CN107682943A - A kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation method and application - Google Patents

A kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation method and application Download PDF

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CN107682943A
CN107682943A CN201710850758.8A CN201710850758A CN107682943A CN 107682943 A CN107682943 A CN 107682943A CN 201710850758 A CN201710850758 A CN 201710850758A CN 107682943 A CN107682943 A CN 107682943A
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graphene
mass parts
electric heating
multifunctional
acid
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CN107682943B (en
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王俊中
王聪伟
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The invention discloses a kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation method and application.Preparation method includes：（1）By carrying out modification to graphene microchip, introducing can induce esterified, cross-linking reaction functional group；（2）By the graphene after modification with can esterified, cross-linking reaction emulsion, all kinds of liquid additives mix；Inducing above-mentioned dispersion liquid to occur, original position is esterified, cross-linking reaction forms graphene-based homogeneous electric heating slurry；（3）Modification is modified to electric heating slurry load matrix, to strengthen electric heating slurry and matrix material interface performance；（4）Graphene electric heating slurry is combined with different substrate materials and prepares electric heating products.Graphene thermo electric material of the present invention has resistivity, adjustable using voltage, the efficiency of heating surface, have far infrared heating, fire-retardant concurrently, can have wide range of applications, safety, energy-conservation the advantages that, available for manufacture household building materials, personal care, air equipment, Medical Devices, transport pipeline, the multiple fields such as automobile.

Description

A kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation Methods and applications
Technical field
The present invention relates to a kind of multifunctional graphite vinyl electric heating slurry and its manufactured Multifunctional electrothermic film and preparation method and Using belonging to thermo electric material field.
Background technology
China's atmosphere pollution is mainly coal-smoke pollution, in recent years national consumption of coal, particularly warming coal Amount is high.Carry out having and save land used, environmental, safe and reliable, the easy electrical heating technique of charge, in energy-conservation, section About in terms of maintenance cost and administrative effort, there is obvious advantage.Electric radiant Heating Film is a kind of thin-film material of energy spontaneous heating after energization, It is to be formed, built by the special ink of electrically conductive heating, metal current-carrying bar, matrix material, the part such as protective layer and temperature control, sensing The fields such as heating, dry, the petrochemical pipe insulation of industrial oven are built to have a wide range of applications.Extraordinary electrically conductive ink assigns Electric-heating coatings electric conductivity, conductive filler mainly have several classes such as metal alloy class, carbon material.Gold, silver, platinum electric conductivity in metal system Can be superior but expensive, only limit the use of in military and space industry；Copper, aluminium are oxidizable to be caused hydraulic performance decline and limits its use Place；Nickel powder density is big, easily sink to the bottom cause it is inconvenient for use.Carbon material has light, nontoxic, not oxidizable, cheap etc. Advantage, in electric-heating coatings, particularly Low-temp. electrothermal materialses field using more.
The two dimensional crystal material being made up of single layer of carbon atom layer, graphene, it is a kind of emerging carbon material.It has excellent Electric property (electron mobility is up to 2 × 105 cm at room temperature2/ Vs), prominent heat conductivility (5000 W/mK), surpass High specific surface area (2630 m2/ g) etc. performance while, also have concurrently light, pliability is good, can large area use, it is not oxidizable The advantages that, there is the far-infrared radiated property more prominent than other carbon materials, manufactured heating component has sendible temperature High, the characteristics of thermal comfort is good, therefore graphene possesses as the characteristics of excellent thermo electric material and potentiality.
A of Chinese patent CN 105906832 A, CN 104219797 B, CN 104517664 B, CN 106255238 etc. Use graphene oxide to be aided with different fillers, auxiliary agent as main conductive exothermic material, prepare graphene-based electric heating slurry and Its electrothermal film device, show more excellent electric heating conversion efficiency, the advantage such as heating rate and safe and environment-friendly, energy-conservation.But due to oxygen Graphite alkene crystal structure has been destroyed by strong oxidizer in preparatory phase, conductive heat transfer property can not compared with intrinsic graphene, Need just recover its crystal structure by electronation, this will lengthen electric heating slurry and its film Product Process route, increase energy Consumption and cost.The A of Chinese patent CN 106304435 A, CN 105884251, although A of CN 105898906 etc. have been used such as Mechanical stripping graphene etc. is used as conductive exothermal material, but its preparation process is by graphene raw material and various additives, helped Agent machinery liquid phase mixes, and is stirred by mechanical shear stress scattered, and core exothermic material graphene and each filler are largely It is upper to rely on physical absorption and parcel, lack the combination of chemical bond yardstick, easily occur during follow-up storage and use effective Composition cluster, hot-spot is easily caused after device is made, forms potential safety hazard.In addition, existing patented technology focuses on electric heating slurry The preparation of material and related process, concern is lacked to the surface nature of slurry carrier substrate, fails effectively to enter substrate material surface The corresponding pretreatment of row, strengthening slurry/basal body interface adhesion, especially for flexible electric heating device, it is installing and using process Different degrees of bending can be faced, the interface binding power of slurry and matrix is the key factor for determining its service life and safety.
