of IPDI, polyethylene glycol and dibutyl tin laurate are mixed, react a period of time at a certain temperature after, add end hydroxy butadiene, add the methyl alcohol end-blocking at last, obtain amphipathic polyurethane.Be reflected in the nitrogen atmosphere and carry out, it is as follows that the raw material of amphipathic polyurethane is formed mass fraction:
IPDI I 18
End hydroxy butadiene 56
Methyl alcohol 2
Dibutyl tin laurate 0.3
Two, the preparation of emulsion.
Get a certain amount of amphipathic polyurethane, add a certain amount of paraffin and styrene in proportion, heating mixes, and adds deionized water again.Adopt high-shearing dispersion emulsifying machine 10000r/min emulsification to obtain even pre-emulsion, the composition mass fraction of emulsion is as follows:
Amphipathic polyurethane 12
Styrene 3
Deionized water 70
Three, emulsion polymerisation.
Above-mentioned emulsion is warmed up to 70 ℃, adds initiator ammonium persulfate, the reaction certain hour makes Nano capsule.
The gained emulsion is uniform and stable, average grain diameter 605nm.Emulsion is through behind the decompress filter, and low-temperature freeze-dry is removed moisture and solvent, and the gained dried particle carries out dsc analysis, and its enthalpy of phase change reaches 105J/g.Dry particle adds in the entry, stirs and can be suspended in the water again with glass bar.
Claims (6)
1. the preparation method of a nano capsule phase change material, it is characterized in that: preparation process need not to add emulsifying agent, cyst wall is the composite of amphipathic polyurethane material or amphipathic polyurethane and a small amount of other alkene monomer polymer, core is an organic phase change material, at first disperse phase-change material and vinyl monomer with amphipathic polyurethane, carry out the emulsion polymerisation that free radical causes then, make cyst wall generation chemical crosslinking, obtain Nano capsule.
2. method according to claim 1 is characterized in that having hydrophilic radical, oleophylic segment and unsaturated double-bond simultaneously on the molecular structure of amphipathic polyurethane, and hydrophilic radical can be that ionic also can be a nonionic.
3. method according to claim 1, it is characterized in that with the compound vinyl monomer of polyurethane be esters of acrylic acid reactive diluents such as styrene, methyl methacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, neopentylglycol diacrylate.
4. method according to claim 1, it is characterized in that amphipathic polyurethane and phase-change material or vinyl monomer mix, add entry, under high speed shear, polyurethane can be dispersed in phase-change material and a small amount of vinyl monomer in the water, form steady suspension or emulsion, do not need to add emulsifying agent.
5. method according to claim 1 is characterized in that, it is as follows that polyurethane disperses the prescription of phase-change material and vinyl monomer to form mass fraction, and the quality of vinyl monomer is no more than 50% of polyurethane, and the cyst wall main component is a polyurethane:
Amphipathic polyurethane 20～99
Organic phase change material 1～80
Vinyl monomer 1～25.
6. method according to claim 1 is characterized in that, the initator that can produce free radical, Ammonium Persulfate 98.5, potassium peroxydisulfate, azo-bis-isobutyl cyanide etc. are adopted in emulsion polymerisation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450439A (en) * | 2013-09-26 | 2013-12-18 | 青岛科技大学 | Oleyl alcohol terminated polyurethane, preparation method thereof and usage thereof |
| WO2014114838A3 (en) * | 2013-01-25 | 2015-03-05 | Ecopol Tech, S.L. | Method for producing a microencapsulate and corresponding reactive amphiphilic compound, microencapsulate and composition. |
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| CN104645907A (en) * | 2015-02-06 | 2015-05-27 | 顺德职业技术学院 | Preparation method of hot cross-linking type nano paraffin phase-change energy-storage capsule |
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| WO2023092286A1 (en) * | 2021-11-23 | 2023-06-01 | 广州市白云化工实业有限公司 | Polyurethane phase-change nanocapsule, phase-change polyurethane pouring sealant and preparation method therefor |
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2010
- 2010-03-24 CN CN2010101378122A patent/CN102198386A/en active Pending
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| WO2014114838A3 (en) * | 2013-01-25 | 2015-03-05 | Ecopol Tech, S.L. | Method for producing a microencapsulate and corresponding reactive amphiphilic compound, microencapsulate and composition. |
| CN103450439A (en) * | 2013-09-26 | 2013-12-18 | 青岛科技大学 | Oleyl alcohol terminated polyurethane, preparation method thereof and usage thereof |
| CN104645908A (en) * | 2015-02-06 | 2015-05-27 | 顺德职业技术学院 | Preparation method of photo cross-linking type nano paraffin phase-change energy-storage capsule |
| CN104645907A (en) * | 2015-02-06 | 2015-05-27 | 顺德职业技术学院 | Preparation method of hot cross-linking type nano paraffin phase-change energy-storage capsule |
| CN104645907B (en) * | 2015-02-06 | 2016-08-17 | 顺德职业技术学院 | A kind of preparation method of heat cross-linked type nanometer wax phase change energy storage capsule |
| CN108903100A (en) * | 2018-06-27 | 2018-11-30 | 徐玉玉 | A kind of intelligence clothes new material and preparation method thereof |
| CN114015415A (en) * | 2021-11-23 | 2022-02-08 | 广州市白云化工实业有限公司 | Polyurethane phase-change nanocapsule, phase-change polyurethane pouring sealant and preparation method thereof |
| WO2023092286A1 (en) * | 2021-11-23 | 2023-06-01 | 广州市白云化工实业有限公司 | Polyurethane phase-change nanocapsule, phase-change polyurethane pouring sealant and preparation method therefor |
| CN114015415B (en) * | 2021-11-23 | 2023-10-24 | 广州市白云化工实业有限公司 | Polyurethane phase-change nanocapsules, phase-change polyurethane pouring sealant and preparation method thereof |
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