CN118240270A - Shaping phase change cold storage material with double-network structure and preparation method thereof - Google Patents
Shaping phase change cold storage material with double-network structure and preparation method thereof Download PDFInfo
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- CN118240270A CN118240270A CN202410364303.5A CN202410364303A CN118240270A CN 118240270 A CN118240270 A CN 118240270A CN 202410364303 A CN202410364303 A CN 202410364303A CN 118240270 A CN118240270 A CN 118240270A
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- phase change
- cold storage
- storage material
- polyvinyl alcohol
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- 230000008859 change Effects 0.000 title claims abstract description 43
- 239000011232 storage material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000007493 shaping process Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 46
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229940047670 sodium acrylate Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 claims 1
- 239000000017 hydrogel Substances 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000012827 research and development Methods 0.000 abstract 1
- 229920002125 Sokalan® Polymers 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004584 polyacrylic acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
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- 239000007787 solid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 201000009240 nasopharyngitis Diseases 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a shaping phase change cold storage material with a double-network structure and a preparation method thereof. According to the invention, by constructing the polyvinyl alcohol/acrylic hydrogel double-network structure, the water absorption and water binding capacity of the shaped phase change cold storage material are improved, and the mechanical property of the shaped phase change cold storage material is enhanced through hydrogen bond interaction and a mixed porous structure, so that the shaped phase change cold storage material has better cold storage performance, and the serious water leakage phenomenon in the water phase change process is inhibited, so that a new thought is provided for the research and development of the shaped phase change cold storage material.
Description
Technical Field
The invention belongs to the technical field of polyvinyl alcohol-based shaped phase change cold storage materials, relates to a shaped phase change cold storage material with a double-network structure and a preparation method thereof, and in particular relates to a shaped phase change cold storage material with a polyvinyl alcohol/acrylic hydrogel double-network structure and a preparation method thereof. The polyvinyl alcohol foam is obtained through thermoplastic foaming, acrylic hydrogel is polymerized in situ in the foam to form a double-network structure, the water absorption and binding capacity of the composite material are improved through hydrogen bond interaction and a mixed porous structure, the shape stability and the cold storage capacity are enhanced, water leakage can be prevented under the action of external force, and the polyvinyl alcohol foam can be applied to the field of cold chain transportation.
Background
With the development of fresh electronic commerce and the increase of demands of people, the demands for perishable products and biological products are increased, and the development of cold chain logistics is promoted. Cold chain transportation is the core of cold chain logistics, and traditional cold chain transportation adopts mechanical refrigeration, has the problems of expensive and heavy equipment, low refrigeration efficiency, high energy consumption, portability, flexibility and the like. With the rapid development of fresh electric suppliers, small-batch and short-time cold chain transportation is important, and mechanical refrigeration cannot meet the requirement.
The water is used as an inorganic phase change material, has the characteristics of low price, wide sources, no toxicity, economy and the like, and is a common cold chain phase change material. At present, the novel ice-making machine is widely applied to short-distance and small-scale transportation and usually exists in the forms of ice cubes, ice bags and the like. But has the problems of inconvenient carrying, large volume, easy melting, water leakage and the like.
Polyvinyl alcohol (PVA) is a hydrophilic, environmentally friendly, non-toxic polymer. The polyvinyl alcohol has a polyhydroxy structure, forms a hydrogen bond with water molecules, and has the functions of water absorption and water retention. Based on the polyvinyl alcohol thermoplastic foaming technology established by us, the polyvinyl alcohol foam material with a large number of uniform pores and a large specific surface area can be easily prepared, and the porous structure is favorable for water absorption, combination and storage, but the mechanical property and shape stability of the polyvinyl alcohol foam material need to be improved.
The inventor of the invention provides a polyvinyl alcohol porous material and a preparation method thereof in the granted patent of the invention (ZL 201611031825.5), wherein the pore diameter of the prepared polyvinyl alcohol porous material is 5-300 mu m, and the aperture ratio of the prepared polyvinyl alcohol porous material is 10-50%. The porous structure is favorable for absorbing water, but partial water leakage can occur when solid ice is transformed into liquid water through phase change, the mechanical strength is limited, and the volume change caused by the phase change of water or the water absorbed by the solid ice can be extruded out due to collision, so that the cold storage performance of the solid ice is influenced when the solid ice is repeatedly used.
