CN107987518A - A kind of magnetic base organic composite shaping phase-change material and preparation method thereof - Google Patents
A kind of magnetic base organic composite shaping phase-change material and preparation method thereof Download PDFInfo
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- CN107987518A CN107987518A CN201711309116.3A CN201711309116A CN107987518A CN 107987518 A CN107987518 A CN 107987518A CN 201711309116 A CN201711309116 A CN 201711309116A CN 107987518 A CN107987518 A CN 107987518A
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- Prior art keywords
- change material
- phase
- magnetic
- particle
- polyurethane
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- 239000012782 phase change material Substances 0.000 title claims abstract description 124
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000007493 shaping process Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 239000004814 polyurethane Substances 0.000 claims abstract description 30
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 59
- 229910052681 coesite Inorganic materials 0.000 claims description 37
- 229910052906 cristobalite Inorganic materials 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 229910052682 stishovite Inorganic materials 0.000 claims description 37
- 229910052905 tridymite Inorganic materials 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 229920000620 organic polymer Polymers 0.000 claims description 18
- 239000012188 paraffin wax Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 15
- 229910017163 MnFe2O4 Inorganic materials 0.000 claims description 15
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims description 15
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- -1 poly- ammonia Ester Chemical class 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 claims description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- OLLIIJJXEVDDNZ-UHFFFAOYSA-N dihydroxy-(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical class OP(O)(=S)OC1=CC=CC=C1N=C=O OLLIIJJXEVDDNZ-UHFFFAOYSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 claims description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- BKOKNVYSTQLYIJ-UHFFFAOYSA-N N(=C=O)C1=C(C=CC=C1)OP(O)(O)=O Chemical class N(=C=O)C1=C(C=CC=C1)OP(O)(O)=O BKOKNVYSTQLYIJ-UHFFFAOYSA-N 0.000 claims description 4
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 4
- 239000004519 grease Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- 235000019766 L-Lysine Nutrition 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- MAHHNNHFKWSQST-PYYKYHENSA-N [(2R,3S)-2,3,4-tri(octadecanoyloxy)butyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC MAHHNNHFKWSQST-PYYKYHENSA-N 0.000 claims description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229960001947 tripalmitin Drugs 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 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 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 claims 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- 239000005639 Lauric acid Substances 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 26
- 230000009466 transformation Effects 0.000 abstract description 25
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000002105 nanoparticle Substances 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000011232 storage material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000015 thermotherapy Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PCYHIVMEYKSVOT-UHFFFAOYSA-N CC.N=C=O.N=C=O.N=C=O Chemical compound CC.N=C=O.N=C=O.N=C=O PCYHIVMEYKSVOT-UHFFFAOYSA-N 0.000 description 1
- MAMABHFMIUQTIY-UHFFFAOYSA-N CC1=CC=CC=C1.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC=C1.N=C=O.N=C=O.N=C=O MAMABHFMIUQTIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002907 paramagnetic material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of magnetic base organic composite shaping phase-change material and preparation method thereof, belong to the technical field of high molecular material.A kind of magnetic base organic composite shaping phase-change material, it is characterised in that：The composite material is made of the organic shaping phase-change material of polyurethane and the magnetic nano-particle being dispersed in it, wherein, by mass percentage, magnetic nano-particle：1~4%, the organic shaping phase-change material of polyurethane：96~99% wherein, and magnetic nano-particle is the particle with core shell structure, wherein, karyosome footpath is 80~150nm, and shell thickness is 20~40nm.The magnetic base organic composite shaping phase-change material can realize that magnetic thermal energy is changed, and by thermal energy storage in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Description
Technical field
The present invention relates to a kind of magnetic base organic composite shaping phase-change material and preparation method thereof, belong to the skill of high molecular material
Art field.
