CN111303467B - Preparation method of graphene heat conduction and dissipation film for floor - Google Patents
Preparation method of graphene heat conduction and dissipation film for floor Download PDFInfo
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- CN111303467B CN111303467B CN202010295961.5A CN202010295961A CN111303467B CN 111303467 B CN111303467 B CN 111303467B CN 202010295961 A CN202010295961 A CN 202010295961A CN 111303467 B CN111303467 B CN 111303467B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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
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- C09K5/14—Solid materials, e.g. powdery or granular
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2475/04—Polyurethanes
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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Abstract
The invention discloses a preparation method of a graphene heat conduction and dissipation film for a floor, which comprises the following specific preparation steps: s1, adding graphene powder into the polyurethane emulsion, adding a surfactant, and uniformly stirring to obtain a graphene mixed emulsion; s2, uniformly coating the graphene mixed emulsion on a modified PET film, and coating the graphene mixed emulsion on the PET film by using a desktop coating machine, wherein the thickness of the graphene mixed emulsion is 10-20 microns; s3, drying the coated modified PET film at 70-90 ℃ for 8-16h to obtain a semi-finished graphene heat-conducting and heat-dissipating film; s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat conduction and dissipation film by using a double-roller rolling machine to obtain the graphene heat conduction and dissipation film; according to the invention, the polyurethane emulsion is used as a solvent to disperse the graphene powder, so that the graphene is uniformly coated on the surface of the modified PET film, and meanwhile, the polyurethane emulsion forms a crosslinked cured layer after drying, so that the modified PET film is conveniently attached to a floor substrate, and the graphene sheet layer is protected.
Description
Technical Field
The invention relates to the technical field of graphite materials, in particular to a preparation method of a graphene heat conduction and dissipation film for a floor.
Background
The floor heating floor is suitable for heating a low-temperature hot water floor, real floor heating floors need a plurality of specific technical parameters, and the floor heating floors must have good heat conduction and heat dissipation performance, so that a plurality of existing floor heating floors are developed to be more environment-friendly and made of floor materials with good heat conduction and heat dissipation performance.
Graphite is a material excellent in heat conductivity, and in recent years, a heat conductive graphite film, which is also called a heat conductive graphite sheet, a heat dissipating graphite film, a graphite heat dissipating film, or the like, has been developed rapidly. The heat-conducting graphite film is a novel heat-conducting and radiating material, and the heat-conducting and radiating effect is very obvious. Low-dimensional carbon nanomaterials, such as graphene and carbon nanotubes, have thermal conductivities as high as 3000-6000W/m.K due to their extremely high elastic constants and mean free paths. The Graphene (Graphene) has the thickness of only 0.335nm, and has an ultra-large specific surface area, excellent electric and thermal conductivity and good chemical stability. These good properties make graphene-based materials an ideal thermal conducting material.
Most of the existing heat conducting films are graphite and polyimide or graphene-graphite composite heat dissipation films, and most of the existing heat conducting films are applied to electronic products.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene heat conduction and dissipation film for a floor, which can solve the following problems:
1. the polyurethane emulsion is used as a solvent to disperse the graphene powder, so that the wetting capacity of the graphene slurry is improved when the surface of the modified PET film is coated, the graphene is uniformly coated on the surface of the modified PET film, and meanwhile, the polyurethane emulsion forms a cross-linked cured layer after being dried, so that the modified PET film is conveniently attached to a floor substrate, and the graphene sheet layer is protected;
2. the graphene oxide and the polymerization monomer of PET are subjected to copolymerization reaction together, and the graphene oxide is reduced to have sp by utilizing the heat energy in the high-temperature polymerization process2The modified PET has the original good mechanical properties, corrosion resistance, water resistance and the like of the PET, and has excellent heat conduction and heat dissipation of the graphene, in addition, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid is added into the modified PET during preparation, and the modified PET has the advantages that the modified PET has the original good mechanical properties, corrosion resistance, water resistance and the like, and the modified PET has the excellent heat conduction and heat dissipation of the graphene, and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid is added into a PET molecular chainThe introduction of phosphorus-containing groups makes up the flammability defect of PET.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graphene heat conduction and dissipation film for a floor comprises the following specific preparation steps:
s1, adding graphene powder into the polyurethane emulsion, adding a surfactant, and uniformly stirring to obtain a graphene mixed emulsion;
s2, uniformly coating the graphene mixed emulsion on a modified PET film, and coating the graphene mixed emulsion on the PET film by using a desktop coating machine, wherein the thickness of the graphene mixed emulsion is 10-20 microns;
s3, drying the coated modified PET film at 70-90 ℃ for 8-16h to obtain a semi-finished graphene heat-conducting and heat-dissipating film;
s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat conduction and dissipation film by using a pair-roller rolling machine to obtain the graphene heat conduction and dissipation film.
