CN115322511B - Elastic film of phase-change heat storage material and preparation method thereof - Google Patents
Elastic film of phase-change heat storage material and preparation method thereof Download PDFInfo
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- CN115322511B CN115322511B CN202211115594.1A CN202211115594A CN115322511B CN 115322511 B CN115322511 B CN 115322511B CN 202211115594 A CN202211115594 A CN 202211115594A CN 115322511 B CN115322511 B CN 115322511B
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- Prior art keywords
- monomer
- phase
- emulsion
- heat storage
- elastic film
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- 238000005338 heat storage Methods 0.000 title claims abstract description 31
- 239000011232 storage material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 144
- 239000000839 emulsion Substances 0.000 claims abstract description 58
- -1 mixing Substances 0.000 claims abstract description 48
- 239000004698 Polyethylene Chemical group 0.000 claims abstract description 29
- 229920000573 polyethylene Chemical group 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000002562 thickening agent Substances 0.000 claims abstract description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 7
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 4
- 230000008859 change Effects 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 11
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 239000012987 RAFT agent Substances 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 239000002775 capsule Substances 0.000 abstract description 7
- 239000011162 core material Substances 0.000 abstract description 6
- 229920001400 block copolymer Polymers 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 24
- 239000012071 phase Substances 0.000 description 20
- 239000002313 adhesive film Substances 0.000 description 14
- 239000011257 shell material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012782 phase change material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Abstract
The invention discloses a phase-change heat storage material elastic membrane and a preparation method thereof, comprising the following steps: step 1, mixing phase-change wax and a monomer A to form an oily solution; step 2, adding the oily solution into an aqueous solution containing RAFT to disperse to obtain miniemulsion; step 3, deoxidizing the miniemulsion and then heating up for reaction; step 4, adding the monomer B into the reaction emulsion to continue the reaction emulsion; step 5, adding a wetting agent and a thickening agent into the emulsion, mixing, and coating the emulsion on a release film to obtain an elastic film; the monomer A is ethyl acrylate, and the monomer B is styrene and polyethylene monomer. According to the invention, phase-change wax is used as a core material, and the emulsion is coated by using an acrylic ester block copolymer with an AB type structure as a capsule emulsion of an outer shell layer to finally prepare the aqueous phase-change heat storage elastic film with elasticity higher than 300% and high breaking elongation, high breaking strength, high temperature resistance and high rebound resilience.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a phase-change heat storage material elastic membrane and a preparation method thereof.
Background
The phase change material (PCM-Phase Change Material) refers to a substance that changes a state of a substance and can provide latent heat without changing a temperature. The process of converting physical properties is called a phase change process, and the phase change material absorbs or releases a large amount of latent heat, so that the phase change material can be widely used as a high-efficiency heat energy storage and temperature control medium in the fields of electronic device heat management, building energy conservation, waste heat recovery, cold chain transportation, solar energy-heat energy conversion/storage, battery heat management and the like.
In the prior art, the phase change material is generally microencapsulated and encapsulated, for example, CN1695788A discloses a technology for synthesizing a phase change energy storage microcapsule by adopting an emulsion core-shell polymerization method, wherein an oil-soluble organic phase change material is taken as a core, a vinyl or divinyl free radical monomer is taken as a shell polymer, water is taken as a polymerization stop, and the phase change microcapsule is obtained by emulsion core-shell polymerization encapsulation, so that the phase change energy storage microcapsule is suitable for mixing with textile materials and the like.
CN102127395a discloses a paraffin phase-change energy-storage material and a preparation method thereof, paraffin is used as a core material, high-density polyethylene is used as a supporting material, and a microcapsule phase-change material is obtained by a fusion method, so that the problems of low paraffin doping amount, poor energy storage performance, easiness in leakage and the like in the phase-change material are solved.