The content of the invention
The invention provides a kind of multifunctional graphite vinyl electric heating slurry, strengthens conductive hair in a manner of esterified, crosslinking in situ etc. Hot material graphene and each filler, emulsion binding ability, structure electric heating slurry are chemically bonded with substrate interface；Possess electricity heating, Infrared emission, fire-retardant, resistivity, operating voltage and the functions such as heating power is adjustable.
Present invention also offers the preparation method and application of the electric heating slurry.The electric heating slurry and its device can be applied to people The multiple fields such as body nursing, air equipment, pipe insulation, Medical Devices, household electrical appliance, indoor heating, automobile.
Present invention also offers Multifunctional electrothermic film and preparation method made of above-mentioned multifunctional graphite vinyl electric heating slurry And application.
The invention provides a kind of multifunctional graphite vinyl electric heating slurry, it is prepared from the following materials：
Graphene：1-10 mass parts,
Dispersion liquid solvent：20-2000 mass parts,
Surfactant：0.5-10 mass parts,
Surface Oxygen agent：10-100 mass parts,
Esterification, the reaction emulsion of crosslinking：1-20 mass parts,
Auxiliary agent：0.1-8 mass parts,
Above-mentioned auxiliary agent includes following several：
Dispersant：0-0.5 mass parts,
Coalescents：0-0.5 mass parts,
Preservative：0-0.5 mass parts,
Binding agent：0-2.5 mass parts,
Defoamer：0-0.5 mass parts,
Fire retardant：0-2 mass parts,
Functional filler：0-1.5 mass parts,
Adhesive promoter；0-0.5 mass parts.
The invention provides a kind of preparation method of multifunctional graphite vinyl electric heating slurry, comprise the following steps：
（1）Different sizes, the graphene powder of thickness or dispersions in liquids are chosen, is carried out pre-dispersed；
（2）Physical modification or chemical modification are carried out to the graphene after pre-dispersed；
（3）By different size graphite alkene after modification and the reaction emulsion that in situ can induce esterified crosslinking, all kinds of auxiliary agent liquid phases Mixing, is dispersed with stirring；
（4）The pre-dispersed mixed liquor of above-mentioned graphene is heated to certain temperature uniform stirring, the reactions such as esterification, crosslinking occur for induction Form graphene-based homogeneous electric heating slurry.
Such as step（1）Described graphene raw material can be used prepares graphene with electrochemical stripping graphite paper, is specifically shown in Shen Please numbers 201310659172.5, a kind of entitled method of electrochemistry swelling preparing graphite alkene, or patent CN 104264179 B, a kind of entitled process patent that graphene is prepared by graphite raw ore electrolysis.
Such as step（1）Described graphene can be powder or liquid slurry.
Such as step（1）Described graphene raw material should have following technical indicators, powder outward appearance, black gray expandable powder；Graphite The nm of alkene thickness ＜ 5,0.3~50 μm of lateral dimension, crystal structure is complete.
Such as step（1）Described graphene dispersions in liquids solvent include water, fat hydrocarbon solvent, aromatic hydrocarbon solvent, One kind in alcohols solvent, ketones solvent, alcohol ethers solvent.
Such as step（1）Described graphene dispersions in liquids concentration is 0.5 mg/mL -50 mg/mL.
Such as step（2）Described carries out modification to graphene microchip, can be divided into physical modification and chemical modification.
Such as step（2）The physical modification, graphene microchip surface tension and solvent table are made using addition surfactant For face tension force close to improve solution dispersion, surfactant includes but is not limited to APEO, acetylbutyrylcellulose, Tween-80, polyvinyl alcohol, lauryl sodium sulfate, neopelex.
Such as step（2）The chemical modification, method of modifying is chemically bonded using introducing, i.e., graphenic surface is carried out controllable Oxidation, optimization introduce carboxyl, hydroxyl and epoxy radicals active group, anti-using the chemistry between above-mentioned group and other bioactive molecules afterwards Covalent bond should be introduced or ion exchange carries out chemical modification.