The graphene powder is dispersed by using the polyurethane emulsion as a solvent, the wetting capacity of graphene slurry in the surface coating of a modified PET film is improved, the graphene is uniformly coated on the surface of the modified PET film, the surfactant is used, the interlayer spacing between graphene oxides can be widened after the polyurethane emulsion is added into the graphene powder, the graphene is more easily dispersed in the emulsion, moisture can enter an interlayer structure of the graphene, the graphene can form a single-layer laminated structure by evaporation of the moisture contained in the interlayer structure of the graphene when the graphene is dried, the heat conduction and heat dissipation efficiency of a film layer is improved, the polyurethane emulsion forms a crosslinked curing layer after the polyurethane emulsion is dried, the modified PET film is conveniently attached to a floor substrate, and the graphene laminated layer is protected.
Preferably, the preparation method of the polyurethane emulsion in step S1 is as follows:
a1, adding isophorone diisocyanate, polycarbonate diol, 1, 4-butanediol and dibutyltin dilaurate into a reaction bottle under the protection of nitrogen, heating to 80-90 ℃, reacting for 3-5h, adding 2, 2-dimethylolpropionic acid, and continuing to react for 3-5h at 80-90 ℃ to obtain a prepolymer I;
a2, adding methyl methacrylate, triethylamine and deionized water into the prepolymer I, and stirring and mixing for 15-30min to obtain a polyurethane dispersion liquid;
a3, heating the polyurethane dispersion liquid to 70-90 ℃, adding azobisisobutyronitrile, reacting for 2-3h, and removing the solvent by reduced pressure distillation to obtain the polyurethane emulsion.
Isophorone diisocyanate, polycarbonate diol, 1, 4-butanediol and 2, 2-dimethylolpropionic acid are used as raw materials, a polymerization reaction is carried out under the catalysis of dibutyltin dilaurate to obtain a waterborne polyurethane prepolymer, the prepolymer can be cross-linked and polymerized to form a polyurethane film layer under the initiation of an initiator azodiisobutyronitrile, water is used as a dispersion medium for the waterborne polyurethane, an emulsion of the waterborne polyurethane has higher wear resistance and film forming property, and acrylate is added into the waterborne polyurethane, so that the acrylate has the characteristics of higher mechanical strength, weather resistance, yellowing resistance, good water resistance and the like, but the defects of poor heat resistance and poor wear resistance exist, the advantages of the acrylate and the waterborne polyurethane can be complemented with the advantages of the waterborne polyurethane, the polyurethane can carry out a chemical reaction with hydroxyl groups through isocyanate groups in the components to form carbamate groups, and both the carbamate groups and the isocyanate groups have active hydrogen, the waterborne polyurethane can form hydrogen bonds with the surfaces of various materials to achieve a good bonding effect, and in addition, the waterborne polyurethane takes water as a solvent, so that the environmental pollution in the use process is avoided, and the environmental protection requirement of the floor can be greatly met.
Preferably, the mass ratio of the isophorone diisocyanate, the polycarbonate diol, the 1, 4-butanediol, the dibutyltin dilaurate and the 2, 2-dimethylolpropionic acid in the step A1 is 1: 0.7-1:0.2-0.3:0.005-0.01:0.05-0.1.
Preferably, the mass ratio of the prepolymer I, the methyl methacrylate, the triethylamine and the deionized water in the step A2 is 1: 0.1-0.2: 0.05-0.1: 3-4.
Preferably, the mass ratio of the polyurethane dispersion liquid to the azobisisobutyronitrile in the step A3 is 1: 0.001-0.01.
Preferably, the mass ratio of the graphene powder, the polyurethane emulsion and the surfactant in step S1 is 1: 3-5: 0.5-1.2, and the surfactant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.