However, the traditional phase change heat storage material generally utilizes the solid-liquid phase change behavior to store energy and control temperature, the finally prepared product is mostly in a powder solid state, the shell material of the finally phase change capsule is not flexible due to high rigidity, and the finally prepared product cannot be directly applied to the thermal management of a flexible wearable device, is difficult to directly prepare an elastic membrane, and has good flexibility, elasticity and good mechanical property.
Disclosure of Invention
Aiming at the problem that the flexibility and the rigidity of the phase-change energy storage material are not compatible, the invention provides a phase-change heat storage elastic film applicable to flexible wearable devices, which takes phase-change wax as a core material, takes an acrylic ester segmented copolymer with an AB structure prepared by a miniemulsion RAFT polymerization method as a capsule emulsion of an outer shell layer, and finally prepares the water-based phase-change heat storage elastic film with the elasticity higher than 300 percent, high breaking strength, high temperature resistance and high rebound resilience after the emulsion is dried by means of coating and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a phase-change heat storage material elastic film comprises the following steps:
step 1, mixing 30-70 parts by weight of phase change wax and 22.5-66.5 parts by weight of A monomer except polyethylene monomer to form oily solution; dissolving 0.2-2.0 parts by weight of RAFT reagent in 150-400 parts by weight of water to obtain an aqueous solution containing RAFT;
step 2, adding the oily solution into an aqueous solution containing RAFT, stirring and dispersing for 0.5-2 hours to obtain a coarse emulsion, and further shearing and crushing the coarse emulsion to obtain a miniemulsion;
step 3, the temperature of the miniemulsion is raised to 45-95 ℃ after deoxidization, a water-soluble initiator is added, a pH regulator is added after reaction for 30-90 min, a polyethylene monomer in the monomer A is added after continuous reaction for 2-4h, and the continuous reaction is carried out for 2-4h;
step 4, adding 1.5-17.5 parts by weight of B monomer into the reaction emulsion in the step 3, adding a water-soluble initiator after reacting for 2-6 hours, continuing to react for 1-4 hours, cooling to room temperature, and filtering to obtain emulsion;
step 5, adding a wetting agent and a thickening agent into the emulsion, mixing, coating the emulsion on a release film, and drying to obtain the phase-change heat storage material elastic film;
the monomer A comprises main monomer ethyl acrylate, water-soluble monomer accounting for 0-5% of the total amount of the monomer A, functional monomer accounting for 0-25% of the total amount of the monomer A and polyethylene monomer accounting for 0.1-5% of the total amount of the monomer A;
the B monomer comprises 80-99% of styrene and 1-20% of polyethylene monomer by mass ratio.
According to the invention, the phase change heat storage material elastic film is obtained by a miniemulsion reversible addition fragmentation chain transfer free radical polymerization (RAFT) method, the RAFT emulsion polymerization of the miniemulsion is adopted, the controllable growth of a polymerized monomer from outside to inside can be realized, phase change wax is used as a core material, an acrylic ester segmented copolymer with an AB structure is used as a shell layer, a block formed by taking an A monomer as a soft monomer is arranged at the outermost layer of the shell layer and is used as an elastic layer, excellent elasticity and low temperature resistance of a polymer shell are provided, a B monomer is a hard monomer, a microphase separation structure is formed between the B monomer and the A block in the polymer, and excellent mechanical strength and high temperature resistance of the segmented copolymer are provided as physical crosslinking points. The phase change material film has apparent solid-solid phase change characteristics, the phase change enthalpy and the phase change temperature are adjustable within the temperature range of 5-80 ℃, and stable phase change performance is still shown after 1000 times of cold and hot circulation from-20 ℃ to 80 ℃, so that the performance of the elastic film of the phase change material is kept intact. In addition, the phase change material elastic film has excellent elasticity and flexibility, is foldable, can be used for preparing a large-size film, and can also be used for directly spraying the obtained phase change heat storage material aqueous emulsion on a special-shaped surface or a position inconvenient to construct, and after the phase change material aqueous emulsion is dried, a layer of compact heat storage elastic coating is formed on the surface of equipment.