Disclosure of Invention
The invention aims to solve the problems of the prior art, and provides a shaping phase-change cold-storage material with a double-network structure and a preparation method thereof.
To achieve the above object, the present invention adopts the following technical means.
The invention provides a preparation method of a shaping phase change cold storage material with a double-network structure, which mainly comprises the following steps:
(1) The polyvinyl alcohol raw material and the water-containing plasticizing modifier are mixed according to the mass ratio of (6-8): (2-4) mixing, plasticizing and modifying for 24-96 hours at the temperature of 40-80 ℃ with stirring, and preparing plasticized and modified polyvinyl alcohol;
(2) Filling the plasticized and modified polyvinyl alcohol prepared in the step (1) into a die of a flat vulcanizing machine, maintaining the pressure for 5-15 min at 170-190 ℃ and 10-15 MPa, opening the die, releasing the die to normal pressure, and cooling to obtain the polyvinyl alcohol porous material;
(3) Taking 100-150 mL of phase change solution, 5-10 mL of acrylic monomer, 0.1-0.5 g of initiator and 0.5-1.0 g of cross-linking agent as raw materials, and uniformly mixing to prepare a prepolymer;
(4) Soaking the polyvinyl alcohol porous material prepared in the step (2) in the prepolymer liquid prepared in the step (3), standing for 6-8 h, and then continuously standing for 2-3 h at the temperature of 60-80 ℃ to obtain the shaped phase change cold storage material with the double-network structure.
In one technical scheme, the water-containing plasticizing modifier in the step (1) is water or is formed by compounding water and a substance with a larger saturated vapor pressure, wherein the substance with the larger saturated vapor pressure is selected from at least one of ethanol, ethylene glycol, acetone, isopropanol and propanol; in the water-containing plasticizing modifier, water accounts for 60-100% and substances with larger saturated vapor pressure account for 0-40% in mass fraction.
In this context, the phase change solution in step (3) is selected from any one or more of deionized water, sodium chloride aqueous solution, potassium chloride aqueous solution, sodium phosphate aqueous solution, glycerin aqueous solution, polyethylene glycol aqueous solution, and lauric acid aqueous solution.
In this context, the acrylic monomer in the step (3) is a monomer having an acrylic acid and acrylic acid structure capable of forming a hydrogel, and the acrylic monomer suitable for preparing a hydrogel can be selected by itself with reference to the prior art document related to hydrogels.
In one embodiment, the acrylic monomer in the step (3) is selected from any one of acrylic acid, sodium acrylate, acrylamide, N-isopropyl acrylamide, methyl methacrylate and methacrylic acid.
In this context, the initiator described in step (3) is a conventional initiator for the preparation of polyacrylic hydrogels based on acrylic acid, reference being made to the initiators in the prior art documents for the preparation of polyacrylic hydrogels using acrylic acid either directly.
In one technical scheme, the initiator in the step (3) is selected from any one of ammonium persulfate, potassium persulfate, sodium persulfate and potassium perphosphate.
In this context, the crosslinker described in step (3) is a conventional crosslinker for the preparation of polyacrylic hydrogels based on acrylic acid, reference being made to the crosslinker in the prior art documents for the preparation of polyacrylic hydrogels by direct use of acrylic acid.
In one of the technical schemes, the cross-linking agent in the step (3) is selected from any one of N, N' -methylene bisacrylamide, methylene bisacrylamide and N, N-dimethyl formamide.
The shaping phase change cold storage material with the double-network structure prepared by the method is characterized in that the water content of the material ranges from 60% to 88%, the latent heat of phase change is 260-310J/g, the water leakage rate is less than 10wt%, and the material can still maintain the complete structure after compression deformation is 0-60%.
The invention has the following effects:
1. According to the preparation method provided by the invention, the acrylic monomer is polymerized in situ in the polyvinyl alcohol porous material to form a double-network structure, the polyvinyl alcohol foam is used as a supporting framework, and hydrogel polymerized by the acrylic monomer is filled in the polyvinyl alcohol foam holes to form a structure with a large Kong Baoxiao holes, so that sufficient space is provided for storing aqueous solution.
