CN108929584B - Energy-saving and environment-friendly composite film for surface of household appliance - Google Patents
Energy-saving and environment-friendly composite film for surface of household appliance Download PDFInfo
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- CN108929584B CN108929584B CN201810858090.6A CN201810858090A CN108929584B CN 108929584 B CN108929584 B CN 108929584B CN 201810858090 A CN201810858090 A CN 201810858090A CN 108929584 B CN108929584 B CN 108929584B
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- polyvinyl alcohol
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- energy storage
- composite film
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 70
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 70
- 238000004146 energy storage Methods 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 238000007789 sealing Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 239000002775 capsule Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229940057995 liquid paraffin Drugs 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000008098 formaldehyde solution Substances 0.000 claims description 11
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000012782 phase change material Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an energy-saving and environment-friendly composite film for the surface of a household appliance, which comprises the following specific preparation processes: firstly, preparing crosslinked polyvinyl alcohol resin, then preparing a terminated polyvinyl alcohol colloid, then polishing the surface of an electric appliance through fine gauze, then uniformly coating the terminated polyvinyl alcohol colloid on the polished surface of the electric appliance by using a coating roller, forming a transparent energy storage anticorrosive film on the surface of the electric appliance, spraying a layer of wear-resistant film sealing liquid on the surface of the energy storage anticorrosive film, and air-drying at normal temperature to obtain a two-layer composite film. The energy storage anticorrosive film is prepared by compounding the energy storage anticorrosive film and the wear-resistant layer, the energy storage anticorrosive film has high bonding performance and can be firmly combined with the wear-resistant layer, the energy storage anticorrosive film cannot be damaged due to friction through the outer layer protection effect of the wear-resistant layer, and the service life of the composite film is further effectively prolonged.
Description
Technical Field
The invention belongs to the technical field of environment-friendly materials, and relates to an energy-saving environment-friendly composite film for the surface of a household appliance.
Background
In order to realize surface corrosion resistance of the existing refrigerator, one layer of anticorrosive paint is generally coated or one layer of protective film is compounded on the surface of an electric appliance, but the wear resistance of the existing protective film is poor, the surface damage of the protective film can be caused after long-time use, so that the protective performance is reduced, the heat conductivity and the electric conductivity of the existing protective film are poor, the energy loss of household appliances is easily caused, the environmental protection and energy saving consciousness is enhanced, the existing energy-saving household appliance panel generally uses a color-coated steel plate, the phase-change paint is directly coated on the surface of the steel plate, so that the energy saving purpose is achieved, but the phase-change paint is directly coated and then is subjected to multiple times of friction, the content of the phase-change material in the coating is reduced, the heat conductivity of the coating is improved.
Disclosure of Invention
The invention aims to provide an energy-saving environment-friendly composite film for the surface of a household appliance, which is prepared by compounding an energy storage anticorrosive film and a wear-resistant layer, wherein the energy storage anticorrosive film has higher adhesive property and can be firmly combined with the wear-resistant layer, the energy storage anticorrosive film is not damaged due to friction under the protection action of the outer layer of the wear-resistant layer, so that the service life of the composite film is effectively prolonged, and the problems that the content of a phase-change material in a coating is reduced due to repeated friction after the surface of the conventional appliance is directly coated with a phase-change coating, the heat conductivity of the coating is improved, and the service life of the coating is shortened are solved.
The invention directly coats liquid paraffin in the capsule by crosslinking action, simultaneously the graphene oxide is of a lamellar structure, the graphene oxide sheet contains a large amount of epoxy functional groups, polyvinyl alcohol chains of the crosslinked polyvinyl alcohol resin are connected by toluene-2, 4-diisocyanate, further the whole crosslinked polyvinyl alcohol resin is of a honeycomb reticular structure, the top end and the bottom end of the honeycomb reticular structure are not sealed, so that the capsule and the nano zinc oxide are easily exposed although being coated in the reticular structure, the two ends of the reticular structure of the crosslinked polyvinyl alcohol contain amino groups, the amino groups and epoxy groups of the graphene sheet layer are subjected to ring-opening reaction, the graphene sheet layer covers the top end and the bottom end of the reticular structure, the sealing of the whole reticular structure is realized, and the prepared end-capped polyvinyl alcohol colloid seals the epoxy energy storage capsule and the nano zinc oxide in the capsule, and then can prolong the energy storage characteristic of complex film, the effectual electrical apparatus that prevents uses for a long time and causes the energy storage performance to reduce.