The phase-change temperature of the phase-change wax in the aqueous phase-change heat storage elastic film is 20-80 ℃, the enthalpy value of the phase-change wax is not lower than 180KJ/KG, and the mass ratio of the phase-change wax to the total monomer of the polymer is 3:7-7:3.
The monomer A accounts for 75-95% of the total mass of all the polymerization monomers; preferably, the A monomer accounts for 80-90% of the total mass of all the polymerized monomers, the high content of the B monomer can lead to high system hardness and reduced elasticity, and the excessively low content can lead to the stickiness of a final product, weak mechanical strength and easy occurrence of leakage of phase-change wax.
Preferably, the water-soluble monomer in the A monomer accounts for 0-2% of the total amount of the A monomer, and the polyethylene monomer accounts for 0.5-2% of the total amount of the A monomer; the functional monomer accounts for 5-25% of the total amount of the A monomer;
further preferably, the water-soluble monomer in the monomer A accounts for 0.5-2% of the total amount of the monomer A, and the polyethylene monomer accounts for 0.5-2% of the total amount of the monomer A; the functional monomer accounts for 15-25% of the total amount of the A monomer;
the water-soluble monomer comprises one or more than one of acrylic acid, methacrylic acid, beta-acryloxypropionic acid and itaconic acid, and can further provide hydrogen bonding force along with the introduction of the water-soluble monomer, so that the strength and rebound resilience of a final film can be improved, and the glass transition temperature of an A block is improved very little due to small addition amount, so that the influence on the low-temperature performance of the film is small;
the functional monomer comprises one or more of styrene, acrylonitrile, methyl acrylate, methyl methacrylate and ethyl methacrylate, and the performances of elongation at break, breaking strength, surface hardness of the elastic film and the like of the final elastic film can be adjusted to a certain extent through the addition of the functional monomer.
The polyethylene monomer comprises at least one of Ethylene Glycol Dimethacrylate (EGDMA), allyl methacrylic acid, ethylene glycol diacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane triacrylate, maleic diene acrylate, 1, 6-hexanediol di (meth) acrylate and divinylbenzene. The polyethylene monomer can improve the crosslinking density of the system and the coating rate of the phase change material. The crosslinking density is improved, the total monomer usage amount is reduced, the mechanical strength of the shell is improved, and the thickness is reduced.
The monomer B accounts for 5-25% of the total mass of all the polymerization monomers; preferably, the B monomer comprises 10 to 20% of the total mass of all the polymerized monomers.
Further preferably, the B monomer comprises 85-95% of styrene and 5-15% of polyethylene monomer by mass ratio.
Preferably, the polyethylene monomer in the B monomer comprises at least one of Ethylene Glycol Dimethacrylate (EGDMA), allyl methacrylic acid, ethylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol tetramethyl acrylate, trimethylolpropane triacrylate, maleic diene acrylate, 1, 6-hexanediol di (meth) acrylate, divinylbenzene;
the polyethylene monomer in the B block is preferably divinylbenzene with high glass transition temperature, and the monomer is a hard monomer, has high glass transition temperature, ensures mechanical property and high temperature property, and can improve crosslinking density, thereby improving the coating rate of the phase change material.
The block copolymer with the AB structure taking ethyl acrylate and styrene as main monomers in the polymer is taken as a shell layer, so that the phase-change wax can be well ensured not to permeate and leak under the conditions of stretching process and temperature change, the film of the shell layer becomes more compact along with the improvement of the crosslinking density, more core material phase-change wax can be ensured to be added in the capsule, and the phase-change latent heat of the heat storage elastic film is improved.
