CN115322511A - Phase-change heat storage material elastic film and preparation method thereof - Google Patents
Phase-change heat storage material elastic film and preparation method thereof Download PDFInfo
- Publication number
- CN115322511A CN115322511A CN202211115594.1A CN202211115594A CN115322511A CN 115322511 A CN115322511 A CN 115322511A CN 202211115594 A CN202211115594 A CN 202211115594A CN 115322511 A CN115322511 A CN 115322511A
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- monomer
- phase
- emulsion
- heat storage
- change
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- 238000005338 heat storage Methods 0.000 title claims abstract description 34
- 239000011232 storage material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000006243 chemical reaction Methods 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
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- 238000003756 stirring Methods 0.000 claims description 8
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
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- 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-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
- 229920002554 vinyl polymer Polymers 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
- 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 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
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- 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
- 230000001502 supplementing effect Effects 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- 239000012987 RAFT agent Substances 0.000 claims 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
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Classifications
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a phase-change heat storage material elastic membrane and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, mixing phase-change wax and A monomer to form an oily solution; step 2, adding the oily solution into an aqueous solution containing RAFT to obtain a miniemulsion through dispersion; step 3, deoxidizing the miniemulsion, and then heating for reaction; step 4, adding a monomer B into the reaction emulsion to continue reacting the 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. The invention takes the phase-change wax as the core material, and the acrylic ester segmented copolymer with the AB type structure as the capsule emulsion of the shell layer, and the aqueous phase-change heat storage elastic film with the elasticity higher than 300 percent of elongation at break, high breaking strength, high and low temperature resistance and high resilience is finally prepared by coating the emulsion.
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
A Phase Change Material (PCM-Phase Change Material) refers to a substance that changes the state of a substance at a constant temperature and can provide latent heat. The process of converting the physical property is called a phase change process, and at the moment, the phase change material can absorb or release a large amount of latent heat and can be widely applied to 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 as a high-efficiency heat energy storage and temperature control medium.
In the prior art, phase change materials are usually microencapsulated to encapsulate the phase change materials, for example, CN1695788A discloses a technology for synthesizing phase change energy storage microcapsules 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 radical monomer is taken as a shell polymer, water is taken as a polymerization cut-off, and the phase change microcapsules are obtained by emulsion core-shell polymerization and encapsulation, so that the phase change microcapsules are suitable for mixing with textile materials and the like.
CN102127395A discloses a paraffin phase change energy storage material and a preparation method thereof, wherein a melting method is adopted to obtain a microcapsule phase change material by taking paraffin as a core material and high-density polyethylene as a support material, so that the problems of low paraffin doping amount, poor energy storage performance, easy 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, and the shell material of the final phase change capsule has no flexibility due to large rigidity, cannot be directly applied to the thermal management of a flexible wearable device, is difficult to directly prepare the shell material into an elastic membrane, and has good flexibility and elasticity and good mechanical property.
Disclosure of Invention
The invention provides a phase-change heat storage elastic membrane suitable for a flexible wearable device aiming at the problem that the flexibility and the rigidity of a phase-change energy storage material cannot be obtained simultaneously, wherein phase-change wax is used as a core material, an acrylate block copolymer with an AB type structure prepared by a miniemulsion RAFT polymerization method is used as a capsule emulsion of an outer shell layer, and the aqueous phase-change heat storage elastic membrane with the elasticity higher than 300% of breaking elongation, high breaking strength, high and low temperature resistance and high resilience is finally prepared after the emulsion is dried by coating and other modes.
In order to achieve the purpose, the invention adopts the technical scheme that:
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 monomer A 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 h to obtain a coarse emulsion, and further shearing and crushing the coarse emulsion to obtain a fine emulsion;
step 3, heating the miniemulsion to 45-95 ℃ after deoxidizing, adding a water-soluble initiator, adding a pH regulator after reacting for 30-90 min, continuing to react for 2-4h, adding a polyethylene monomer in the monomer A, and continuing to react for 2-4h;
step 4, adding 1.5-17.5 parts by weight of B monomer into the reaction emulsion obtained in the step 3, reacting for 2-6h, supplementing a water-soluble initiator, continuing to react for 1-4h, cooling to room temperature, and filtering to obtain an 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 a main monomer ethyl acrylate, and also comprises a water-soluble monomer accounting for 0-5% of the total weight of the monomer A, a functional monomer accounting for 0-25% of the total weight of the monomer A, and a polyethylene monomer accounting for 0.1-5% of the total weight of the monomer A;
the B monomer comprises 80-99% of styrene and 1-20% of polyethylene monomer by mass.