The invention takes polyvinyl alcohol as a matrix chain to prepare cross-linked polyvinyl alcohol resin, the polyvinyl alcohol has higher adhesive property, the adhesive property is increased by cross-linking, and then the cross-linked polyvinyl alcohol resin can be well adhered to the surface of an electric appliance, so that the surface of the electric appliance is not contacted with the outside air, and the corrosion can be effectively prevented; and because the n-butyl titanate is grafted on the surface of the outer shell, the organic titanium has aging resistance, high temperature resistance and certain hydrophobic property, so that the whole capsule outer shell has the functions of hydrophobicity and high temperature resistance, and the corrosion resistance of the composite film is further improved.
The purpose of the invention can be realized by the following technical scheme:
an energy-saving environment-friendly composite film for the surface of a household appliance is prepared by the following specific preparation process:
firstly, dissolving a certain amount of polyvinyl alcohol in boiled water at 95 ℃, then adding epoxy energy storage capsules and nano zinc oxide into the mixture, and stirring and mixing the mixture uniformly; adding 0.13-0.15g of epoxy energy storage capsule and 0.24-0.28g of nano zinc oxide into each gram of polyvinyl alcohol;
secondly, adding toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain crosslinked polyvinyl alcohol resin, and adding 3.2-3.5g of toluene-2, 4-diisocyanate into each gram of polyvinyl alcohol; because both ends of the toluene-2, 4-diisocyanate contain functional groups with-N = C = O, the functional groups can directly generate crosslinking reaction with secondary alcohol groups in the polyvinyl alcohol, two parallel polyvinyl alcohol chains are connected through the functional groups with-N = C = O at both ends of the toluene-2, 4-diisocyanate, and because the polyvinyl alcohol contains a large number of hydroxyl groups, the crosslinked polyvinyl alcohol resin forms a huge network structure, and the epoxy energy storage capsules and the nano zinc oxide are coated in the whole network structure;
adding graphite powder, sodium nitrate, potassium permanganate and concentrated sulfuric acid into a reaction container, reacting for 3 hours in an ice water bath, then heating to 70 ℃ for reacting for 2 hours, cooling to room temperature, slowly dropwise adding hydrogen peroxide until the color of the solution becomes dark yellow, and then centrifugally drying to obtain graphene oxide; adding 27-29mL of concentrated sulfuric acid solution into each gram of graphite powder, adding 0.5g of sodium nitrate, and adding 3g of potassium permanganate into each gram of graphene;
fourthly, dissolving the prepared graphene oxide in an ethanol solution, performing ultrasonic dispersion for 5-10min, adding the dispersed graphene oxide into crosslinked polyvinyl alcohol resin, heating to 70 ℃, stirring and reacting for 4-5h to obtain viscous end-capped polyvinyl alcohol colloid, wherein 0.11-0.13g of graphene oxide is added into each gram of crosslinked polyvinyl alcohol resin; graphene oxide is of a lamellar structure, a large number of epoxy functional groups are contained on graphene oxide sheets, polyvinyl alcohol chains of cross-linked polyvinyl alcohol resin are connected through toluene-2, 4-diisocyanate, the whole cross-linked polyvinyl alcohol resin is of a honeycomb network structure, the top end and the bottom end of the honeycomb network structure are not sealed, so that epoxy energy storage capsules and nano zinc oxide are easily exposed although being wrapped in the network structure, amino groups are contained at two ends of the network structure of the cross-linked polyvinyl alcohol, the amino groups and epoxy groups of graphene sheet layers are subjected to ring-opening reaction, the graphene sheet layers are covered at the top end and the bottom end of the network structure, the whole network structure is sealed, the epoxy energy storage capsules and the nano zinc oxide are sealed by the prepared end-capped polyvinyl alcohol colloid, and the resin is prepared by using the polyvinyl alcohol as a matrix chain, the coating has high bonding performance, the bonding performance is improved through crosslinking, and the coating can be well adhered to the surface of an electric appliance, so that the surface of the electric appliance is not contacted with the outside air, the coating can be effectively prevented from corrosion, and the surface of the electric appliance can still be prevented from being corroded under the action of the nano zinc oxide when the coated composite film is worn;