The addition amount of the water-soluble initiator in the step 3 and the step 4 is 0.001 to 0.07 weight part respectively, and the pH value of the system reaches 6 to 8 after the pH regulator is added;
the addition amount of the wetting agent and the thickening agent in the step 5 is 0.1-2 parts by weight respectively.
Preferably, a high heat conduction material is further added into the emulsion obtained in the step 4, wherein the addition amount of the high heat conduction material is 0-20% of the total weight of the emulsion.
The high heat conduction material comprises any one or more of graphite powder, graphene, expandable graphite, carbon nano tubes, nano ceramics, boron nitride, silicon carbide, nano-grade diamond powder and superfine aluminum oxide microspheres.
The RAFT reagent has a chemical structural formula as follows:
wherein: x is alkylthio or alkyl; m is styrene or an acrylate monomer; z is an acrylic acid monomer or a methacrylic acid monomer; y is isopropyl or acetic acid; n1 and n2 are average polymerization degrees, n1=3 to 15, n2=10 to 50;
further preferably, X is C8-C16 alkylthio; m is styrene, butyl acrylate, methyl methacrylate; n1=4-10, n2=15-30.
The methacrylate monomer comprises any one of methyl methacrylate, acrylonitrile, vinyl acetate, ethyl methacrylate, butyl acrylate, isooctyl acrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate;
the water-soluble initiator includes, but is not limited to, any one of ammonium persulfate, potassium persulfate, hydrogen peroxide and derivatives thereof, VA-061, VA-044, V501, V50;
the pH regulator is a conventional acid-base regulator, including but not limited to any one or more of sodium hydroxide, sodium bicarbonate, ammonia water, ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and triethylamine;
the wetting agent and the thickening agent are used for the conventional acrylate emulsion in the industry and are not described in detail herein.
The shearing and crushing adopts a strong shearing force device, including but not limited to an ultrasonic crusher, a high-pressure homogenizer, a supergravity generating device and the like, the coarse emulsion can reach nano-level liquid drop micelle after passing through the strong shearing force device, and nano-level emulsion particles are further prepared through polymerization.
The invention also provides the phase-change heat storage material elastic film prepared by the preparation method, which has excellent elongation at break, very good flexibility and good mechanical strength, and can be applied to various flexible devices as an energy storage material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the phase change wax capsule obtained by adopting the miniemulsion RAFT active emulsion polymerization mode, as the shell layer is the acrylic ester block copolymer, the polymer of the shell layer forms a film to form a continuous phase and the polymer has a nano-scale microphase separation structure, so that the shell layer has excellent mechanical property and elongation at break and also has excellent high and low temperature resistance, and still has excellent mechanical property and elasticity after long-time high and low temperature alternating environment.
(2) The ethyl acrylate is adopted as a main soft monomer of the acrylic ester block copolymer, namely, the elasticity of an elastic film of the water-based phase-change heat storage elastic film is ensured, and the copolymer of the ethyl acrylate and the styrene is adopted as a main monomer, has very good performance for preventing the leakage of paraffin, and ensures that the leakage of phase-change wax can not occur in long-time use.
(3) Overcomes the defect of the traditional rigid phase change heat storage material, so that the material has excellent elasticity and flexibility, can be folded and can be used for preparing large-size films.
(4) The emulsion obtained in the preparation step 5 can be directly applied to various flexible curved surfaces such as special-shaped surfaces, complex surfaces and the like by adopting modes such as spraying, brushing and the like, and the high-elasticity compact heat storage film is directly obtained on the surface of the emulsion after the emulsion is dried.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
In the embodiment of the invention, the RAFT reagent is adopted for the inventor to synthesize by oneself to obtain other commodities which are all purchased in the market, and the structural formula of the RAFT reagent is shown as follows:
the strong shearing device of the miniemulsion is a Nano DeBEE experimental ultra-high pressure homogenizer with the model of Nano DeBEE45-4;
acrylic monomers, styrene, acrylonitrile, etc. are derived from micarin reagent.