The invention obtains a phase-change heat storage material elastic membrane by a miniemulsion reversible addition fragmentation chain transfer radical polymerization (RAFT) method, adopts RAFT emulsion polymerization of miniemulsion to realize controllable growth of a polymerization monomer from outside to inside, takes phase-change wax as a core material, takes an acrylate block copolymer with an AB structure as a shell layer, takes a monomer A as a soft monomer to form a block at the outermost layer of the shell layer, and provides an elastic layer with excellent elasticity and low temperature resistance of the polymer shell layer, and takes a monomer B as a hard monomer to form a micro-phase separation structure with the block A in a polymer, and provides excellent mechanical strength and high temperature resistance of the block copolymer as a physical cross-linking point. 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 ℃, the stable phase-change performance is still shown after 1000 times of cold-heat circulation from-20 ℃ to 80 ℃, and the completeness of the performance of the phase-change material elastic film is kept. In addition, the phase-change material elastic membrane has excellent elasticity and flexibility, can be folded, can be used for preparing a large-size membrane, and can also be used for directly spraying the obtained phase-change heat storage material water-based emulsion on a special-shaped surface or a position inconvenient for construction, and after drying, a 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 membrane 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.
The monomer A accounts for 75-95% of the total mass of all the polymerized monomers; preferably, the monomer A accounts for 80-90% of the total mass of all the polymerized monomers, the high content of the monomer B can cause high system hardness and reduced elasticity, and the low content can cause the final product to be sticky and have weak mechanical strength and easy phase-change wax leakage.
Preferably, the water-soluble monomer in the monomer A accounts for 0-2% 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 5-25% of the total amount of the monomer A;
more 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 monomer A;
the water-soluble monomer comprises one or more of acrylic acid, methacrylic acid, beta-acryloxypropionic acid and itaconic acid, and can further provide hydrogen bond force with the introduction of the water-soluble monomer, so that the strength and resilience of the final film can be improved, and the influence on the low-temperature performance of the film is small due to the small addition amount of the water-soluble monomer on the glass transition temperature of the A block;
the functional monomer comprises one or more of styrene, acrylonitrile, methyl acrylate, methyl methacrylate and ethyl methacrylate, and the properties of the final elastic film such as elongation at break, breaking strength, surface hardness of the elastic film and the like can be adjusted to a certain degree through the addition amount of the functional monomer.
The polyvinyl 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 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 can improve 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 to 25 percent of the total mass of all the polymerized monomers; preferably, the B monomer comprises 10-20% of the total mass of all polymerized monomers.
More preferably, the B monomer comprises 85-95% of styrene and 5-15% of polyethylene monomer by mass.
Preferably, the polyvinyl 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 tetramethacrylate, trimethylolpropane triacrylate, maleic acid diene acrylate, 1, 6-hexanediol di (meth) acrylate, divinylbenzene;
the polyethylene monomer in the B block is preferably divinylbenzene with high glass transition temperature, the monomer is a hard monomer, has high glass transition temperature, ensures the mechanical property and high temperature property and can improve the crosslinking density, thereby improving the coating rate of the phase-change material.
The block copolymer of AB structure with ethyl acrylate and styrene as main monomers in the polymer is taken as a shell layer, so that the phase-change wax can not be leaked by permeation in the stretching process and under the condition of temperature change, the film of the shell layer becomes more compact along with the increase of cross-linking density, more core material phase-change wax can be added into the capsule, and the phase-change latent heat of the heat storage elastic film is increased.
In the step 3 and the step 4, the addition amount of the water-soluble initiator is 0.001-0.07 part by weight respectively, and the pH of the system reaches 6-8 after the pH regulator is added;
in the step 5, the addition amount of the wetting agent and the thickening agent is 0.1-2 parts by weight respectively.
Preferably, the emulsion obtained in step 4 is further added with a high thermal conductive material, and the addition amount of the high thermal conductive 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-scale diamond powder and superfine aluminum oxide microspheres.
The RAFT reagent has a chemical structural general 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 an isopropenyl or acetoxy group; n1 and n2 are average polymerization degrees, n1= 3-15, and n2= 10-50;
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 comprises but is not limited to any one of ammonium persulfate, potassium persulfate, hydrogen peroxide and derivatives thereof, VA-061, VA-044, V501 and V50;
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;
the wetting agent and the thickening agent are used in the industry of conventional acrylate emulsion and are not described in detail herein.
The shearing and crushing adopts strong shearing force equipment, 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-scale liquid drop micelles after passing through the strong shearing force equipment, and the nano-scale emulsion particles are further prepared by polymerization.