Background technology
Phase-changing energy storage material is to carry out thermal energy storage and temperature using heat absorption of the material in phase transition process and exothermic effect
The material of regulation and control, is energy-saving and environment-friendly optimal environmentally protective carrier, but phase-change material there is also it is certain the problem of, such as mostly
Phase-change material easy firing, easily leakage, there is very big limitation in practical applications.Composite phase-change energy storage material is at work substantially
Reveal macroscopically solid-to-solid transition, shape does not change, service life length, No leakage, corrosiveness of the material to container
It is small, therefore it is to realize that phase-change material is widely used in necessary to heat management and field of storage to develop composite phase-change energy storage material
(Khudhair AM,Farid M M.A review on energy conservation in building
applications with thermal storage by latent heat using phase change materials
[J].Energy conversion and management,2004,45(2):263-275.)。
Magnetic nanoparticle is because it has unique chemical and physical features, as magnetic susceptibility is of a relatively high, zero coercivity,
Zero remanent magnetism etc., the excellent magnetothermal effect in alternating magnetic field is therefore, compound with shaping phase-change material by magnetic material, Ke Yishi
Existing magnetic-thermal energy conversion, thermal energy is stored in a manner of latent heat, and then utilizes.
The content of the invention
The object of the present invention is to provide a kind of conversion of magnetic-thermal energy and thermal energy storage organic composite shaping phase-change material, this
Kind material is using magnetic material as magnetic-thermal energy converting function material, using phase-change material as energy storage material, the two is compound, obtains
Phase transformation enthalpy is high, dimensionally stable, and the good new heat accumulation of heat endurance and heat management material, have broad application prospects.
A kind of magnetic base organic composite shaping phase-change material, the composite material is by the organic shaping phase-change material of polyurethane and
The even magnetic nano-particle composition being dispersed in it, wherein, by mass percentage,
Magnetic nano-particle：1~4%, the organic shaping phase-change material of polyurethane：96~99%
Wherein, magnetic nano-particle is the particle with nucleocapsid structure, wherein, karyosome footpath is 80~150nm, and shell thickness is
20~40nm, is specially Fe3O4@SiO2、Fe3O4@TiO2、Fe3O4@ZrO2、CoFe2O4@SiO2、CoFe2O4@TiO2、CoFe2O4@
ZrO2、NiFe2O4@SiO2、NiFe2O4@TiO2、NiFe2O4@ZrO2、MnFe2O4@SiO2、MnFe2O4@TiO2、MnFe2O4@ZrO2
At least one of.
Preferably, the organic shaping phase-change material of the polyurethane is obtained by polyurethane organic polymer and phase-change material are compound
Arrive,
Wherein, the mass fraction of phase-change material is 50%~80% in the organic shaping phase-change material of the polyurethane, described
Polyurethane organic polymer is by polyethylene glycol and L-lysine triisocyanate, 4,4 ', and 4 "-three isocyanatophenyl phosphates,
4,4 ', 4 "-three isocyanatophenyl thiophosphates, 2,2 '-dimethyl -3,3,5,5- triphenyl methanes tetraisocyanate or triphen
The crosslinking polycondensation of methylmethane triisocyanate obtains, and molecular weight polyethylene glycol is 200~20000；
The phase-change material is paraffin, aliphatic acid, alcohol compound, grease.
Further preferably, the paraffin is paraffin of the fusing point at 20~60 DEG C；The aliphatic acid is certain herbaceous plants with big flowers acid, 12
Acid, tetradecylic acid, pentadecanoic acid, palmitic acid, stearic acid；The alcohol compound is lauryl alcohol, tetradecyl alchohol, hexadecanol, molecular weight 200
~20000 polyethylene glycol；The grease is erythritol tetrastearate, four palmitate of erythritol, galactitol six
Palmitate, six stearic acid of galactitol, glyceryl tristearate, tripalmitin, three myristins, stearic acid
Butyl ester.
Preferably, the magnetic nano-particle is made as follows：To the dispersion liquid containing 100mg magnetic Nano clusters
Middle addition 3mL ammonium hydroxide, after ultrasonic 5min, continues ultrasound 5min, injection under mechanical stirring aoxidizes after adding 100mL absolute ethyl alcohols
The presoma of thing, continues to stir, and stops after reacting 1h, obtains magnetic nano-particle.
The magnetic Nano cluster is Fe3O4、CoFe2O4、NiFe2O4、MnFe2O4；The presoma for ethyl orthosilicate,
Butyl titanate and tetrabutyl zirconate, the addition of presoma is 300~500 μ L.
Further, the solid-to-liquid ratio of the dispersion liquid containing 100mg magnetic Nano clusters is 0.1：100~2：100.
Magnetic base organic composite shaping phase-change material of the present invention, is preferably made as follows：In proportion, by phase transformation material
Solvent dissolving is added after material fusing, ultrasonic mixing is uniform at 60 DEG C with polyurethane organic polymer soln, adds magnetic Nano
The alcohol dispersion liquid of particle, ultrasonic mixing is uniform again, and 80 DEG C of vacuum drying 24h, obtain magnetic base organic composite fixed phase change material
Material.