fifthly, polishing the surface of the electric appliance through fine gauze, then uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance, and at the moment, completely drying the surface of the film;
sixthly, adding epoxy resin and acetone into a stirring kettle, stirring and mixing for 5-10min, then adding silica sol, molybdenum disulfide and polytetrafluoroethylene into the stirring kettle, stirring and mixing uniformly, adding a certain amount of acrylamide, mixing uniformly to obtain a wear-resistant film sealing liquid, spraying the wear-resistant film sealing liquid on the surface of an energy storage anticorrosive film which is not completely dried, and air-drying at normal temperature to obtain a two-layer composite film, wherein the wear-resistant film sealing liquid comprises the following components in parts by weight: 40-45 parts of epoxy resin, 12-14 parts of silica sol, 3-4 parts of molybdenum disulfide, 2-5 parts of polytetrafluoroethylene, 21-24 parts of acrylamide and 60 parts of acetone; the prepared film has high wear resistance, and simultaneously contains silica sol to ensure that the outer layer film has certain hydrophobic capability, so as to further realize the corrosion resistance, and simultaneously, the inner layer energy storage corrosion-resistant film is not easy to damage through coating and fixing of the outer layer film, so as to prolong the energy storage characteristic;
the specific preparation process of the epoxy energy storage capsule is as follows:
firstly, adding a certain amount of liquid paraffin and sodium dodecyl benzene sulfonate into a formaldehyde solution, and ultrasonically dispersing for 5-10min, wherein the liquid paraffin is uniformly dissolved in the formaldehyde solution to obtain a core-spun solution; adding 9.1-9.5mL of formaldehyde solution into each gram of liquid paraffin, and simultaneously adding 0.21-0.23g of sodium dodecyl benzene sulfonate into each gram of liquid paraffin;
dissolving bisphenol A epoxy resin in acetone, adding concentrated ammonia water, heating to 60 ℃, reacting for 3-4h, adding butyl titanate after the temperature is reduced to room temperature, and uniformly mixing to obtain a prepolymerization mixed solution; adding 3.4-3.8mL of concentrated ammonia water into per gram of bisphenol A epoxy resin, and adding 2.7-2.9g of n-butyl titanate;
thirdly, heating the core-spun solution to 90 ℃, then adding the pre-polymerization mixed solution into the core-spun solution, stirring and mixing for 3-5min, dropwise adding dibutyltin dilaurate into the core-spun solution at constant temperature while stirring, heating to 110 ℃ after complete dropwise addition to react for 5h, and then filtering and washing to obtain the epoxy energy storage capsule; wherein 3.2-3.4g of prepolymerization mixed solution is added into each gram of the core-spun solution; because the liquid paraffin is dissolved in the formaldehyde, the liquid paraffin is surrounded by the formaldehyde, the bisphenol A epoxy resin is opened into a ring under the action of ammonia water, so that amino and secondary hydroxyl are formed at two ends of the resin, when the temperature reaches 90 ℃, the amino at two ends in the opened bisphenol A epoxy resin is crosslinked with the formaldehyde solvent, because the liquid paraffin is uniformly distributed in the formaldehyde solution, the liquid paraffin is wrapped in the liquid paraffin in the crosslinking process, and simultaneously, the dealcoholization polymerization reaction is carried out between the tetrabutyl titanate and the hydroxyl in the opened bisphenol A epoxy resin under the catalysis of dibutyltin dilaurate, the dealcoholization polymerization reaction is carried out between the tetrabutyl titanate and the hydroxyl in the opened bisphenol A epoxy resin, the tetrabutyl titanate is grafted on the surface of the shell, and the gap on the surface of the shell is filled by the tetrabutyl titanate, so that the prepared capsule has good sealing performance; and because the n-butyl titanate is grafted on the surface of the outer shell, the organic titanium has aging resistance, high temperature resistance and certain hydrophobic property, so that the whole capsule outer shell has the functions of hydrophobicity and high temperature resistance.