Such as step（2）Controllable oxidization in described chemical modification, the oxidant of use include the concentrated sulfuric acid, and concentrated nitric acid is double Oxygen water, potassium permanganate.
Such as step（2）In described chemical modification, with graphenic surface contained by carboxyl, hydroxyl and epoxy radicals active group send out Biochemical bonding（Comprising covalent bonding, non-covalent bonding, hydrogen bonding, ion exchange bonding etc.）Modified bioactive molecule includes Gamma-methyl allyl acyloxypropyl trimethoxysilane, hexamethylene diisocyanate, methyl methacrylate, the poly- second of cyclopenta Glycol methyl ether, polylysine, polyethylene glycol, doxorubicin hydrochloride, 4- propynyloxy base diazobenzene tetrafluoroborates, nitrogen base polyethylene glycol Carboxylic acid.
Such as step（3）In, each component quality proportioning is：Graphene 1-10 mass parts, esterified, crosslinking reaction breast can be induced Liquid 1-20 mass parts, each analog assistant 0.1-5 mass parts.
Such as step（3）In, reaction is anti-comprising esterification, isocyanation esterification reaction, carboxyl acylation reaction, crosslinking curing Should.
Such as step（3）In the reaction emulsion, including hydroxyl class emulsion and the emulsion of class containing carboxyl；Hydroxyl class emulsion bag Include but be not limited to polyvinyl alcohol, melamine resin, polyethylene glycol, neopentyl glycol, trimethylolpropane, hydroxy ethyl fiber Element, polyurethane, neopentyl glycol；The emulsion of class containing carboxyl includes but is not limited to sodium carboxymethylcellulose, polyacrylic acid, aliphatic acid, N, N- methylene-bisacrylamides, itaconic acid, methacrylic acid, maleic anhydride, terephthalic acid (TPA), 2- chloroethyl isocyanates, oneself Diacid.
Such as step（3）In described carboxyl acylation reaction, reaction emulsion includes 2- (7- azepine -1-H- BTAs -1- Base) -1,1,3,3- tetramethylureas hexafluorophosphoric acid, propargyl alcohol, polyethyleneimine.
Such as step（3）In described cross-linking reaction, reaction emulsion include polyamide fat, polyvinyl alcohol, dimethylbenzene, formic acid, Glutaraldehyde, ethylene-vinyl acetate copolymer, silane coupler.
Such as step（3）Described each analog assistant includes dispersant, coalescents, preservative, binding agent, and defoamer is fire-retardant Agent, functional filler, the one or more in adhesive promoter.
Further, described dispersant include polyethenoxy ether metacrylic acid ester, APEO acrylate, Polyethenoxy ether acrylate, fatty acid polyethylene glycol ester, polyol ester, aliphatic amine polyoxyethylene ether；Described coalescents Including one kind in lauryl alcohol ester, neopelex, propandiol butyl ether, propylene glycol methyl ether acetate；Described anti-corrosion Agent is potassium sorbate；Described binding agent includes aqueous polyurethane, water-based chlorine vinegar, water-based saturated polyester resin, epoxy resin, phenol Urea formaldehyde, organic siliconresin, fluorocarbon resin, acrylate quasi-oligomer and activated monomer, alkyd resin, vinylite, conjunction Into cellulose, polyamide, polyvinylidene fluoride resin, synthetic rubber；Described defoamer include silicone oil, tallow acid amides, Aluminum stearate；Described fire retardant includes one kind in antimony oxide, magnesium hydroxide, aluminium hydroxide；Described feature is filled out Material includes titanium dioxide, zirconium oxide, one kind in zinc oxide and aluminum oxide；Described adhesive promoter is AP-3000, poly- two Methylsiloxane, gum dammar, one kind of acrylic acid dicyclopentadiene ester monomer.
Such as step（4）In, stirring at low speed, stir speed (S.S.) 200-700 r/min are taken, until forming homogenous disperse liquid；It is right The homogenous disperse liquid carries out sieving processing, removes reunion graphene and undissolved auxiliary agent, screen cloth number is 100-300 mesh.
Such as step（4）In described whipping process, temperature according to different induced reaction types, whipping temp scope 60- 150 ℃；Reaction time range is in 30 min -12 h, until graphene is formed with emulsion, auxiliary agent slurry after all kinds of reactions Matter dispersion liquid.