Further, the solvent is ethanol, toluene or tetrahydrofuran, and the ratio of phase-change material and solvent is 1：1~1：5；
The solid-to-liquid ratio of the alcohol dispersion liquid of the magnetic nano-particle is 0.1：100~2：100.
It is a further object of the present invention to provide the preparation method of above-mentioned magnetic base organic composite shaping phase-change material.
A kind of preparation method of magnetic base organic composite shaping phase-change material, the described method includes following step：
(1) 3mL ammonium hydroxide is added into the dispersion liquid containing 100mg magnetic Nano clusters, after ultrasonic 5min, adds 100mL
Continue ultrasound 5min after absolute ethyl alcohol, inject the presoma of oxide under mechanical stirring, continue to stir, stop after reacting 1h,
Obtain magnetic nano-particle；
(2) by average molecular weight be 200~20000 polyethylene glycol under the conditions of 80 DEG C vacuum dehydration 48h, then with L-
Lysine triisocyanate, 4,4 ', 4 "-three isocyanatophenyl phosphates, 4,4 ', 4 "-three isocyanatophenyl thiophosphates, 2,
2 '-dimethyl -3,3,5,5- triphenyl methanes tetraisocyanate or triphenylmethane triisocyanate in molar ratio 3:2 be dissolved in it is molten
In agent, and catalyst is added in a solvent, in N2Above-mentioned raw materials are placed in the there-necked flask with stirring in environment, in 80 DEG C of reactions
6h obtains polyurethane organic polymer, the preferred dibutyl tin laurate of catalyst；
The catalyst is dibutyl tin laurate, it is 1 with polyethylene glycol mass ratio：80~150；The solvent with
The mass ratio of polyethylene glycol is 5~10：1；The solvent for tetrahydrofuran, dioxane, petroleum ether, acetone, butanone, chloroform,
Dichloromethane, carbon tetrachloride, carbon disulfide, DMF, DMSO, benzene,toluene,xylene, nitrobenzene, chlorobenzene, hexamethylene or n-hexane
In 1~3 kind；
(3) solvent dissolving is added after phase-change material is melted, in proportion, with polyurethane organic polymer soln at 60 DEG C
Ultrasonic mixing is uniform, adds the alcohol dispersion liquid of magnetic nano-particle, and ultrasonic mixing is uniform again, and 80 DEG C of vacuum drying 24h, obtain
To magnetic base organic composite shaping phase-change material,
Wherein, the mass ratio of the phase-change material and polyurethane organic polymer is 5:5~8:2.
Beneficial effects of the present invention are：Magnetic nano-particle is dispersed in the organic shaping phase-change material of polyurethane；It is logical
Cross polyurethane organic polymer (TTIPU) and phase-change material is compound obtains organic shaping phase-change material.Polyurethane organic polymer
Compound with phase-change material, obtained organic composite shaping phase-change material (PCM) has high phase transformation enthalpy；Organic composite setting phase
It is compound with magnetic nano-particle again to become material, finally obtains magnetic base organic composite shaping phase-change material.The magnetic base organic composite is determined
Shape phase-change material can realize magnetic-thermal energy conversion, and by thermal energy storage in phase-change material.The material has high enthalpy of phase change
Value, high heat endurance, excellent shape stability.
Brief description of the drawings
Fig. 1 is Fe described in embodiment 13O4@SiO2The scanning electron microscope (SEM) and transmission electron microscope (TEM) of magnetic nano-particle
Figure.
Fig. 2 is paraffin, TTIPU and Fe described in embodiment 13O4@SiO2The XRD diagram of/PCM.
Fig. 3 is paraffin, PCM and Fe described in embodiment 13O4@SiO2The DSC curve figure of/PCM.
Fig. 4 is paraffin, TTIPU and Fe described in embodiment 13O4@SiO2TG the and DTG curve maps of/PCM.
Fig. 5 is Fe described in embodiment 13O4@SiO2Magnetic-hot-cast socket of/PCM magnetic base organic composite shaping phase-change materials with
Thermal energy storage curve map (alternating magnetic field frequency is 1.36MHz).