The polyethylene monomer in the monomer A adopts Ethylene Glycol Dimethacrylate (EGDMA), and the polyethylene monomer in the monomer B adopts divinylbenzene from a microphone reagent.
The wetting agent is OT-75 of Soxhlet;
the thickener is a Pasteur high-efficiency acrylic acid-base swelling thickener Rheovis AS 1125;
the phase-change wax is selected from FPC36 of Zhejiang Royal chemical company, and has a phase-change temperature of 36 ℃ and a phase-change enthalpy of 200KJ/KG.
The double column tensile machine is KJ-1066A of Guangdong Instrument Co.
Emulsion film forming mode:
according to the requirements of GBT528-2009 'measurement of tensile stress strain property of vulcanized rubber or thermoplastic rubber', a certain amount of prepared emulsion is added into a dumbbell-shaped tetrafluoro disc, film formation is carried out for 5-7 days at room temperature, the film is taken out from the tetrafluoro disc, further dried for 2 hours at 60 ℃, dried for 30 minutes at 120 ℃ under high vacuum, and the film is taken out and cooled.
Mechanical property test: and 3 adhesive films are taken, and the adhesive film breaking strength and breaking elongation are tested by a tensile machine according to the GBT528-2009 standard test requirements.
And (3) cold and hot cycle testing of the adhesive film: and (3) taking 3 adhesive films, placing the adhesive films in a cold and hot impact tester to circulate for 1000 times at the temperature of between 20 ℃ below zero and 80 ℃, taking out the adhesive films to observe the surfaces of the films, judging whether phase-change wax leaks or not, and testing the mechanical properties.
Examples 1 to 3
The following preparation was carried out according to the contents of the components in Table 1:
step 1, dissolving and mixing phase-change wax and a monomer A except a polyethylene monomer to obtain an oily solution; adding 0.5 weight part of RAFT reagent into 300 weight parts of water, and stirring until the RAFT reagent is completely dissolved;
step 2, adding the oily solution obtained in the step 1 into an aqueous solution containing RAFT, mechanically stirring and dispersing for 1h to obtain a coarse emulsion, and further crushing the coarse emulsion by using a homogenizer for 3 times to obtain a miniemulsion;
step 3, raising the temperature of the miniemulsion obtained in the step 2 to 70 ℃ after deoxidizing in a reactor, adding 0.015 part by weight of potassium persulfate, reacting for 30min, adding 0.2 part by weight of sodium hydroxide until the pH of the system is 6.8, continuing to react for 2h, adding polyethylene monomer EGDMA in the monomer A, and continuing to react for 2h;
and step 4, adding the B monomer into the reaction emulsion in the step 3, reacting for 4 hours, continuously adding 0.015 part by weight of potassium persulfate, continuously reacting for 2 hours, cooling to room temperature, and filtering to obtain the product emulsion.
And 5, adding 0.4 part by weight of OT-75 and 0.2 part by weight of AS 1125 into the emulsion, mixing, coating the emulsion on a release film, and drying to obtain the phase-change heat storage material elastic film.
TABLE 1 raw material compositions of examples 1-3
Examples 4 to 6
The following preparation was carried out according to the contents of the components in Table 2:
dissolving and mixing phase-change wax and a monomer A except a polyethylene monomer to obtain an oily solution; adding 0.3 weight part of RAFT reagent into 300 weight parts of water, and stirring until the RAFT reagent is completely dissolved;
step 2, adding the oily solution obtained in the step 1 into an aqueous solution containing RAFT, mechanically stirring and dispersing for 1h to obtain a coarse emulsion, and further crushing the coarse emulsion by using a homogenizer for 3 times to obtain a miniemulsion;
step 3, raising the temperature of the miniemulsion obtained in the step 2 to 70 ℃ after deoxidizing in a reactor, adding 0.09 weight part of potassium persulfate, reacting for 30min, adding 0.12 weight part of sodium hydroxide until the pH value of the system is 7.0, continuing to react for 1.5h, adding polyethylene monomer EGDMA in the monomer A, and continuing to react for 2h;
and step 4, adding the B monomer into the reaction emulsion in the step 3, reacting for 3 hours, continuously adding 0.015 part by weight of potassium persulfate, continuously reacting for 2 hours, cooling to room temperature, and filtering to obtain the product emulsion.