The invention provides Multifunctional electrothermic film, multifunctional electro-heating made of a kind of above-mentioned multifunctional graphite vinyl electric heating slurry The preparation process of film is as follows：
（1）Modification is modified to base material：Base material use is physically or chemically modified；
（2）Graphene electric heating slurry and carrier substrate are carried out to be compounded to form graphene conductive heating layer, more work(are obtained after drying Can Electric radiant Heating Film.
The preparation process of Multifunctional electrothermic film is further described below：
Such as step（1）Described substrate carrier is including but not limited to wooden, macromolecule resin base material, pottery matrix material；Base Material shape is including but not limited to sheet material, wire rod, tubing, fabric, in addition to irregular odd-shaped substrates.
Such as step（1）Described base material can be used and is either physically or chemically modified.
Such as step（1）Described substrate material physical is modified：Using mechanical grinding, plasma technique, irradiation, ultrasonic immersing, Sided corona treatment, the method for super low temperature improve substrate surface tension, strengthening slurry and basal body binding force.
Such as step（1）Described base material chemical modification makes graphite using liquid impregnation, spraying method pretreating substrates surface Alkene slurry is formed with base material and is chemically bonded.The modifying agent used includes stearoylketene methacrylate and dimethylamino-ethyl isobutyl Olefin(e) acid ester copolymer, chromic anhydride or coupling agent.
In above-mentioned modifying agent, stearoylketene methacrylate and dimethylamino-ethyl methacrylate（The copolymer of formation） Enhancing base materials/slurry interface adhesion, chromic anhydride (CrO3/ H2SO4) oxidizing process improve hydrophily with improve surface roughness, and The coupling agent that is adapted with above-mentioned graphene electric heating slurry of part, the coupling agent include silane coupler, titanate coupling agent, One or more in aluminate coupling agent, zircoaluminate coupling agent.
Such as step（2）Described graphene conductive heating layer thickness is 0.001- 0.5mm.
Such as step（2）The resistivity value of described graphene electric heating slurry is 0.2-200 Ω cm.
Such as step（2）Described electric heating slurry is with the compound method of base material including but not limited to thermal spraying, silk-screen printing, leaching Stain method, spread one kind in method, roll printing method.
Such as step（2）Described graphene electrothermal layer, which is dried, takes the stage to be incubated, and drying temperature is 60-150 DEG C；Drying side Method includes one kind in dry closed oven drying, infrared light irradiation, volume to volume drying, UV dryings.
Such as step（2）Insulating protective layer should be covered outside described graphene conductive heating layer：, need to be when making Electric radiant Heating Film Covering insulating protective layer outside electric heating layer.
The insulating protective layer is combined on the outside of heating layer by coating, spraying method, and thickness is 0.01-0.5 mm, is protected Jacket material is one kind in polyurethane, ABS resins, polyamide, polysulfones, polyimides or PEI.
Such as step（2）Described operating voltage is 3-220 V.
Such as step（2）Described operating voltage can select 3-36V in safe voltage, and its reason is graphene-based electric heating Slurry combination various types of filler auxiliary agent, resistivity can Optimum Regulation, can be adapted to low-resistivity slurry in safe voltage, meet plus Thermal power demand.
Such as step（2）Described Multifunctional electrothermic film, its effective operating temperature section are controllable at 30-120 DEG C.
Such as step（2）Described Multifunctional electrothermic film, it is from room temperature（25℃）Electrified regulation is to stabilized operating temperature 90% Time is controllable in 1-10 mim.
Such as step（2）Described Multifunctional electrothermic film, its power density is in 30-500W/m2Scope is adjustable.
Beneficial effects of the present invention：
（1）It is electric heating material by using electrochemical stripping high-quality graphene, compared with other carbon materials, graphene has Relatively low proportion, thermo electric material weight can be effectively reduced, can be used with large area；Graphene has excellent mechanical property, can To bend and keep good electric conductivity, machinability is high, variously-shaped, application the demand of adaptation；Graphene has higher The coefficient of heat conduction, quickly heat can be distributed, temperature is uniform and stable, service life length.Meanwhile with redox graphene Compare, the electrochemical stripping graphene crystal structure that uses of the present invention is more complete, and its electric heating property is closer to intrinsic graphene.
（2）The emulsion of the reactions such as esterified, crosslinking in situ and each analog assistant can occur by being added in graphene dispersing solution, Can be by the physical bond of graphene and filler in existing patented technology（Absorption, parcel etc.）It is improved to the chemistry after reaction in-situ Bond is closed, and strengthens the adhesion of exothermic material and filler, makes thermo electric material stable, safe, service life extends.