The invention also provides the phase-change heat storage material elastic membrane prepared by the preparation method, and the elastic membrane 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 a miniemulsion RAFT active emulsion polymerization mode, the shell layer is the acrylate 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 excellent high and low temperature resistance, and still shows excellent mechanical property and elasticity after a long-time high and low temperature alternating environment.
(2) The ethyl acrylate is used as the main soft monomer of the acrylate block copolymer, so that the elasticity of the elastic membrane of the aqueous phase-change heat storage elastic membrane is ensured, and the copolymer taking the ethyl acrylate and the styrene as the main monomers has very good performance for preventing the leakage of paraffin, so that the leakage of the phase-change wax cannot occur after long-term use.
(3) The traditional rigid phase-change heat storage material is overcome, so that the material has excellent elasticity and flexibility, can be folded and can be used for preparing large-size films.
(4) The aqueous emulsion obtained in the preparation step 5 can be directly used, and the emulsion is directly applied to various flexible curved surfaces such as special-shaped surfaces, complex surfaces and the like by adopting spraying, brushing and the like, and a high-elasticity compact heat storage film is directly obtained on the surface of the emulsion after the emulsion is dried.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
In the embodiment of the invention, the RAFT reagent is adopted by the inventor to obtain other commodities which are purchased from the market, and the structural formula of the RAFT reagent is shown as follows:
the strong shearing device of the miniemulsion selects a NanoDeBEE experimental type ultrahigh pressure homogenizer with the model of NanoDeBEE45-4;
acrylate monomers, styrene, acrylonitrile, and the like are from Michael's reagents.
The polyethylene monomer in the monomer A adopts Ethylene Glycol Dimethacrylate (EGDMA), and the polyethylene monomer in the monomer B adopts divinyl benzene which is all from Michael's reagent.
The wetting agent is OT-75 of Solvay;
the thickener is a Basff high-efficiency acrylic acid alkali swelling thickener Rheovis AS 1125;
the phase-change wax is selected from FPC36 of Huangjiang chemical company Limited, the phase-change temperature is 36 ℃, and the phase-change enthalpy is 200KJ/KG.
The double column tensile machine is KJ-1066A of Guangdong Kejian apparatus Co.
Emulsion film forming mode:
according to the requirements of GBT528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, a certain amount of prepared emulsion is added into a dumbbell-shaped tetrafluoro disc, the film is formed for 5-7 days at room temperature, the film is taken out from the tetrafluoro disc and further dried for 2 hours at 60 ℃, the film is dried for 30 minutes at 120 ℃ under high vacuum, and the film is taken out and cooled.
And (3) testing mechanical properties: taking 3 adhesive films, and testing the breaking strength and the breaking elongation of the adhesive films by using a tensile machine according to the standard test requirements of GBT 528-2009.
And (3) testing the cold and hot circulation of the adhesive film: and (3) placing the 3 adhesive films in a cold-hot impact testing machine at the temperature of-20-80 ℃ for circulating for 1000 times, taking out the adhesive films, observing the film surfaces, judging whether phase-change wax leaks or not, and testing the mechanical properties.
Examples 1 to 3
The preparation is carried out according to the content of each component in the table 1 as follows:
step 1, dissolving and mixing phase-change wax and A monomers except polyethylene monomers to obtain an oily solution; adding 0.5 part by weight of RAFT reagent into 300 parts by weight 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 for 3 times by using a homogenizer to obtain a fine emulsion;
step 3, heating the miniemulsion obtained in the step 2 to 70 ℃ after deoxygenation 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 value of the system is 6.8, continuing to react for 2h, adding a polyethylene monomer EGDMA in the monomer A, and continuing to react for 2h;
and 4, adding a B monomer into the reaction emulsion obtained 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 a product emulsion.
And 5, adding 0.4 weight part of OT-75 and 0.2 weight part 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 feed composition for examples 1-3
Examples 4 to 6
The preparation method comprises the following steps of:
dissolving and mixing the phase-change wax and the monomer A except the polyethylene monomer to obtain an oily solution; adding 0.3 part by weight of RAFT reagent into 300 parts by weight 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 for 3 times by using a homogenizer to obtain a fine emulsion;
step 3, heating the miniemulsion obtained in the step 2 to 70 ℃ after deoxidizing in a reactor, adding 0.09 weight part of potassium persulfate, adding 0.12 weight part of sodium hydroxide after reacting for 30min till the pH value of the system is 7.0, continuing to react for 1.5h, adding a polyethylene monomer EGDMA in the monomer A, and continuing to react for 2h;
and 4, adding a monomer B into the reaction emulsion obtained 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 a product emulsion.