The invention has the beneficial effects that:
1. the energy storage anticorrosive film is prepared by compounding the energy storage anticorrosive film and the wear-resistant layer, the energy storage anticorrosive film has high adhesive property and can be firmly combined with the wear-resistant layer, the energy storage anticorrosive film is not damaged due to friction under the protection action of the outer layer of the wear-resistant layer, the service life of the composite film is further effectively prolonged, and the problems that the content of a phase-change material in a coating is reduced due to repeated friction after the phase-change coating is directly coated on the surface of the existing electric appliance, the heat-conducting property of the coating is improved, and the service life of the coating is shortened are further solved.
2. The invention directly coats liquid paraffin in the capsule by crosslinking action, simultaneously the graphene oxide is of a lamellar structure, the graphene oxide sheet contains a large amount of epoxy functional groups, polyvinyl alcohol chains of the crosslinked polyvinyl alcohol resin are connected by toluene-2, 4-diisocyanate, further the whole crosslinked polyvinyl alcohol resin is of a honeycomb reticular structure, the top end and the bottom end of the honeycomb reticular structure are not sealed, so that the capsule and the nano zinc oxide are easily exposed although being coated in the reticular structure, the two ends of the reticular structure of the crosslinked polyvinyl alcohol contain amino groups, the amino groups and epoxy groups of the graphene sheet layer are subjected to ring-opening reaction, the graphene sheet layer covers the top end and the bottom end of the reticular structure, the sealing of the whole reticular structure is realized, and the prepared end-capped polyvinyl alcohol colloid seals the epoxy energy storage capsule and the nano zinc oxide in the capsule, and then can prolong the energy storage characteristic of complex film, the effectual electrical apparatus that prevents uses for a long time and causes the energy storage performance to reduce.
3. The invention takes polyvinyl alcohol as a matrix chain to prepare cross-linked polyvinyl alcohol resin, the polyvinyl alcohol has higher adhesive property, the adhesive property is increased by cross-linking, and then the cross-linked polyvinyl alcohol resin can be well adhered to the surface of an electric appliance, so that the surface of the electric appliance is not contacted with the outside air, and the corrosion can be effectively prevented; and because the n-butyl titanate is grafted on the surface of the outer shell, the organic titanium has aging resistance, high temperature resistance and certain hydrophobic property, so that the whole capsule outer shell has the functions of hydrophobicity and high temperature resistance, and the corrosion resistance of the composite film is further improved.
Detailed Description
Example 1:
the specific preparation process of the epoxy energy storage capsule is as follows:
adding 100g of liquid paraffin and 21g of sodium dodecyl benzene sulfonate into 910mL of formaldehyde solution, and ultrasonically dispersing for 5-10min, wherein the liquid paraffin is uniformly dissolved in the formaldehyde solution to obtain a core-spun solution;
dissolving 100g of bisphenol A epoxy resin in acetone, adding 340mL of concentrated ammonia water, heating to 60 ℃, reacting for 3-4h, adding 270g of n-butyl titanate after the temperature is reduced to room temperature, and uniformly mixing to obtain a pre-polymerization mixed solution;
thirdly, heating 20g of the core-spun solution to 90 ℃, then adding 64g of the pre-polymerization mixed solution, stirring and mixing for 3-5min, dropwise adding dibutyltin dilaurate at constant temperature, stirring while dropwise adding, heating to 110 ℃ after complete dropwise adding, reacting for 5h, and then filtering and washing to obtain the epoxy energy storage capsule.