Fig. 6 is paraffin, TTIPU, PCM and Fe described in embodiment 13O4@SiO2/ PCM is heated at 35 DEG C, 45 DEG C, 55 DEG C
Digital photograph after 20min.
Embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
Magnetic base organic composite shaping phase-change material described in following embodiments is made as follows：
(1) 3mL ammonium hydroxide is added into the dispersion liquid containing 100mg magnetic Nano clusters, and (mass fraction is 25~28%
Ammonium hydroxide), after ultrasonic 5min, continue ultrasound 5min after adding 100mL absolute ethyl alcohols, be rapidly injected oxide under mechanical stirring
Presoma, continues to stir, and stops after reacting 1h, obtains magnetic nano-particle,
Wherein, the solid-to-liquid ratio of the dispersion liquid containing 100mg magnetic Nano clusters is 0.1：100~2：100；
The magnetic Nano cluster is Fe3O4、CoFe2O4、NiFe2O4、MnFe2O4；The presoma for ethyl orthosilicate,
Butyl titanate and tetrabutyl zirconate, the addition of presoma is 300~500 μ L；
(2) by polyethylene glycol that average molecular weight is 200~20000 under the conditions of 80 DEG C vacuum dehydration 48h, then with three
Phenylmethane triisocyanate in molar ratio 3:2 are dissolved in solvent, and add catalyst in a solvent, in N2Will be above-mentioned in environment
Raw material is placed in the there-necked flask with stirring, and reacting 6h at 80 DEG C obtains polyurethane organic polymer；
The catalyst is dibutyl tin laurate, it is 1 with polyethylene glycol mass ratio：80~150；The solvent with
The mass ratio of polyethylene glycol is 5~10：1；The solvent for tetrahydrofuran, dioxane, petroleum ether, acetone, butanone, chloroform,
Dichloromethane, carbon tetrachloride, carbon disulfide, DMF, DMSO, benzene,toluene,xylene, nitrobenzene, chlorobenzene, hexamethylene or n-hexane
In 1~3 kind.
(3) solvent dissolving is added after phase-change material is melted, in proportion with polyurethane organic polymer soln at 60 DEG C
Ultrasonic mixing is uniform, adds the alcohol dispersion liquid of magnetic nano-particle, and ultrasonic mixing is uniform again, and 80 DEG C of vacuum drying 24h, obtain
To magnetic base organic composite shaping phase-change material,
Wherein, the mass ratio of the phase-change material and polyurethane organic polymer is 5:5~8:2；The solvent for ethanol,
The ratio of toluene or tetrahydrofuran, phase-change material and solvent is 1：1~1：5；The alcohol dispersion liquid of the magnetic nano-particle is consolidated
Liquor ratio is 0.1：100~2：100.
In following embodiments, the superparamagnetic nanoparticle is Fe3O4@SiO2、Fe3O4@TiO2、Fe3O4@ZrO2、
CoFe2O4@SiO2、CoFe2O4@TiO2、CoFe2O4@ZrO2、NiFe2O4@SiO2、NiFe2O4@TiO2、NiFe2O4@ZrO2、
MnFe2O4@SiO2、MnFe2O4@TiO2、MnFe2O4@ZrO2, wherein karyosome footpath is 80~150nm, and shell thickness is 20~40nm.
Embodiment 1
3mL ammonium hydroxide, ultrasonic 5min are added into the ferroferric oxide magnetic nano cluster dispersion liquid 20mL containing 100mg
Afterwards, continue ultrasound 5min after adding 100mL absolute ethyl alcohols, inject the tetraethyl orthosilicate of 325 μ L under mechanical stirring, continue to stir
Mix, stop after reacting 1h, obtain magnetic nano-particle Fe3O4@SiO2；By the polyethylene glycol (10g) that average molecular weight is 10000
The vacuum dehydration 48h under the conditions of 80 DEG C, then with triphenylmethane triisocyanate in molar ratio 3:2 are dissolved in 30ml toluene,
And 2 drop dibutyl tin laurates are added in toluene, in N2Above-mentioned raw materials are placed in the there-necked flask with stirring in environment,
80 DEG C of reaction 6h obtain polyurethane organic polymer；After 24g paraffin is added mixing, addition contains 1.36g magnetic nano-particles
Fe3O4@SiO2Alcohol dispersion liquid 68ml, ultrasonic mixing is uniform, 80 DEG C vacuum drying 24h, obtain magnetic base organic composite setting phase
Become material.