（3）By carrying out surface modification to carrier substrate, electric heating slurry and substrate interface performance are improved, prevents electric heating slurry After use is dried, particularly come off in mechanical deflection with the stripping occurred during vibration, improve electrothermal film material service life With security.
（4）Resistivity is adjustable after electric heating slurry drying, is adapted to different operating voltage, particularly can be in human-body safety Operating at voltages.
（5）Electric heating slurry and multifunctional electro-heating membrane material prepared by the present invention, it can be widely applied to rule and irregular shape Shape and various material matrixes, such as ceramics, timber, high polymer material etc.；Application field is warmed oneself comprising indoor and outdoor（Floor heating, wall It is warm, decoration painting heating, the heating snow removing of motion lawn, ice, greenhouse etc.）, transport pipeline insulation deicing（Chemical industry, petroleum pipeline）, fly Inside and outside row device（Deicing, heating etc.）, individual health care（All kinds of local heating physiotherapys）, communications and transportation（Railway road key facility is antifreeze） Deng.
Brief description of the drawings
Fig. 1 be with（a）Graphite paper is raw material（Embodiment 1）With（b）Microlite ink powder is raw material（Embodiment 3）, electrochemistry Prepare graphene projection Electronic Speculum（TEM）Photo, insertion figure is electron diffraction spot.
Fig. 2 be with（a）Graphite paper is raw material（Embodiment 1）With（b）Microlite ink powder is raw material（Embodiment 3）, electrochemistry Prepare graphene ESEM（SEM）Photo.
Fig. 3 is that graphene-based electric heating slurry coats PET fexible film Electric radiant Heating Film photos in embodiment 3.
Fig. 4 is（a）Graphene-based electric heating slurry coats more base material electrothermal film material schematic diagrames（Embodiment 6）,（b）Graphene Base electricity heating layer schematic diagram（Embodiment 6）.
Fig. 5 is graphene/PET Electric radiant Heating Films in embodiment 13 under safe voltage（5-20V）Heating curves.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1
Graphene powder is prepared using electrochemical stripping method, graphene thickness is 0.5-3 nm, and lateral dimension is about 30-50 μm, crystal structure is complete, refers to accompanying drawing 1（a）, accompanying drawing 2（a）, graphene microchip is soft, transparent, and crystal formation keeps good.Take 1 matter The graphene powder of part is measured, is scattered in deionized water, dispersion liquid concentration is 0.5 mg/mL, adds lauryl sodium sulfate and makees For hydrophilizing agent（Physical modification agent）, ultrasonic vibration 60min disperseed.
1 mass parts methylene-bisacrylamide is added in the dispersion liquid, 1 mass parts polyacrylic acid is used as reaction emulsion, Totally 0.5 mass parts auxiliary agent, include 0.1 mass parts polyethenoxy ether metacrylic acid ester（Dispersant）, 0.1 mass parts lauryl alcohol ester （Coalescents）, 0.05 mass parts potassium sorbate（Preservative）, 0.05 mass parts silicone oil（Defoamer）, 0.1 mass parts hydroxide Magnesium（Fire retardant）, 0.1 mass parts AP-3000（Adhesive promoter）.Stirred under 200 r/min rotating speeds, cross 100 mesh sieves Net, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 80 DEG C of stirring 30min, induction crosslinks reaction, forms stone Mertenyl electric heating slurry.
Selection wood substrate is carrier, and using mechanical grinding method, plank is polished, and increases surface roughness, is used Plasma spray technology covers graphene-based electric heating slurry on wood substrates surface, is put into baking oven, program phase property insulation 60-80-90 ℃.Resistivity is 0.2 Ω cm after electric heating slurry drying.Poly terephthalic acid second two is covered to Electric radiant Heating Film using hot-pressing technique Alcohol ester protective layer, thickness are 50 μm.
During wood electric heating film operating voltage 30V, effective operating temperature is 35 DEG C, is heated to temperature operating temperature 90% Time is 3min, and thermal power density is 30 W/m2。
Embodiment 2
Graphene powder is prepared using electrochemical stripping method, graphene thickness is 1-5 nm, and lateral dimension is about 2-10 μm, Crystal structure is complete.The graphene powder of 5 mass parts is taken, is scattered in ethanol/water mixed liquor, dispersion liquid concentration is 5 mg/ ML, 3 mass parts potassium permanganate are added as oxidant, introduce the functional groups such as hydroxyl, carboxyl.After scrubbed, hexa-methylene is added Carboxyl or hydroxyl reaction on diisocyanate, with graphene microchip, amido link or amino-formate bond activated graphene are formed, Ultrasonic vibration is disperseed.