Example 2:
the specific preparation process of the epoxy energy storage capsule is as follows:
adding 100g of liquid paraffin and 23g of sodium dodecyl benzene sulfonate into 950mL of formaldehyde solution, and ultrasonically dispersing for 5-10min, wherein the liquid paraffin is uniformly dissolved in the formaldehyde solution to obtain a core-spun solution;
dissolving 100g of bisphenol A epoxy resin in acetone, adding 380mL of concentrated ammonia water, heating to 60 ℃, reacting for 3-4h, adding 290g of n-butyl titanate after the temperature is reduced to room temperature, and uniformly mixing to obtain a pre-polymerization mixed solution;
thirdly, heating 20g of the core-spun solution to 90 ℃, then adding 68g of the pre-polymerization mixed solution, stirring and mixing for 3-5min, dropwise adding dibutyltin dilaurate at constant temperature, stirring while dropwise adding, heating to 110 ℃ after complete dropwise adding, reacting for 5h, and then filtering and washing to obtain the epoxy energy storage capsule.
Example 3:
an energy-saving environment-friendly composite film for the surface of a household appliance is prepared by the following specific preparation process:
firstly, dissolving 100g of polyvinyl alcohol in 95 ℃ boiled water, then adding 13g of the epoxy energy storage capsule prepared in the embodiment 1 and 24g of nano zinc oxide, and stirring and mixing uniformly;
secondly, adding 320g of toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain crosslinked polyvinyl alcohol resin;
adding 10g of graphite powder, 5g of sodium nitrate, 30g of potassium permanganate and 270mL of concentrated sulfuric acid into a reaction container, reacting for 3 hours in an ice-water bath, heating to 70 ℃ for reacting for 2 hours, cooling to room temperature, slowly dropwise adding hydrogen peroxide until the color of the solution becomes dark yellow, and then centrifugally drying to obtain graphene oxide;
fourthly, dissolving 55g of prepared graphene oxide in an ethanol solution, ultrasonically dispersing for 5-10min, adding the dispersed graphene oxide into 50g of crosslinked polyvinyl alcohol resin, heating to 70 ℃, stirring and reacting for 4-5h to obtain viscous end-capped polyvinyl alcohol colloid;
fifthly, polishing the surface of the electric appliance through fine gauze, then uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance, and at the moment, completely drying the surface of the film;
sixthly, adding 400g of epoxy resin and 600g of acetone into a stirring kettle, stirring and mixing for 5-10min, then adding 120g of silica sol, 30g of molybdenum disulfide and 20g of polytetrafluoroethylene, stirring and mixing uniformly, adding 210g of acrylamide, mixing uniformly to obtain a wear-resistant film sealing liquid, spraying the wear-resistant film sealing liquid on the surface of the incompletely dried energy storage anticorrosive film, and air-drying at normal temperature to obtain a two-layer composite film.
Example 4:
an energy-saving environment-friendly composite film for the surface of a household appliance is prepared by the following specific preparation process:
firstly, dissolving 100g of polyvinyl alcohol in 95 ℃ boiled water, then adding 15g of epoxy energy storage capsules and 28g of nano zinc oxide, and stirring and mixing uniformly;
step two, adding 350g of toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain crosslinked polyvinyl alcohol resin;
adding 10g of graphite powder, 5g of sodium nitrate, 30g of potassium permanganate and 290mL of concentrated sulfuric acid into a reaction container, reacting for 3 hours in an ice-water bath, then heating to 70 ℃ for reacting for 2 hours, cooling to room temperature, slowly dropwise adding hydrogen peroxide until the color of the solution becomes dark yellow, and then centrifugally drying to obtain graphene oxide;
fourthly, dissolving 65g of prepared graphene oxide in an ethanol solution, ultrasonically dispersing for 5-10min, adding the dispersed graphene oxide into 50g of crosslinked polyvinyl alcohol resin, heating to 70 ℃, stirring and reacting for 4-5h to obtain viscous end-capped polyvinyl alcohol colloid;
fifthly, polishing the surface of the electric appliance through fine gauze, then uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance, and at the moment, completely drying the surface of the film;
sixthly, adding 450g of epoxy resin and 600g of acetone into a stirring kettle, stirring and mixing for 5-10min, then adding 140g of silica sol, 40g of molybdenum disulfide and 50g of polytetrafluoroethylene, stirring and mixing uniformly, adding 240g of acrylamide, mixing uniformly to obtain a wear-resistant film sealing liquid, spraying the wear-resistant film sealing liquid on the surface of the incompletely dried energy storage anticorrosive film, and air-drying at normal temperature to obtain a two-layer composite film.