Preferably, the preparation method of the modified PET film in step S2 is as follows:
b1, adding the dried graphene oxide into ethylene glycol, performing ultrasonic dispersion for 1-2h, adding terephthalic acid, antimony trioxide and triphenyl phosphite, uniformly mixing, putting into a polymerization kettle, and reacting for 5-10h at the temperature of 230 ℃ and 0.3-0.4MPa to obtain a PET prepolymer;
b2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid into the PET prepolymer, heating to 250 ℃ and 270 ℃, continuing to react for 5-8h, stopping the reaction, discharging, granulating and drying to obtain modified PET, wherein the modified PET has the following structure:
and B3, carrying out melt extrusion on the modified PET, and carrying out casting cooling, corona treatment and edge cutting and rolling treatment to obtain the modified PET film, wherein the thickness of the modified PET film is 20-30 μm.
PET is a semi-crystalline polymer, has strong intermolecular force, regular structure and easy crystallization, and has better mechanical property. Because the structure has no strong hydrophilic group, polar molecules such as water, dye and the like are not easy to adsorb, the PET is easy to store, and is resistant to nonpolar solvents such as hydrocarbon, gasoline, kerosene and the like, and is not influenced by polar solvents such as acetone, chloroform, methanol and the like at room temperature, so that the PET can meet various use scenes of floors.
By using a direct esterification method, graphene oxide, terephthalic acid and ethylene glycol are uniformly mixed, a polymerization reaction is carried out under the condition that antimony trioxide is used as a catalyst and triphenyl phosphite is used as a heat stabilizer to obtain a PET prepolymer, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid is added into the PET prepolymer, hydroxyl in a molecular chain of the PET prepolymer and carboxyl of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid are subjected to a condensation reaction, a phosphorus-containing group is introduced into the molecular chain of the PET to increase the flame retardance of a PET layer and make up the defect of flammability of PET materials, compared with an ester exchange method, the direct esterification method is used for preparing the PET film, the cost for producing the PET is reduced because the procedures of recovering methanol and the like are omitted, no catalyst is needed in an esterification stage, the reaction can be generated by directly utilizing the autocatalysis of carboxyl in the terephthalic acid, the reaction byproduct is water, the reaction process is safer and more environment-friendly, and the cost is saved.
Preferably, the mass ratio of the terephthalic acid, the ethylene glycol, the antimony trioxide, the triphenyl phosphite, the graphene oxide and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid in the steps B1 and B2 is 1: 1-2:0.001-0.01:0.01-0.02:0.01-0.05: 0.1-0.2.
Preferably, the temperature of the upper die of the double-roller rolling machine in the step S4 is 90-100 ℃, the temperature of the lower die is 90-100 ℃, and the rotating speed is 30-60 r/min.
Preferably, the graphene heat conduction and dissipation film is suitable for any variety of laminate flooring, solid wood composite floor, ceramic floor and bamboo floor, and the graphene heat conduction and dissipation film is attached to the bottom end face of the flooring, and is in a position relation with the flooring as shown in fig. 1.
The invention has the beneficial effects that:
according to the invention, the polyurethane emulsion is used as a solvent to disperse graphene powder, so that the wetting capacity of graphene slurry in the process of coating the surface of a modified PET film is improved, the graphene is uniformly coated on the surface of the modified PET film, the surfactant is used, the interlayer spacing between graphene oxides can be widened after the polyurethane emulsion is added into the graphene powder, so that the graphene is more easily dispersed in the emulsion, moisture can enter an interlayer structure of the graphene, and when the graphene is dried, the moisture contained in the interlayer structure of the graphene is evaporated to form a single-layer laminated structure, so that the heat conduction and heat dissipation efficiency of a film layer is improved, the polyurethane emulsion forms a crosslinked cured layer after being dried, the modified PET film is conveniently attached to a floor substrate, and the graphene laminated layer is protected;