2. The method for preparing the shaped phase change cold storage material with the double-network structure comprises the steps of firstly immersing and filling the pre-polymerized liquid in polyvinyl alcohol cells, and secondly carrying out in-situ polymerization on a framework, so that the shaped phase change cold storage material with different shapes can be prepared according to the shape of the polyvinyl alcohol foam, and the shaped phase change cold storage material is more attached to the surface of an article to be cooled, thereby achieving a better cold insulation effect.
3. The shaped phase change cold storage material prepared by the method has a double-network structure, can improve mechanical properties, has good shape stability, and can effectively prevent leakage of aqueous solution under collision and extrusion conditions or in a phase change process through capillary force and hydrogen bonding action of the double-network structure, thereby achieving the aim of repeated use.
4. The shaping phase change cold storage material with the double-network structure has good water storage capacity, and has water storage capacity of the double-network structure and water absorption of polyvinyl alcohol, so that high water storage capacity and high phase change latent heat are realized.
Drawings
FIG. 1 is a cross-sectional scanning electron micrograph of a sample and intermediate prepared according to the present invention. In the figure, figure a shows a polyvinyl alcohol porous material, figure b shows a polyacrylic acid (PAA) gel after freeze drying, and figure c shows a sample prepared by the invention after freeze drying. It can be obviously seen that the polyvinyl alcohol porous material has a typical three-dimensional porous structure, the average pore diameter is larger than that of the porous structure for preparing the polyacrylic acid gel, and in the shaping phase change cold storage material with a double-network structure, the macropores of the polyvinyl alcohol porous material wrap the micropores of the polyacrylic acid gel, so that a novel double-network structure is formed.
FIG. 2 is an infrared signature of samples, materials and intermediates prepared in accordance with the present invention. In the figure, AA is acrylic acid used, PAA is polyacrylic acid (PAA) gel obtained by polymerization of a prepolymer solution, PVA foam is an intermediate product polyvinyl alcohol porous material, and PVA/PAA is a sample prepared by the method and is subjected to freeze drying; wherein Acrylic Acid (AA) has a C=C vibration peak at 1636cm -1, and the polyacrylic acid gel after freeze drying and the shaped phase change cold storage material have no C=C vibration peak, which proves that acrylic acid is polymerized.
FIG. 3 is a graph showing the comparison of the samples prepared according to the present invention with polyacrylic acid (PAA) gel before and after compression. In the figure, FPCMPFs is the sample shaping phase change cold storage material prepared by the invention, and PAA gel is polyacrylic acid (PAA) gel obtained by polymerization of a prepolymer; it can be seen that at 60% compression set, the polyacrylic acid gel breaks, and the shaped phase change cold storage material maintains a complete structure.
FIG. 4 is a graph showing the comparison of the shape stability and the quality change of the samples and the comparison samples prepared according to the present invention on a hot stage (30 ℃ C.). In the figure, FPCMPFs is a sample shaping phase change cold storage material prepared by the invention, and W/PVA is water-absorbing polyvinyl alcohol foam obtained by impregnating a polyvinyl alcohol porous material with deionized water; the W/PVA phase transition has leakage, and FPCMPFs has good shape stability due to the double-network structure, no obvious leakage and less than 10wt% of mass loss.
Detailed Description
The present application will be explained in further detail with reference to examples. These examples are provided for illustrative purposes only and are not intended to limit the application.
Examples
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The application should not be construed as being limited to the particular embodiments described.