It can be seen that Fe before coating from the SEM figures and TEM figures (attached drawing 1) of magnetic nano-particle3O4The average grain of nano-cluster
Footpath is 103nm, gained Fe after cladding3O4@SiO2Nano-particle average grain diameter is 150nm.Can from the XRD (attached drawing 2) of material
Go out, the characteristic peak of TTIPU, but also the characteristic peak containing paraffin not only occurs in gained magnetic base composite shape-setting phase-change material, simply
Peak intensity has a degree of decline, this show in magnetic base composite phase-change material the crystal habit of paraffin and TTIPU not by
The influence compound to the two, material still keep good crystal property, so as to ensure that material has higher latent heat of phase change.From
The DSC curve (attached drawing 3) of material is as can be seen that the phase transformation enthalpy of material illustrate resulting materials with high in 158J/g or so
Energy storage density, and fusing phase transformation enthalpy of the composite phase-change material between 41-47 DEG C (magnetic thermotherapy temperature section) is left for 115J/g
The right side, has higher phase transformation enthalpy, illustrates that this material regulates and controls available for magnetic thermotherapy temperature.From TG the and DTG curve (attached drawings of material
4) as can be seen that Fe3O4@SiO2There are two obvious catabolic phases in/PCM, and at 316.2 DEG C, paraffin is decomposed,
410.7 DEG C of decomposition for TTIPU.The two decomposition temperatures are far above the temperature of materials'use, illustrate that this material has high heat
Stability.Attached drawing 5 shows that material is placed in alternating magnetic field, magnetic Fe3O4@SiO2Nano-particle is due to magnetothermal effect and to surrounding
Function of environment heat emission, organic composite shaping phase-change material temperature raises rapidly, and after 600s, temperature rises to 56 DEG C, and at 36~43 DEG C
There is the platform that increasess slowly of temperature, show that phase in version occurs for the phase transformation component of material in this temperature section, when withdrawing alternating magnetic field
Afterwards, the rapid drop in temperature of composite shape-setting phase-change material, and when temperature drops to 46 DEG C occur again a temperature decline it is slow
Platform, this is the phase transformation component crystallization process in material, shows that this material has magnetic-thermal energy conversion and thermal energy storage characteristic,
Not with super paramagnetic material, compound PCM temperature also slightly raises, it may be possible to caused by coil heating power.It can be seen that from attached drawing 6
Paraffin occurs to melt the phenomenon of leakage at 45 DEG C, and magnetic base Organic composite phase change material and PCM still keep good at 55 DEG C
Solid state, illustrate the shape stability that this material has had.
Embodiment 2
By Fe3O4@SiO2Nano-particle is changed to Fe3O4@TiO2, it is compound to obtain magnetic base organic composite shaping phase-change material, its
His condition is consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize the conversion of magnetic-thermal energy, and by heat
It can be stored in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 3
By Fe3O4@SiO2Nano-particle is changed to Fe3O4@ZrO2, it is compound to obtain magnetic base organic composite shaping phase-change material, its
His condition is consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize the conversion of magnetic-thermal energy, and by heat
It can be stored in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 4
By Fe3O4@SiO2Nano-particle is changed to CoFe2O4@SiO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 5
By Fe3O4@SiO2Nano-particle is changed to CoFe2O4@TiO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 6
By Fe3O4@SiO2Nano-particle is changed to CoFe2O4@ZrO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 7
By Fe3O4@SiO2Nano-particle is changed to NiFe2O4@SiO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 8
By Fe3O4@SiO2Nano-particle is changed to NiFe2O4@ZrO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 9
By Fe3O4@SiO2Nano-particle is changed to NiFe2O4@TiO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 10
By Fe3O4@SiO2Nano-particle is changed to MnFe2O4@SiO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 11
By Fe3O4@SiO2Nano-particle is changed to MnFe2O4@TiO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 12
By Fe3O4@SiO2Nano-particle is changed to MnFe2O4@ZrO2, it is compound to obtain magnetic base organic composite shaping phase-change material,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Embodiment 13-24
Paraffin is changed to polyethylene glycol, other conditions are consistent with embodiment 1~12.Gained magnetic base organic composite fixed phase change
Material can realize magnetic-thermal energy conversion, and by thermal energy storage in phase-change material.The material has high phase transformation enthalpy, high
Heat endurance, excellent shape stability.