isophorone diisocyanate, polycarbonate diol, 1, 4-butanediol and 2, 2-dimethylolpropionic acid are taken as raw materials, a polymerization reaction is carried out under the catalysis of dibutyltin dilaurate to obtain a waterborne polyurethane prepolymer, the prepolymer can be cross-linked and polymerized to form a polyurethane film layer under the initiation of an initiator azobisisobutyronitrile, water is taken as a dispersion medium for waterborne polyurethane, an emulsion of the waterborne polyurethane has higher wear resistance and film forming property, and by adding acrylate into the waterborne polyurethane prepolymer, the acrylate has higher mechanical strength, and has the characteristics of weather resistance, yellowing resistance, good water resistance and the like, but has the defects of poor heat resistance and poor wear resistance, can complement the advantages of the waterborne polyurethane, fully exerts the advantages of the acrylate and the polyurethane, the polyurethane can carry out a chemical reaction with hydroxyl groups through isocyanate groups in the components to form carbamate groups, and both the carbamate groups and the isocyanate groups have active hydrogen, the waterborne polyurethane can form hydrogen bonds with the surfaces of various materials to achieve a good bonding effect, and in addition, the waterborne polyurethane takes water as a solvent, so that the environmental pollution in the use process is avoided, and the environmental protection requirement of the floor can be greatly met;
the graphene oxide and the polymerization monomer of PET are subjected to copolymerization reaction together, and the graphene oxide is reduced to have sp by utilizing the heat energy in the high-temperature polymerization process2The graphene copolymerized modified PET is prepared by hybridizing a conjugated structure, the modified PET not only has the original good mechanical properties, corrosion resistance, water resistance and the like of the PET, but also has excellent heat conduction and heat dissipation of the graphene, in addition, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid is added in the modified PET during preparation, and a phosphorus-containing group is introduced into a PET molecular chain, so that the flammability defect of the PET is overcome.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
Fig. 1 is a position relationship diagram of a graphene heat-conducting and heat-dissipating film and a floor;
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of polyurethane emulsion:
a1, under the protection of nitrogen, adding 100g of isophorone diisocyanate, 70g of polycarbonate diol, 25g of 1, 4-butanediol and 1g of dibutyltin dilaurate into a reaction bottle, heating to 85 ℃, reacting for 3-5h, adding 5g of 2, 2-dimethylolpropionic acid, and continuing to react for 3h at 85 ℃ to obtain a prepolymer I;
a2, adding 15g of methyl methacrylate, 7g of triethylamine and 400g of deionized water into 100g of prepolymer I, and stirring and mixing for 30min to obtain a polyurethane dispersion liquid;
a3, heating 100g of polyurethane dispersion liquid to 80 ℃, adding 0.5g of azobisisobutyronitrile, reacting for 3 hours, and removing the solvent by reduced pressure distillation to obtain polyurethane emulsion A.
Example 2
Preparation of polyurethane emulsion:
a1, under the protection of nitrogen, adding 100g of isophorone diisocyanate, 80g of polycarbonate diol, 20g of 1, 4-butanediol and 1g of dibutyltin dilaurate into a reaction bottle, heating to 85 ℃, reacting for 3-5h, adding 8g of 2, 2-dimethylolpropionic acid, and continuing to react for 3h at 85 ℃ to obtain a prepolymer I;
a2, adding 15g of methyl methacrylate, 7g of triethylamine and 400g of deionized water into 100g of prepolymer I, and stirring and mixing for 30min to obtain a polyurethane dispersion liquid;
a3, heating 100g of polyurethane dispersion liquid to 80 ℃, adding 1g of azobisisobutyronitrile, reacting for 3 hours, and removing the solvent by reduced pressure distillation to obtain polyurethane emulsion B.
Example 3
Preparation of PET film:
b1, adding 5g of dried graphene oxide into 200g of ethylene glycol, performing ultrasonic dispersion for 2h, adding 100g of terephthalic acid, 0.5g of antimony trioxide and 2g of triphenyl phosphite, uniformly mixing, putting into a polymerization kettle, and reacting for 8h at 220 ℃ and 0.3MPa to obtain a PET prepolymer;
b2, adding 10g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid into the PET prepolymer, heating to 260 ℃, continuing to react for 8 hours, stopping the reaction, discharging, granulating and drying to obtain modified PET;
and B3, carrying out melt extrusion on the modified PET, and carrying out casting cooling, corona treatment and edge cutting and rolling treatment to obtain the modified PET film A.
Example 4
Preparation of PET film:
b1, adding dried 5g of graphene oxide into 180g of ethylene glycol, performing ultrasonic dispersion for 2 hours, adding 100g of terephthalic acid, 0.5g of antimony trioxide and 2g of triphenyl phosphite, uniformly mixing, putting into a polymerization kettle, and reacting for 8 hours at 220 ℃ and 0.3MPa to obtain a PET prepolymer;
b2, adding 15g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid into the PET prepolymer, heating to 260 ℃, continuing to react for 8 hours, stopping the reaction, discharging, granulating and drying to obtain modified PET;
and B3, carrying out melt extrusion on the modified PET, and carrying out casting cooling, corona treatment and edge cutting and rolling treatment to obtain a modified PET film B.