Comparative example 1:
an energy-saving environment-friendly composite film for the surface of a household appliance is prepared by the following specific preparation process:
firstly, dissolving 100g of polyvinyl alcohol in 95 ℃ boiled water, then adding 13g of the epoxy energy storage capsule prepared in the embodiment 1 and 24g of nano zinc oxide, and stirring and mixing uniformly;
secondly, adding 320g of toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain crosslinked polyvinyl alcohol resin;
adding 10g of graphite powder, 5g of sodium nitrate, 30g of potassium permanganate and 270mL of concentrated sulfuric acid into a reaction container, reacting for 3 hours in an ice-water bath, heating to 70 ℃ for reacting for 2 hours, cooling to room temperature, slowly dropwise adding hydrogen peroxide until the color of the solution becomes dark yellow, and then centrifugally drying to obtain graphene oxide;
fourthly, dissolving 55g of prepared graphene oxide in an ethanol solution, ultrasonically dispersing for 5-10min, adding the dispersed graphene oxide into 50g of crosslinked polyvinyl alcohol resin, heating to 70 ℃, stirring and reacting for 4-5h to obtain viscous end-capped polyvinyl alcohol colloid;
and fifthly, polishing the surface of the electric appliance through fine gauze, then uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, and forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance.
Comparative example 2:
an energy-saving environment-friendly composite film for the surface of a household appliance is prepared by the following specific preparation process:
firstly, dissolving 100g of polyvinyl alcohol in boiled water at 95 ℃, then adding 13g of liquid paraffin and 24g of nano zinc oxide, and stirring and mixing uniformly;
secondly, adding 320g of toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain g of crosslinked polyvinyl alcohol resin;
adding 10g of graphite powder, 5g of sodium nitrate, 30g of potassium permanganate and 270mL of concentrated sulfuric acid into a reaction container, reacting for 3 hours in an ice-water bath, heating to 70 ℃ for reacting for 2 hours, cooling to room temperature, slowly dropwise adding hydrogen peroxide until the color of the solution becomes dark yellow, and then centrifugally drying to obtain graphene oxide;
fourthly, dissolving 55g of prepared graphene oxide in an ethanol solution, ultrasonically dispersing for 5-10min, adding the dispersed graphene oxide into 50g of crosslinked polyvinyl alcohol resin, heating to 70 ℃, stirring and reacting for 4-5h to obtain viscous end-capped polyvinyl alcohol colloid;
fifthly, polishing the surface of the electric appliance through fine gauze, then uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance, and at the moment, completely drying the surface of the film;
sixthly, adding 400g of epoxy resin and 600g of acetone into a stirring kettle, stirring and mixing for 5-10min, then adding 120g of silica sol, 30g of molybdenum disulfide and 20g of polytetrafluoroethylene, stirring and mixing uniformly, adding 210g of acrylamide, mixing uniformly to obtain a wear-resistant film sealing liquid, spraying the wear-resistant film sealing liquid on the surface of the incompletely dried energy storage anticorrosive film, and air-drying at normal temperature to obtain a two-layer composite film.
Comparative example 3:
an energy-saving environment-friendly composite film for the surface of a household appliance is prepared by the following specific preparation process:
firstly, dissolving 100g of polyvinyl alcohol in 95 ℃ boiled water, then adding 13g of the epoxy energy storage capsule prepared in the embodiment 1 and 24g of nano zinc oxide, and stirring and mixing uniformly;
secondly, adding 320g of toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain crosslinked polyvinyl alcohol resin;
thirdly, polishing the surface of the electric appliance through fine gauze, uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, and forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance, wherein the surface of the film is not completely dried;
and fourthly, adding 400g of epoxy resin and 600g of acetone into a stirring kettle, stirring and mixing for 5-10min, then adding 120g of silica sol, 30g of molybdenum disulfide and 20g of polytetrafluoroethylene into the stirring kettle, stirring and mixing uniformly, adding 210g of acrylamide into the stirring kettle, mixing uniformly to obtain a wear-resistant film sealing liquid, spraying the wear-resistant film sealing liquid on the surface of the incompletely dried energy storage anticorrosive film, and air-drying at normal temperature to obtain a two-layer composite film.