2 mass parts acrylic acid are added in the dispersion liquid, 2 mass parts polyurethane help totally as reaction emulsion, 2 mass parts Agent, include 0.5 mass parts polyethenoxy ether acrylate（Dispersant）, 0.5 mass parts propylene glycol methyl ether acetate（Film forming helps Agent）, 0.5 mass parts epoxy resin（Binding agent）, 0.2 mass parts silicone oil（Defoamer）, 0.3 mass parts magnesium hydroxide（It is fire-retardant Agent）.Stirred under 500 rotating speeds, cross 200 eye mesh screens, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 90 DEG C 60 min are stirred, induction occurs isocyanation esterification reaction, forms graphene-based electric heating slurry.
It is carrier to select wood substrate, using dipping chromic anhydride processing, strengthens interface hydrophilicity, uses screen printing technique Graphene-based electric heating slurry is covered on wood substrates surface, is put into baking oven, program phase property is incubated 50-80-100 DEG C.Electric heating is starched Resistivity is 5 Ω cm after material is dried.ABS resin protective layer is covered to Electric radiant Heating Film using hot-pressing technique, thickness is 10 μm.
During wood electric heating film operating voltage 50V, effective operating temperature is 60 DEG C, is heated to temperature operating temperature 90% Time is 5min, and thermal power density is 50 W/m2。
Embodiment 3
Graphene powder is prepared using electrochemical stripping method, graphene thickness is 3-5 nm, and lateral dimension is about 0.3-5 μ M, refer to accompanying drawing 1（b）, accompanying drawing 2（b）, graphene microchip lateral dimension is smaller, and crystal structure is complete, and conductive performance is excellent.Take 10 The graphene powder of mass parts, add part concentrated nitric acid and pre-oxidized, introduce the functional groups such as hydroxyl, carboxyl.After scrubbed, add Enter gamma-methyl allyl acyloxypropyl trimethoxysilane to react with hydroxyl in graphene microchip, after be stably dispersed in N, N- In dimethylformamide/water mixed liquid, dispersion liquid concentration is 10 mg/mL.
5 mass parts acrylic resins are added in the dispersion liquid, 5 mass parts ammoniacal liquor help totally as reaction emulsion, 5 mass parts Agent, include 0.5 mass parts APEO acrylate（Dispersant）, 0.5 mass parts propandiol butyl ether（Coalescents）, 0.5 Mass parts potassium sorbate（Preservative）, the water-based saturated polyester resin of 2.5 mass parts,（Binding agent）, 0.5 mass parts aluminium hydroxide （Fire retardant）, 0.5 mass parts dimethyl silicone polymer（Adhesive promoter）.Stirred under 700 r/min rotating speeds, mistake 300 eye mesh screens, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 150 DEG C of stirring 3h, induction crosslinks reaction, shape Into graphene-based electric heating slurry.
It is matrix to select macromolecule membrane PET resin, and using sided corona treatment, substrate surface is handled, and increase is hydrophilic Property, using screen printing mode, graphene-based electric heating slurry is coated in pet sheet face, dried using volume to volume, drying temperature is 80-100-120℃.Resistivity is 20 Ω cm after electric heating slurry drying.Electric radiant Heating Film is covered using volume to volume film coating technique poly- Ethylene glycol terephthalate protective layer, thickness are 500 μm, and the visible accompanying drawing 3 of its optical photograph, Electric radiant Heating Film is presented flexibility and can Take volume to volume continuous production mode.
For the PET flexible electrothermal membranes operating voltage in 100V, effective operating temperature is 60 DEG C, is heated to temperature operating temperature 90% time is 5min, and thermal power density is 100 W/m2。
Embodiment 4
Graphene liquid slurry is prepared using electrochemical stripping method, graphene thickness is 1-3 nm, and lateral dimension is about 10-30 μm, crystal structure is complete.Take 3（Solid）Mass parts graphene dispersing solution, add 1 mass parts potassium permanganate powder, microwave treatment 3min, afterwards with hydrochloric acid, water washing, introduce hydroxyl, carboxyl official rank can be rolled into a ball.Imidazoles is added, by ion exchange by vinyl benzyl The edge of graphene is exchanged to, dispersion liquid concentration is 20 mg/mL.