Example 5
Preparing a graphene heat conduction and dissipation film:
s1, adding 10g of graphene powder into 50g of polyurethane emulsion A, adding 5g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a graphene mixed emulsion;
s2, uniformly coating the graphene mixed emulsion on the modified PET film A, and coating the graphene mixed emulsion on the PET film by using a desktop coating machine, wherein the thickness of the graphene mixed emulsion is 20 microns;
s3, drying the coated modified PET film at 85 ℃ for 16h to obtain a semi-finished product A of the graphene heat-conducting and heat-dissipating film;
s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat-conducting and heat-dissipating film by using a double-roller rolling machine, wherein the upper die temperature of the double-roller rolling machine is 90 ℃, the lower die temperature of the double-roller rolling machine is 90 ℃, and the rotating speed of the double-roller rolling machine is 50r/min, so that the graphene heat-conducting and heat-dissipating film A is obtained.
Example 6
Preparing a graphene heat conduction and dissipation film:
s1, adding 10g of graphene powder into 50g of polyurethane emulsion A, adding 5g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a graphene mixed emulsion;
s2, uniformly coating the graphene mixed emulsion on the modified PET film B, and coating the graphene mixed emulsion on the PET film by using a desktop coating machine, wherein the thickness of the graphene mixed emulsion is 20 microns;
s3, drying the coated modified PET film at 85 ℃ for 16h to obtain a semi-finished product A of the graphene heat-conducting and heat-dissipating film;
s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat-conducting and heat-dissipating film by using a double-roller rolling machine, wherein the upper die temperature of the double-roller rolling machine is 90 ℃, the lower die temperature of the double-roller rolling machine is 90 ℃, and the rotating speed of the double-roller rolling machine is 50r/min, so that the graphene heat-conducting and heat-dissipating film B is obtained.
Example 7
Preparing a graphene heat conduction and dissipation film:
s1, adding 10g of graphene powder into 50g of polyurethane emulsion B, adding 5g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a graphene mixed emulsion;
s2, uniformly coating the graphene mixed emulsion on the modified PET film A, and coating the graphene mixed emulsion on the PET film by using a desktop coating machine, wherein the thickness of the graphene mixed emulsion is 20 microns;
s3, drying the coated modified PET film at 85 ℃ for 16h to obtain a semi-finished product A of the graphene heat-conducting and heat-dissipating film;
s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat-conducting and heat-dissipating film by using a double-roller rolling machine, wherein the upper die temperature of the double-roller rolling machine is 90 ℃, the lower die temperature of the double-roller rolling machine is 90 ℃, and the rotating speed of the double-roller rolling machine is 50r/min, so that the graphene heat-conducting and heat-dissipating film C is obtained.
Example 8
Preparing a graphene heat conduction and dissipation film:
s1, adding 10g of graphene powder into 50g of polyurethane emulsion B, adding 5g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a graphene mixed emulsion;
s2, uniformly coating the graphene mixed emulsion on the modified PET film B, and coating the graphene mixed emulsion on the PET film by using a desktop coating machine, wherein the thickness of the graphene mixed emulsion is 20 microns;
s3, drying the coated modified PET film at 85 ℃ for 16 hours to obtain a semi-finished product of the graphene heat-conducting and heat-dissipating film;
s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat-conducting and heat-dissipating film by using a double-roller rolling machine, wherein the upper die temperature of the double-roller rolling machine is 90 ℃, the lower die temperature of the double-roller rolling machine is 90 ℃, and the rotating speed of the double-roller rolling machine is 50r/min, so that the graphene heat-conducting and heat-dissipating film D is obtained.
Example 9
The thermal conductivity of the graphene thermal conductive and heat dissipation films obtained in examples 5 to 8 is detected, and compared with that of a graphene thermal conductive film produced by a company in Changzhou city, the specific detection method is as follows:
and (3) detecting the heat conductivity: a dynamic thermal conductivity measuring instrument (model LK-RB-II, Hengao instruments and meters Co., Ltd., Beijing);
and (3) detecting the thermal diffusion coefficient: detecting according to a GBT22588-2008 method;
the detection results are as follows:
| item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Thermal conductivity W/(m.k) | 1354.67 | 1348.92 | 1343.25 | 1351.52 | 1248.47 |
| Coefficient of thermal diffusion (cm)2/s) | 8.62 | 8.73 | 8.66 | 8.77 | 8.13 |
The graphene heat conduction and dissipation film prepared by the invention has high heat conductivity and heat diffusion coefficient, and is better than the commercial products.