Example 5:
composite membranes prepared in example 3, example 4 and comparative examples 1 to 3 were subjected to performance tests, and specific test results are shown in table 1:
table 1: results of testing the Properties of composite films prepared in example 3, example 4 and comparative examples 1 to 3
| Film thickness (mm) | Thermal conductivity (W/MK) | Anti-frictionPerformance No. (sub) 0# Steel wire ball, 1kg force | |
| Example 3 | 0.92 | 0.38 | 121 |
| Example 4 | 0.92 | 0.37 | 122 |
| Comparative example 1 | 0.68 | 0.21 | 72 |
| Comparative example 2 | 0.91 | 0.34 | 118 |
| Comparative example 3 | 0.93 | 0.35 | 120 |
As can be seen from Table 1, the surface of the composite film after being coated by two layers has higher friction performance, and the thermal conductivity coefficient of the coated composite film is 0.37W/MK;
secondly, the composite films prepared in the examples 3 and 4 and the comparative examples 1 to 3 are respectively rubbed by steel wire balls for 20 times, 40 times, 70 times and 90 times to be tested for the thermal conductivity, and the specific test results are shown in table 2;
table 2: heat-conducting performance test result of composite film after multiple times of friction
As can be seen from table 2, the composite film, which is coated with the capsule and then coated with the cross-linking and terminated with graphene, has durability because the thermal conductivity is maintained after being rubbed several times.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The energy-saving and environment-friendly composite film for the surface of the household appliance is characterized by comprising the following specific preparation processes:
firstly, dissolving a certain amount of polyvinyl alcohol in boiled water at 95 ℃, then adding epoxy energy storage capsules and nano zinc oxide into the mixture, and stirring and mixing the mixture uniformly;
secondly, adding toluene-2, 4-diisocyanate into the first step, keeping the temperature at 95 ℃ and stirring for reacting for 3-4h to obtain crosslinked polyvinyl alcohol resin;
adding graphite powder, sodium nitrate, potassium permanganate and concentrated sulfuric acid into a reaction container, reacting for 3 hours in an ice water bath, then heating to 70 ℃ for reacting for 2 hours, cooling to room temperature, slowly dropwise adding hydrogen peroxide until the color of the solution becomes dark yellow, and then centrifugally drying to obtain graphene oxide;
fourthly, dissolving the prepared graphene oxide in an ethanol solution, performing ultrasonic dispersion for 5-10min, adding the dispersed graphene oxide into crosslinked polyvinyl alcohol resin, heating to 70 ℃, stirring and reacting for 4-5h to obtain viscous end-capped polyvinyl alcohol colloid;
fifthly, polishing the surface of the electric appliance through fine abrasive cloth, then uniformly coating the end-capped polyvinyl alcohol colloid on the polished surface of the electric appliance through a coating roller, standing for 2 hours at normal temperature, forming a layer of transparent energy-storing anticorrosive film on the surface of the electric appliance, and at the moment, completely drying the surface of the film;
sixthly, adding epoxy resin and acetone into a stirring kettle, stirring and mixing for 5-10min, then adding silica sol, molybdenum disulfide and polytetrafluoroethylene into the stirring kettle, stirring and mixing uniformly, adding a certain amount of acrylamide, mixing uniformly to obtain a wear-resistant film sealing liquid, spraying the wear-resistant film sealing liquid on the surface of an energy storage anticorrosive film which is not completely dried, and air-drying at normal temperature to obtain a two-layer composite film;
the specific preparation process of the epoxy energy storage capsule is as follows:
firstly, adding a certain amount of liquid paraffin and sodium dodecyl benzene sulfonate into a formaldehyde solution, and ultrasonically dispersing for 5-10min, wherein the liquid paraffin is uniformly dissolved in the formaldehyde solution to obtain a core-spun solution;
dissolving bisphenol A epoxy resin in acetone, adding concentrated ammonia water, heating to 60 ℃, reacting for 3-4h, adding butyl titanate after the temperature is reduced to room temperature, and uniformly mixing to obtain a prepolymerization mixed solution;
thirdly, heating the core-spun solution to 90 ℃, then adding the pre-polymerization mixed solution into the core-spun solution, stirring and mixing for 3-5min, dropwise adding dibutyltin dilaurate into the core-spun solution at constant temperature while stirring, heating to 110 ℃ after complete dropwise addition, reacting for 5h, and then filtering and washing to obtain the epoxy energy storage capsule.