3 mass parts trimethylolpropanes are added in the dispersion liquid, 3 mass parts acrylic acid are used as reaction emulsion, totally 1 mass Part auxiliary agent, includes 0.2 mass parts fatty acid polyethylene glycol ester（Dispersant）, 0.1 mass parts propylene glycol methyl ether acetate（Film forming helps Agent）, 0.2 mass parts polyamide（Binding agent）, 0.2 mass parts, two antimony of oxidation（Fire retardant）, 0.2 mass parts titanium dioxide （Functional filler）, 0.1 mass parts acrylic acid DCPA（Adhesive promoter）.Stirred under 200 r/min rotating speeds Uniformly, 100 eye mesh screens are crossed, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 120 DEG C of stirring 1h, induction occurs esterified Cross-linking reaction, form graphene-based electric heating slurry.
Ceramic substrate is chosen as carrier substrate, using dipping stearoylketene methacrylate and dimethylamino-ethyl isobutyl Olefin(e) acid ester（The copolymer of formation）Enhancing and electric heating slurry adhesion, graphite is covered in ceramic base plate surface using plasma spray technology Alkenyl electric heating slurry, is put into baking oven, and program phase property is incubated 80-100-120 DEG C.Resistivity is 1 Ω after electric heating slurry drying cm.Polyimide resin protective layer is covered to Electric radiant Heating Film using hot-pressing technique, thickness is 20 μm.
For the ceramic base Electric radiant Heating Film operating voltage in 50V, effective operating temperature is 45 DEG C, is heated to temperature operating temperature 90% time is 3 min, and thermal power density is 40 W/m2。
Embodiment 5
The graphene liquid slurry prepared using electrochemical stripping micro crystal graphite, graphene thickness is 3-5 nm, and lateral dimension is about For 0.3-3 μm, crystal structure is complete.Take 10（Solid）Mass parts graphene dispersing solution, add the peroxidating of 100 mass parts 30% Hydrogen, wash after oxidation reaction 12h, introduce the functional groups such as hydroxyl, carboxyl.Doxorubicin hydrochloride is added, ultrasonic vibration is passed to hydrogen The grapheme modified microplate of key, dispersion liquid concentration are 30 mg/mL.
2 mass parts polyethylene glycol are added in the dispersion liquid, 2 mass parts maleic anhydrides are used as reaction emulsion, totally 2 mass parts Auxiliary agent, include 0.2 mass parts aliphatic amine polyoxyethylene ether（Dispersant）, 0.2 mass parts propandiol butyl ether（Coalescents）, 0.3 Mass parts organic siliconresin（Binding agent）, 0.1 mass parts tallow acid amides（Defoamer）, 0.5 mass parts magnesium hydroxide（It is fire-retardant Agent）, 0.5 mass parts zirconium oxide（Functional stuffing）, 0.2 mass parts gum dammar（Adhesive promoter）.In 500 r/min rotating speeds Under stir, cross 200 eye mesh screens, formed homogenous disperse liquid.The dispersion liquid is carried out to be heated to 50 DEG C of stirring 6h, induction hair Raw esterification reaction, forms graphene-based electric heating slurry.
Ceramic substrate is chosen as carrier substrate, using the enhancing of dipping silane coupler and electric heating slurry adhesion, is used Plasma spray technology covers graphene-based electric heating slurry in ceramic base plate surface, is put into baking oven, program phase property insulation 80-100- 120℃.Resistivity is 10 Ω cm after electric heating slurry drying.Using hot-pressing technique to Electric radiant Heating Film covering polyurethane resin protection Layer, thickness are 30 μm.
For the ceramic base Electric radiant Heating Film operating voltage in 100V, effective operating temperature is 65 DEG C, is heated to temperature operating temperature 90% time is 5 min, and thermal power density is 60 W/m2。
Embodiment 6
The graphene liquid slurry prepared using electrochemical stripping micro crystal graphite, graphene thickness is 3-5 nm, and lateral dimension is about For 1-3 μm, crystal structure is complete.Take 10（Solid）Mass parts graphene dispersing solution, dispersion liquid concentration are 50 mg/mL, are added 1 mass parts acetylbutyrylcellulose（Physical modification agent）, ultrasonic vibration 30min disperseed.
3 mass parts propargyl alcohols, 3 mass parts polyethyleneimines, 1 mass parts 2- (7- azepines -1-H- are added in the dispersion liquid BTA -1- bases) -1,1,3,3- tetramethylurea hexafluorophosphoric acid is as reaction emulsion, and totally 5 mass parts auxiliary agent, includes 1 mass parts Polyol ester（Dispersant）, 0.5 mass parts neopelex（Dispersant）, 0.5 part of potassium sorbate（Preservative）, 1 matter Measure part epoxy resin（Binding agent）, 1 mass parts aluminium hydroxide（Fire retardant）, 1 mass parts zirconium oxide（Functional stuffing）.In 700 r/ Stirred under min rotating speeds, cross 300 eye mesh screens, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 120 DEG C of stirrings 3h, induction occur carboxyl acylation reaction, form graphene-based electric heating slurry.