And 5, adding 0.4 part by weight of OT-75 and 0.2 part by weight of AS 1125 into the emulsion, mixing, coating the emulsion on a release film, and drying to obtain the phase-change heat storage material elastic film.
TABLE 2 raw material compositions for examples 4-6
Comparative examples 1 to 2
In comparative example 1, the capsule shell structure was changed to a random polymer without designing the B block, and the synthesis was carried out in the following synthesis steps, and the specific monomer addition amounts were prepared as shown in table 3:
in comparative example 2, the preparation process of the B block was not designed, and all the monomer ratio composition was identical to all the monomer number ratios in example 1, but the B monomer composition was added to the a monomer to prepare only the a block portion, and the structure was changed to a random polymer synthesis mode according to the following synthesis procedure, and the specific monomer addition amount was prepared according to table 3:
comparative examples 1-2 were prepared by:
step 1, dissolving and mixing phase-change wax and a monomer A except a polyethylene monomer in a list to obtain an oily solution; adding 0.5 weight part of RAFT reagent into 300 weight parts of water, and stirring until the RAFT reagent is completely dissolved;
step 2, adding the oily solution obtained in the step 1 into an aqueous solution containing RAFT, mechanically stirring and dispersing to obtain a coarse emulsion, and further crushing the coarse emulsion for 3 times by using a homogenizer to obtain a miniemulsion;
step 3, raising the temperature of the miniemulsion obtained in the step 2 to 70 ℃ after deoxidizing in a reactor, adding 0.015 part by weight of potassium persulfate, reacting for 30min, adding 0.2 part by weight of sodium hydroxide until the pH of the system is 6.8, continuing to react for 2h, adding polyethylene monomer EGDMA in the monomer A, and continuing to react for 2h; continuously adding 0.015 part by weight of potassium persulfate, continuously reacting for 2 hours, cooling to room temperature, and filtering to obtain a product emulsion.
And 4, adding 0.4 part by weight of OT-75 and 0.2 part by weight of AS 1125 into the emulsion, mixing, coating the emulsion on a release film, and drying to obtain the phase-change heat storage material elastic film.
Comparative example 3
The amount of the A monomer of example 1 was adjusted to 70% of the total monomer amount and the amount of the B block was adjusted to 30% of the total polymerized monomer amount in the same manner as in example 1.
TABLE 3 composition of raw materials for comparative examples 1-3
Emulsion film forming mode and elastic film performance evaluation mode:
according to the requirements of GBT528-2009 "measurement of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber", the emulsions prepared in examples 1-6 were added to a dumbbell-shaped tetrafluoro pan, and the films were formed into films at room temperature for 5-7 days, taken out of the tetrafluoro pan, further dried at 60℃for 2 hours, dried at 120℃under high vacuum for 30 minutes, taken out and cooled, and subjected to film observation and mechanical property test, and the results are shown in Table 4.
Elastic film rebound resilience test mode:
the unstretched elastic film was marked in the middle and the length (L 0 ) Pulling the adhesive film by hand until the elongation of the adhesive film is 200-250%, loosening the hand, and measuring the length (L) of the adhesive film at the marking section after rebound at the fastest speed (within 1 second or less) 1 ) Representation of rebound rate calculation:
wherein: l (L) 0 For the length of the original spline L 1 The length of the sample strip which is instantly recovered after 200-250% of sample strip stretching. In the examples of the present invention, the rebound resilience of the sample (spline) is represented by the rebound resilience R value, and the closer R is to 100%, the better the rebound resilience of the spline is represented, and if less than 95% is represented by the insufficient rebound resilience.