Embodiment 25-36
Paraffin is changed to stearic acid, other conditions are consistent with embodiment 1~12.Gained magnetic base organic composite fixed phase change material
Material can realize magnetic-thermal energy conversion, and by thermal energy storage in phase-change material.The material has high phase transformation enthalpy, high
Heat endurance, excellent shape stability.
Embodiment 37-48
Paraffin is changed to hexadecanol, other conditions are consistent with embodiment 1~12.Gained magnetic base organic composite fixed phase change material
Material can realize magnetic-thermal energy conversion, and by thermal energy storage in phase-change material.The material has high phase transformation enthalpy, high
Heat endurance, excellent shape stability.
Embodiment 49-51
Polyurethane organic composite shaping phase-change material is changed to 100 with superparamagnetic nanoparticle mass ratio:1、100:2、
100:3, other conditions are consistent with embodiment 1~48.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy
Conversion, and by thermal energy storage in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape
Stability.
Embodiment 52-55
Polyurethane organic polymer passes through polyethylene glycol and L-lysine triisocyanate, 4,4 ', 4 "-three isocyanatophenyls
Phosphate, 4,4 ', 4 "-three isocyanatophenyl thiophosphates, 2,2 '-dimethyl -3,3,5,5- triphenyl methanes, four isocyanic acids
Ester or triphenylmethane triisocyanate crosslinking polycondensation obtain, and other conditions are consistent with embodiment 1.Gained magnetic base organic composite is determined
Shape phase-change material can realize magnetic-thermal energy conversion, and by thermal energy storage in phase-change material.The material has high enthalpy of phase change
Value, high heat endurance, excellent shape stability.
Embodiment 56-63
Phase-change material is changed into erythritol tetrastearate, four palmitate of erythritol, six palmitic acid of galactitol
Ester, six stearic acid of galactitol, glyceryl tristearate, tripalmitin, three myristins or butyl stearate,
Other conditions are consistent with embodiment 1.Gained magnetic base organic composite shaping phase-change material can realize magnetic-thermal energy conversion, and will
Thermal energy storage is in phase-change material.The material has high phase transformation enthalpy, high heat endurance, excellent shape stability.
Claims (6)
- A kind of 1. magnetic base organic composite shaping phase-change material, it is characterised in that：The composite material is by the organic setting phase of polyurethane Become material and the magnetic nano-particle being dispersed in it composition, wherein, by mass percentage,Magnetic nano-particle：1~4%, the organic shaping phase-change material of polyurethane：96~99%Wherein, magnetic nano-particle is the particle with nucleocapsid structure, wherein, karyosome footpath is 80~150nm, shell thickness for 20~ 40nm, is specially Fe3O4@SiO2、Fe3O4@TiO2、Fe3O4@ZrO2、CoFe2O4@SiO2、CoFe2O4@TiO2、CoFe2O4@ZrO2、 NiFe2O4@SiO2、NiFe2O4@TiO2、NiFe2O4@ZrO2、MnFe2O4@SiO2、MnFe2O4@TiO2、MnFe2O4@ZrO2In extremely Few one kind.
- 2. material according to claim 1, it is characterised in that：The organic shaping phase-change material of polyurethane is had by polyurethane Machine polymer with phase-change material is compound obtains,Wherein, the mass fraction of phase-change material is 50%~80% in the organic shaping phase-change material of the polyurethane, the poly- ammonia Ester organic polymer is by polyethylene glycol and L-lysine triisocyanate, 4,4 ', and 4 "-three isocyanatophenyl phosphates, 4,4 ', 4 "-three isocyanatophenyl thiophosphates, 2,2 '-dimethyl -3,3,5,5- triphenyl methanes tetraisocyanate or triphenyl first The crosslinking polycondensation of alkane triisocyanate obtains, and molecular weight polyethylene glycol is 200~20000；The phase-change material is paraffin, aliphatic acid, alcohol compound, grease.
- 3. material according to claim 2, it is characterised in that：The paraffin is paraffin of the fusing point at 20~60 DEG C；It is described Aliphatic acid is certain herbaceous plants with big flowers acid, lauric acid/dodecanoic acid, tetradecylic acid, pentadecanoic acid, palmitic acid, stearic acid；The alcohol compound is lauryl alcohol, 14 Alcohol, hexadecanol, the polyethylene glycol of molecular weight 200~20000；The grease is erythritol tetrastearate, erythritol four Palmitate, six palmitate of galactitol, six stearic acid of galactitol, glyceryl tristearate, tripalmitin, three Myristin, butyl stearate.