And 5, adding 0.4 weight part of OT-75 and 0.2 weight part 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 of examples 4 to 6
Comparative examples 1 to 2
In comparative example 1, the B block was not designed, and the capsule shell structure was changed to a random polymer, and the synthesis was carried out according to the following synthesis procedure, with specific monomer addition amounts as shown in table 3:
in comparative example 2, the B block preparation process was not designed, the composition of all monomer ratios was consistent with the proportion of all monomer quantities in example 1, but the B monomer composition was added to the a monomer to prepare only the a block portion, and the polymer synthesis with the structure changed to random was carried out according to the following synthesis procedure, with the specific monomer addition being prepared as in table 3:
preparation of comparative examples 1-2:
step 1, dissolving and mixing phase-change wax in a list and monomers A except polyethylene monomers to obtain an oily solution; adding 0.5 part by weight of RAFT reagent into 300 parts by weight 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 fine emulsion;
step 3, heating the miniemulsion obtained in the step 2 to 70 ℃ after deoxygenation 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 value of the system is 6.8, continuing to react for 2h, adding a polyethylene monomer EGDMA in the monomer A, and continuing to react for 2h; continuously adding 0.015 weight part of potassium persulfate, continuously reacting for 2 hours, cooling to room temperature, and filtering to obtain the product emulsion.
And 4, adding 0.4 weight part of OT-75 and 0.2 weight part 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 synthesis of example 1 was followed with the monomer A of example 1 adjusted to 70% of the total monomer content and the B block to 30% of the total monomer content.
Table 3 raw material composition of comparative examples 1 to 3
Emulsion film forming mode and elastic film performance evaluation mode:
according to the requirements of GBT528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, the prepared emulsion of examples 1-6 is added into a dumbbell-shaped tetrafluoro disc, the film is formed for 5-7 days at room temperature, the film is taken out of the tetrafluoro disc and further dried for 2 hours at 60 ℃, the film is dried for 30 minutes at 120 ℃ under high vacuum, the film is taken out and cooled, and film observation and mechanical property test are carried out, and the results are shown in Table 4.
Resilience test mode of elastic film:
marking the unstretched elastic film in the middle, and accurately measuring the length (L) 0 ) Pulling the adhesive film to an elongation of 200-250% by hand, releasing the hand, and measuring the length (L) of the rebounded adhesive film of the identification section at the highest speed (within 1 second or less) 1 ) The rebound resilience is calculated by the following expression mode:
wherein: l is a radical of an alcohol 0 Is the length of the original sample strip, L 1 The length of the bar that recovers instantaneously after the bar is stretched by 200-250%. In the examples of the present invention, the rebound resilience of the sample (sample bar) is represented by the value of R, wherein the closer R is to 100%, the better the rebound resilience of the sample bar is represented, and the lower R is 95%, the lower the rebound resilience is represented by insufficient rebound resilience.
As can be seen from the data in Table 4, the phase change wax loading of examples 1-3 was 50% and the loading of examples 4-6 was 70%, both of which were able to maintain the final film surface smooth and free of leakage of phase change wax, while maintaining good film elasticity and strength. Examples 4-6 compared to examples 1-3, the film bulk strength increased with the increase of B monomer as a hard monomer, but a significant decrease in elongation at break occurred. 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 elastic film provides very good elasticity, resilience and high and low temperature resistance of the adhesive film.
The phase-change wax filling amount of comparative examples 1 to 3 was 50%, the surface was smooth and no leakage of the phase-change wax, but the films of comparative examples 1 and 2 were highly tacky on the surface and also had poor mechanical strength and elasticity, and particularly, the rebound rate was severely insufficient, which was mainly due to the fact that the whole capsule shell layer was a random copolymer segment using ethyl acrylate as a main monomer and had a low glass transition temperature, and hard monomers without B monomers as a support and lacked a block structure.
Comparative example 3, which uses a higher B block component, compared to example 1, increases the breaking strength significantly with increasing B block, but decreases elongation at break and rebound resilience significantly, and too low a rebound resilience is not suitable for use in situations where frequent film stretching and film recovery are required.
TABLE 4 emulsion film Forming Performance test 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 a cold-hot cycle test of the adhesive film after forming the film, and after placing the film in a cold-hot impact tester for 1000 cycles at a temperature of-20 to 80 ℃, the film was taken out to perform film surface observation, and whether phase-change wax was leaked or not, and a mechanical property test was performed, with the results shown in table 5.