As can be seen from the data in Table 4, examples 1-3 have 50% loading of phase change wax and examples 4-6 have 70% loading, which both maintain a final film surface finish and no leakage of phase change wax, while maintaining good film elasticity and strength. Examples 4-6 showed an increase in film bulk strength with an increase in B monomer as a hard monomer, but a significant decrease in elongation at break, as compared to examples 1-3. After cold and hot impact, the phase-change elastic film basically keeps the same performance, which shows that the elastic film has very good leakage blocking effect on the phase-change wax, and simultaneously, due to the design of an AB structure, the adhesive film has very good elasticity, rebound resilience and high and low temperature resistance.
The phase change wax loading of comparative examples 1-3 was 50%, the surface was smooth and free of phase change wax leakage, but the film surfaces of comparative examples 1, 2 were severe in tackiness, and poor in mechanical strength and elasticity, especially severe in rebound, mainly due to the fact that the entire capsule shell was a random copolymer segment of ethyl acrylate as the main monomer and the glass transition temperature was low, and the hard monomer of the B monomer was not used as a support, and the block structure was lacking.
Comparative example 3 employed a higher B block component, compared to example 1, with a significant increase in break strength with increasing B block, but a significant decrease in elongation at break and rebound, with too low a rebound being unsuitable for use in situations where film stretching and film recovery are required frequently.
TABLE 4 film Forming Performance test of emulsions prepared in examples 1-6 and comparative examples 1-3
The emulsions prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to cold and hot cycle test of the adhesive film after being formed into films, and after being put into a cold and hot impact tester and cycled at a temperature of-20 to 80 ℃ for 1000 times, the adhesive film was taken out to observe the film surface, whether phase-change wax was leaked or not, and mechanical property test was performed, and the results are shown in table 5.
TABLE 5 Performance test after film-forming neck Cold and Hot cycle of emulsions prepared in examples 1-6 and comparative examples 1-3
As can be seen from Table 5, after 1000 cycles of cold and hot impact tests, the adhesive films of examples 1-6 were still smooth in surface and free from leakage of phase-change wax, and meanwhile, the mechanical properties, elongation at break and rebound resilience were all good, but the phase-change wax on the surfaces of comparative examples 1-2 had been remarkably leaked after cold and hot impact, the adhesive films were not substantially molded, and it was difficult to test the mechanical properties, elasticity and the like again.
Claims (8)
1. The preparation method of the elastic film of the phase-change heat storage material is characterized by comprising the following steps:
step 1, mixing 30-70 parts by weight of phase change wax and 22.5-66.5 parts by weight of A monomer except polyethylene monomer to form oily solution; dissolving 0.2-2.0 parts by weight of RAFT reagent in 150-400 parts by weight of water to obtain an aqueous solution containing RAFT;
step 2, adding the oily solution into an aqueous solution containing RAFT, stirring and dispersing for 0.5-2 hours to obtain a coarse emulsion, and further shearing and crushing the coarse emulsion to obtain a miniemulsion;
step 3, the temperature of the miniemulsion is raised to 45-95 ℃ after deoxidization, a water-soluble initiator is added, a pH regulator is added after reaction for 30-90 min, a polyethylene monomer in the monomer A is added after continuous reaction for 2-4h, and the continuous reaction is carried out for 2-4h;
step 4, adding 1.5-17.5 parts by weight of B monomer into the reaction emulsion in the step 3, adding a water-soluble initiator after reacting for 2-6 hours, continuing to react for 1-4 hours, cooling to room temperature, and filtering to obtain emulsion;
step 5, adding a wetting agent and a thickening agent into the emulsion, mixing, coating the emulsion on a release film, and drying to obtain the phase-change heat storage material elastic film;
the monomer A comprises main monomer ethyl acrylate, water-soluble monomer accounting for 0-5% of the total mass of the monomer A, functional monomer accounting for 0-25% of the total mass of the monomer A and polyethylene monomer accounting for 0.1-5% of the total mass of the monomer A;
the B monomer comprises 80-99% of styrene and 1-20% of polyethylene monomer by mass ratio;
the monomer A accounts for 75-95% of the total mass of all the polymerization monomers, and the monomer B accounts for 5-25% of the total mass of all the polymerization monomers;
the water-soluble monomer comprises one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
the functional monomer comprises one or more of styrene, acrylonitrile, methyl acrylate, methyl methacrylate and ethyl methacrylate;
the polyethylene monomer comprises at least one of ethylene glycol dimethacrylate, allyl methacrylic acid, ethylene glycol diacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane triacrylate, maleic acid diene acrylate, 1, 6-hexanediol dimethacrylate and divinylbenzene.