Example 1
According to the parts by weight, 60 parts of polyvinyl alcohol 1797 powder material is added with an aqueous plasticizing modifier consisting of 10 parts of ethanol and 30 parts of water, and then the mixture is fully swelled to the surface of the granules at the temperature of 60 ℃ under the conditions of sealing and stirring, and the granules are dried. Placing the fully swelled and uniformly mixed powder material into a metal mold frame with the length of 10cm multiplied by 0.4cm, and after maintaining the pressure for 10min at 170 ℃ and 10MPa in a flat vulcanizing machine, rapidly opening the mold for pressure relief, and foaming and molding the polyvinyl alcohol porous material. The polyvinyl alcohol porous material is immersed in a prepolymerization solution prepared by taking 100mL of sodium chloride aqueous solution (20 parts of sodium chloride and 80 parts of water), 10mL of acrylic acid, 0.2g of initiator potassium persulfate and 0.695g of cross-linking agent methylene bisacrylamide as proportions, and then is kept stand for 6 hours, and then is kept stand for 3 hours at the temperature of 60 ℃ to prepare the shaping phase change cold storage material with a double-network structure, wherein the phase change latent heat is 296.7J/g.
Example 2
The aqueous plasticizing modifier consisting of 10 parts of ethanol and 20 parts of water is added into 70 parts of polyvinyl alcohol 2099 powder according to parts by weight, and then fully swelled to the surface of the granules at 60 ℃ under the conditions of sealing and stirring, and the granules are dried. Placing the fully swelled and uniformly mixed powder material into a metal mold frame with the length of 10cm multiplied by 0.4cm, maintaining the pressure in a flat vulcanizing machine at 180 ℃ and 10MPa for 10min, rapidly opening the mold and releasing the pressure, and foaming and forming the polyvinyl alcohol porous material. The preparation method comprises the steps of immersing a polyvinyl alcohol porous material in a pre-polymerization solution prepared by taking 100mL of deionized water, 7.5mL of sodium acrylate, 0.15g of initiator sodium persulfate and 0.95g of cross-linking agent N, N' -methylene bisacrylamide as a proportion, standing for 6h, and then continuously standing for 3h at the temperature of 60 ℃ to obtain the shaped phase change cold storage material with a double-network structure, wherein the compression strength of the shaped phase change cold storage material is 58% higher than that of hydrogel under 40% compression deformation.
Claims (6)
1. The preparation method of the shaped phase change cold storage material with the double-network structure is characterized by mainly comprising the following steps of:
(1) The polyvinyl alcohol raw material and the water-containing plasticizing modifier are mixed according to the mass ratio of (6-8): (2-4) mixing, plasticizing and modifying for 24-96 hours at the temperature of 40-80 ℃ with stirring, and preparing plasticized and modified polyvinyl alcohol;
(2) Filling the plasticized and modified polyvinyl alcohol prepared in the step (1) into a die of a flat vulcanizing machine, maintaining the pressure for 5-15 min at 170-190 ℃ and 10-15 MPa, opening the die, releasing the die to normal pressure, and cooling to obtain the polyvinyl alcohol porous material;
(3) Taking 100-150 mL of phase change solution, 5-10 mL of acrylic monomer, 0.1-0.5 g of initiator and 0.5-1.0 g of cross-linking agent as raw materials, and uniformly mixing to prepare a prepolymer;
(4) Soaking the polyvinyl alcohol porous material prepared in the step (2) in the prepolymer liquid prepared in the step (3), standing for 6-8 h, and then continuously standing for 2-3 h at the temperature of 60-80 ℃ to obtain the shaped phase change cold storage material with the double-network structure.
2. The method of manufacture of claim 1, wherein: the phase change solution in the step (3) is selected from any one or more of deionized water, sodium chloride water solution, potassium chloride water solution, sodium phosphate water solution, glycerol water solution, polyethylene glycol water solution and lauric acid water solution.
3. The method of manufacture of claim 1, wherein: the acrylic monomer in the step (3) is selected from any one of acrylic acid, sodium acrylate, acrylamide, N-isopropyl acrylamide, methyl methacrylate and methacrylic acid.
4. The method of manufacture of claim 1, wherein: the initiator in the step (3) is selected from any one of ammonium persulfate, potassium persulfate, sodium persulfate and potassium perphosphate.
5. The method of manufacture of claim 1, wherein: the cross-linking agent in the step (3) is selected from any one of N, N' -methylene bisacrylamide, methylene bisacrylamide and N, N-dimethyl formamide.
6. The shaped phase change cold storage material with the double network structure prepared by the preparation method of the shaped phase change cold storage material with the double network structure of claim 1.
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