2. The energy-saving and environment-friendly composite film for the surfaces of household appliances according to claim 1, characterized in that 0.13-0.15g of epoxy energy storage capsules and 0.24-0.28g of nano zinc oxide are added into each gram of polyvinyl alcohol in the first step.
3. The energy-saving environment-friendly composite film for the surfaces of household appliances according to claim 1, characterized in that 3.2 to 3.5g of toluene-2, 4-diisocyanate is added to each gram of polyvinyl alcohol in the second step.
4. The energy-saving and environment-friendly composite film for the surfaces of household appliances according to claim 1, characterized in that in the third step, 27-29mL of concentrated sulfuric acid solution is added to each gram of graphite powder, 0.5g of sodium nitrate is added, and 3g of potassium permanganate is added to each gram of graphene.
5. The energy-saving environment-friendly composite film for the surfaces of household appliances according to claim 1, characterized in that 0.11 to 0.13g of graphene oxide is added to each gram of crosslinked polyvinyl alcohol resin in the fourth step.
6. The energy-saving environment-friendly composite film for the surfaces of household appliances according to claim 1, wherein in the sixth step, the wear-resistant film sealing solution comprises the following components in parts by weight: 40-45 parts of epoxy resin, 12-14 parts of silica sol, 3-4 parts of molybdenum disulfide, 2-5 parts of polytetrafluoroethylene, 21-24 parts of acrylamide and 60 parts of acetone.
7. The energy-saving environment-friendly composite film for the surfaces of household appliances as claimed in claim 1, wherein in the step (i), each gram of liquid paraffin is added into 9.1-9.5mL of formaldehyde solution, and simultaneously, each gram of liquid paraffin is added with 0.21-0.23g of sodium dodecyl benzene sulfonate.
8. The energy-saving environment-friendly composite film for the surfaces of household appliances according to claim 1, characterized in that 3.4-3.8mL of concentrated ammonia water and 2.7-2.9g of n-butyl titanate are added into per gram of bisphenol A epoxy resin in the step (II).
9. The energy-saving environment-friendly composite film for the surfaces of household appliances according to claim 1, characterized in that 3.2-3.4g of pre-polymerization mixed solution is added into each gram of core-spun solution in the step (iii).
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| JP4759157B2 (en) * | 2001-03-30 | 2011-08-31 | 新田ゼラチン株式会社 | Crosslinking agent for gelatin |
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| US20110223405A1 (en) * | 2005-11-18 | 2011-09-15 | Northwestern University | Composite polymer film with graphene nanosheets as highly effective barrier property enhancers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4759157B2 (en) * | 2001-03-30 | 2011-08-31 | 新田ゼラチン株式会社 | Crosslinking agent for gelatin |
| CN103214772A (en) * | 2012-01-18 | 2013-07-24 | 广西格润科技有限公司 | Novel heat-dissipation material and preparation method thereof |
| CN103805142A (en) * | 2013-12-30 | 2014-05-21 | 清华大学深圳研究生院 | Silicon nitride-modified phase-change and energy-storage microcapsule and preparation method thereof |
| CN104176781A (en) * | 2014-08-11 | 2014-12-03 | 华东师范大学 | Flaky nanometer molybdenum disulfide material, nanometer composite metal anticorrosive coating material and preparation method of flaky nanometer molybdenum disulfide material and nanometer composite metal anticorrosive coating material |
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