TABLE 5 Performance testing of emulsions prepared in examples 1-6 and comparative examples 1-3 after film formation after neck Cold thermal cycling
As can be seen from Table 5, after the hot and cold impact test of 1000 cycles, the adhesive films of examples 1-6 still have smooth surfaces and no phase-change wax leakage, and the mechanical strength, elongation at break and resilience thereof are all kept good, but the adhesive films of comparative examples 1-2 have obviously leaked phase-change wax on the surfaces after the hot and cold impact, and the adhesive films are not formed basically, and are difficult to test the mechanical properties, elasticity and the like again.
Claims (10)
1. A preparation method of a phase-change heat storage material elastic film 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 monomer A 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 h to obtain a coarse emulsion, and further shearing and crushing the coarse emulsion to obtain a fine emulsion;
step 3, heating the miniemulsion to 45-95 ℃ after deoxidizing, adding a water-soluble initiator, adding a pH regulator after reacting for 30-90 min, continuing to react for 2-4h, adding a polyethylene monomer in the monomer A, and continuing to react for 2-4h;
step 4, adding 1.5-17.5 parts by weight of B monomer into the reaction emulsion obtained in the step 3, reacting for 2-6h, supplementing a water-soluble initiator, continuing to react for 1-4h, cooling to room temperature, and filtering to obtain an 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 a main monomer ethyl acrylate, and also comprises a water-soluble monomer, a functional monomer and a polyethylene monomer, wherein the water-soluble monomer accounts for 0-5% of the total mass of the monomer A, the functional monomer accounts for 0-25% of the total mass of the monomer A, and the polyethylene monomer accounts for 0.1-5%;
the B monomer comprises 80-99% of styrene and 1-20% of polyethylene monomer by mass.
2. The preparation method of the elastic membrane of the phase-change heat storage material as claimed in claim 1, wherein the phase-change temperature of the phase-change wax in the aqueous phase-change heat storage elastic membrane is 20-80 ℃, the enthalpy value of the phase-change wax is not less than 180KJ/KG, and the mass ratio of the phase-change wax to the total monomers of the polymer is 3.
3. The method for preparing the elastic film of the phase-change heat storage material as claimed in claim 1, wherein the monomer A accounts for 75-95% of the total mass of all the polymerized monomers, and the monomer B accounts for 5-25% of the total mass of all the polymerized monomers.
4. 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 monomer A;
the B monomer comprises 85-95% of styrene and 5-15% of polyethylene monomer by mass.
5. The method for preparing the elastic film of the phase-change heat storage material as claimed in claim 1, wherein the water-soluble monomer comprises one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
and/or the functional monomer comprises one or more of styrene, acrylonitrile, methyl acrylate, methyl methacrylate and ethyl methacrylate;
and/or the polyvinyl monomer comprises at least one of ethylene glycol dimethacrylate, allyl methacrylic acid, ethylene glycol diacrylate, butylene glycol 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.
6. The method for preparing the elastic film of the phase-change heat storage material according to claim 1, wherein the polyethylene monomer in the monomer A is ethylene glycol dimethacrylate; and the polyethylene monomer in the B monomer is divinylbenzene.
7. The method for preparing the elastic film of the phase-change heat storage material according to claim 1, wherein the addition amounts of the water-soluble initiator in the step 3 and the step 4 are 0.001 to 0.07 part by weight, respectively, and the pH of the system reaches 6 to 8 after the pH regulator is added;
and/or, in the step 5, the addition amount of the wetting agent and the thickening agent 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.
8. The method for preparing the elastic film of the phase-change heat storage material according to claim 7, wherein the high heat conduction material comprises any one or more of graphite powder, graphene, expandable graphite, carbon nanotubes, nano ceramic, boron nitride, silicon carbide, nano diamond powder and nano silicon dioxide.
9. The method for preparing the elastic film of the phase-change heat storage material as claimed in 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 monomer or a methacrylic monomer; y is an isopropanoyl or acetoxy group; n1 and n2 are average polymerization degrees, n1= 3-15, and n2= 10-50;
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;
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 pH 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;
and/or, the oxidizing agent comprises tert-butyl hydroperoxide;
and/or the reducing agent comprises any one or more of ascorbic acid, rongalite and sodium bisulfite.
10. The elastic film of the phase-change heat storage material prepared by the preparation method of any one of claims 1 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20200122110A1 (en) * | 2018-10-18 | 2020-04-23 | Encapsys, Llc | Microencapsulation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20200122110A1 (en) * | 2018-10-18 | 2020-04-23 | Encapsys, Llc | Microencapsulation |
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