2. The method for preparing the elastic film of the phase-change heat storage material according to claim 1, wherein the phase-change temperature of the phase-change wax in the elastic film of the phase-change heat storage material is 20-80 ℃, the enthalpy value of the phase-change wax is not lower than 180KJ/KG, and the mass ratio of the phase-change wax to the total monomer of the polymer is 3:7-7:3.
3. The method for preparing the elastic film of the phase-change heat storage material according to claim 1, wherein the water-soluble monomer in the monomer A accounts for 0-2% of the total mass of the monomer A, and the polyethylene monomer accounts for 0.5-2% of the total mass of the monomer A; the functional monomer accounts for 5-25% of the total amount of the A monomer;
the monomer B comprises 85-95% of styrene and 5-15% of polyethylene monomer by mass ratio.
4. The method for preparing the elastic film of the phase-change heat storage material according to claim 1, wherein the polyethylene monomer in the A monomer is ethylene glycol dimethacrylate; the polyethylene monomer in the B monomer is divinylbenzene.
5. The method for preparing an elastic film of a phase-change heat storage material according to claim 1, wherein the addition amount of the water-soluble initiator in the step 3 and the step 4 is 0.001-0.07 weight part respectively, and the pH of the system reaches 6-8 after the pH regulator is added;
and/or, the addition amount of the wetting agent and the thickening agent in the step 5 is 0.1-2 parts by weight respectively;
and/or adding a high heat conduction material into the emulsion obtained in the step 4, wherein the addition amount of the high heat conduction material is 0-20% of the total weight of the emulsion.
6. The method according to claim 5, wherein the high thermal conductivity material comprises any one or more of graphite powder, graphene, expandable graphite, carbon nanotubes, nanoceramics, boron nitride, silicon carbide, nanoscale diamond powder, and nanosilica.
7. The method for preparing an elastic film of a phase change heat storage material according to claim 1, wherein the RAFT agent has a chemical structural formula:
wherein: x is alkylthio or alkyl; m is styrene or an acrylate monomer; z is an acrylic acid monomer or a methacrylic acid monomer; y is isopropyl or acetic acid; n1 and n2 are average polymerization degrees, n1=3 to 15, n2=10 to 50;
and/or the water-soluble initiator comprises any one of ammonium persulfate, potassium persulfate, hydrogen peroxide and derivatives thereof, VA-061, VA-044, V501 and V50;
and/or the pH regulator is a conventional acid-base regulator, and comprises any one or more of sodium hydroxide, sodium bicarbonate, ammonia water, ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and triethylamine.
8. The phase change heat storage material elastic film produced by the production method according to any one of claims 1 to 7.
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|---|---|---|---|---|
| CN1693317A (en) * | 2005-05-11 | 2005-11-09 | 浙江大学 | Process for preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent |
| CN101544712A (en) * | 2009-04-02 | 2009-09-30 | 浙江大学 | Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization |
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| CN115322511A (en) | 2022-11-11 |
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