- 4. material according to claim 1, it is characterised in that：The magnetic nano-particle is made as follows：Xiang Han Have and 3mL ammonium hydroxide is added in the dispersion liquid of 100mg magnetic Nano clusters, after ultrasonic 5min, continue to surpass after adding 100mL absolute ethyl alcohols Sound 5min, injects the presoma of oxide, continues to stir under mechanical stirring, stops after reacting 1h, obtains magnetic nano-particle；The magnetic Nano cluster is Fe3O4、CoFe2O4、NiFe2O4、MnFe2O4；The presoma is ethyl orthosilicate, metatitanic acid Four butyl esters and tetrabutyl zirconate, the addition of presoma is 300~500 μ L.
- 5. material according to claim 1 or 2, it is characterised in that：The magnetic base organic composite shaping phase-change material is pressed The method of stating is made：Solvent dissolving is added after phase-change material is melted, in proportion with polyurethane organic polymer soln at 60 DEG C Ultrasonic mixing is uniform, adds the alcohol dispersion liquid of magnetic nano-particle, and ultrasonic mixing is uniform again, and 80 DEG C of vacuum drying 24h, obtain To magnetic base organic composite shaping phase-change material.
- 6. the preparation method of magnetic base organic composite shaping phase-change material described in claim 1, it is characterised in that：The described method includes Following step：(1) 3mL ammonium hydroxide is added into the dispersion liquid containing 100mg magnetic Nano clusters, after ultrasonic 5min, it is anhydrous to add 100mL Continue ultrasound 5min after ethanol, inject the presoma of oxide under mechanical stirring, continue to stir, stop after reacting 1h, obtain Magnetic nano-particle；(2) by average molecular weight be 200~20000 polyethylene glycol under the conditions of 80 DEG C vacuum dehydration 48h, then rely ammonia with L- Sour triisocyanate, 4,4 ', 4 "-three isocyanatophenyl phosphates, 4,4 ', 4 "-three isocyanatophenyl thiophosphates, 2,2 '- Dimethyl -3,3,5,5- triphenyl methanes tetraisocyanate or triphenylmethane triisocyanate in molar ratio 3:2 are dissolved in solvent In, and catalyst is added in a solvent, in N2Above-mentioned raw materials are placed in the there-necked flask with stirring in environment, react 6h at 80 DEG C Obtain polyurethane organic polymer；The catalyst is dibutyl tin laurate, it is 1 with polyethylene glycol mass ratio：80~150；The solvent and poly- second The mass ratio of glycol is 5~10：1；The solvent is tetrahydrofuran, dioxane, petroleum ether, acetone, butanone, chloroform, dichloro In methane, carbon tetrachloride, carbon disulfide, DMF, DMSO, benzene,toluene,xylene, nitrobenzene, chlorobenzene, hexamethylene or n-hexane 1~3 kind；(3) solvent dissolving is added after phase-change material is melted, ultrasonic mixing is equal at 60 DEG C with polyurethane organic polymer soln It is even, the alcohol dispersion liquid of magnetic nano-particle is added, ultrasonic mixing is uniform again, and 80 DEG C of vacuum drying 24h, it is organic to obtain magnetic base Composite shape-setting phase-change material,Wherein, the mass ratio of the phase-change material and polyurethane organic polymer is 5:5~8:2.
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| CN109772284A (en) * | 2019-03-21 | 2019-05-21 | 周玉芳 | A kind of graphene composite catalyst and preparation method thereof that catalytic performance is good |
| CN111253913A (en) * | 2020-02-29 | 2020-06-09 | 复旦大学 | Heat storage material based on graphene composite framework structure and preparation method thereof |
| CN113462367A (en) * | 2021-07-23 | 2021-10-01 | 苏州双碳新材料有限公司 | Optical energy and magnetic energy dual-drive composite phase change material |
| CN114015225A (en) * | 2021-09-30 | 2022-02-08 | 河北大学 | Magnetic-drive shape memory material and preparation method and application thereof |
| CN114316574A (en) * | 2022-01-25 | 2022-04-12 | 大连理工大学 | Cross-linked polyurethane-based flexible shape-stabilized phase change material film and preparation method thereof |
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