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 forms 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 understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A preparation method of a graphene heat conduction and dissipation film for a floor is characterized by comprising the following specific preparation steps:
s1, adding graphene powder into the polyurethane emulsion, adding a surfactant, and uniformly stirring to obtain a graphene mixed emulsion;
s2, uniformly coating the graphene mixed emulsion on the modified PET film;
s3, drying the coated modified PET film at 70-90 ℃ for 8-16h to obtain a semi-finished graphene heat-conducting and heat-dissipating film;
s4, carrying out hot rolling treatment on the semi-finished product of the graphene heat conduction and dissipation film by using a double-roller rolling machine to obtain the graphene heat conduction and dissipation film;
the preparation method of the modified PET film in step S2 is as follows:
b1, adding the dried graphene oxide into ethylene glycol, performing ultrasonic dispersion for 1-2h, adding terephthalic acid, antimony trioxide and triphenyl phosphite, uniformly mixing, putting into a polymerization kettle, and reacting for 5-10h at the temperature of 230 ℃ and 0.3-0.4MPa to obtain a PET prepolymer;
b2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid into the PET prepolymer, heating to 250 ℃ and 270 ℃, continuing to react for 5-8h, stopping the reaction, discharging, granulating and drying to obtain modified PET;
and B3, carrying out melt extrusion on the modified PET, and carrying out casting cooling, corona treatment and edge cutting and rolling treatment to obtain the modified PET film.
2. The method for preparing the graphene heat conduction and dissipation film for the floor as claimed in claim 1, wherein the method for preparing the polyurethane emulsion in step S1 is as follows:
a1, adding isophorone diisocyanate, polycarbonate diol, 1, 4-butanediol and dibutyltin dilaurate into a reaction bottle under the protection of nitrogen, heating to 80-90 ℃, reacting for 3-5h, adding 2, 2-dimethylolpropionic acid, and continuing to react for 3-5h at 80-90 ℃ to obtain a prepolymer I;
a2, adding methyl methacrylate, triethylamine and deionized water into the prepolymer I, and stirring and mixing for 15-30min to obtain a polyurethane dispersion liquid;
a3, heating the polyurethane dispersion liquid to 70-90 ℃, adding azobisisobutyronitrile, reacting for 2-3h, and removing the solvent by reduced pressure distillation to obtain the polyurethane emulsion.
3. The method for preparing the graphene heat conduction and dissipation film for the floor as claimed in claim 2, wherein the mass ratio of isophorone diisocyanate, polycarbonate diol, 1, 4-butanediol, dibutyltin dilaurate and 2, 2-dimethylolpropionic acid in step A1 is 1: 0.7-1:0.2-0.3:0.005-0.01:0.05-0.1.
4. The preparation method of the graphene heat-conducting and heat-dissipating film for the floor as claimed in claim 2, wherein the mass ratio of the prepolymer I, the methyl methacrylate, the triethylamine and the deionized water in the step A2 is 1: 0.1-0.2: 0.05-0.1: 3-4.
5. The method for preparing the graphene heat conduction and dissipation film for the floor as claimed in claim 2, wherein the mass ratio of the polyurethane dispersion liquid to the azobisisobutyronitrile in the step A3 is 1: 0.001-0.01.
6. The method for preparing the graphene heat conduction and dissipation film for the floor as claimed in claim 1, wherein the mass ratio of the graphene powder, the polyurethane emulsion and the surfactant in step S1 is 1: 3-5: 0.5-1.2, and the surfactant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.
7. The method for preparing the graphene heat conduction and dissipation film for the floor as claimed in claim 1, wherein the mass ratio of the terephthalic acid, the ethylene glycol, the antimony trioxide, the triphenyl phosphite, the graphene oxide and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid in steps B1 and B2 is 1: 1-2:0.001-0.01:0.01-0.02:0.01-0.05: 0.1-0.2.
8. The preparation method of the graphene heat-conducting and heat-dissipating film for the floor as claimed in claim 1, wherein in step S4, the temperature of the upper mold of the roll-to-roll press is 90-100 ℃, the temperature of the lower mold is 90-100 ℃, and the rotation speed is 30-60 r/min.
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