Selection wood substrate is carrier, and using mechanical grinding method, plank is polished, and increases surface roughness, is used Plasma spray technology covers graphene-based electric heating slurry on wood substrates surface, is put into baking oven, program phase property insulation 60-100- 150℃.Resistivity is 50 Ω cm after electric heating slurry drying.Poly terephthalic acid second is covered to Electric radiant Heating Film using hot-pressing technique Diol ester protective layer, thickness be 50 μm, as shown in the schematic diagram of accompanying drawing 4, grapheme material be uniformly distributed in exothermic material and with Film direction is consistent.
During wood electric heating film operating voltage 220V, effective operating temperature is 120 DEG C, is heated to temperature operating temperature 90% Time be 3min, thermal power density is 300 W/m2。
Embodiment 7
The graphene powder prepared using electrochemical stripping micro crystal graphite, graphene thickness is 3-5 nm, and lateral dimension is about 1-3 μm, crystal structure is complete.Take 10 mass parts graphene powders, add the 10 mass parts concentrated sulfuric acids, mechanical agitation 30min, after Through washing, the functional groups such as hydroxyl, carboxyl are introduced.5 mass parts cyclopenta methoxypolyethylene glycols are added, ultrasonic vibration is passed to altogether Valence link and grapheme modified microplate, dispersion liquid concentration are 15 mg/mL.
10 mass parts polyethyleneimines are added in the dispersion liquid, 10 mass parts carboxymethyl celluloses are used as reaction emulsion, Totally 5 mass parts auxiliary agent, include 0.5 part of polyol ester（Dispersant）, 0.5 mass parts propylene glycol methyl ether acetate（Coalescents）, 1 Mass parts aqueous polyurethane（Binding agent）, 0.5 mass parts tallow aluminium（Defoamer）, 1 mass parts magnesium hydroxide（Fire retardant）, 1.5 mass parts titanium dioxide（Functional stuffing）.Stirred under 200 r/min rotating speeds, cross 150 eye mesh screens, form homogeneous point Dispersion liquid.The dispersion liquid is carried out to be heated to 90 DEG C of 60 min of stirring, induction occurs carboxyl acylation reaction, forms graphene-based electricity Hot slurry.
It is matrix to select polyphosphazene polymer ester film, and using sided corona treatment, substrate surface is handled, and increases hydrophily, Using screen printing mode, graphene-based electric heating slurry is coated in polyester film surface, dried using volume to volume, drying temperature For 60-70-80 DEG C.Resistivity is 200 Ω cm after electric heating slurry drying.Electric radiant Heating Film is covered using hot-pressing technique poly- to benzene Naphthalate protective layer, thickness are 30 μm.
During the wooden polyester film Electric radiant Heating Film operating voltage 220V, effective operating temperature is 60 DEG C, is heated to temperature work temperature The time of degree 90% is 5min, and thermal power density is 100 W/m2。
Embodiment 8
The graphene powder prepared using electrochemical stripping micro crystal graphite, graphene thickness is 4-5 nm, and lateral dimension is about 0.3-1.5 μm, crystal structure is complete.10 mass parts graphene powders are taken, are scattered in ethanol solution, add the poly- mountain of 1 mass parts The surfactant of pear ester -80, the obtained graphene dispersing solution of ultrasound, dispersion liquid concentration is 20 mg
10 mass parts polyamide fat, 7 mass parts dimethylbenzene and 1 mass parts silane coupler are added in the dispersion liquid as reaction Emulsion, totally 5 mass parts auxiliary agent, includes 0.5 mass parts polyethenoxy ether acrylate（Dispersant）, 0.5 mass parts propane diols fourth Ether（Coalescents）, 1 mass parts organic siliconresin（Binding agent）, 2 mass parts magnesium hydroxides（Fire retardant）, 1 mass parts zirconium oxide （Functional stuffing）.Stirred under 500 r/min rotating speeds, cross 300 eye mesh screens, form homogenous disperse liquid.The dispersion liquid is entered Row is heated to 80 DEG C of 90 min of stirring, and induction crosslinks reaction, forms graphene-based electric heating slurry.
It is matrix to select high-molecular polyamide, using the enhancing of dipping titanate coupling agent and electric heating slurry adhesion, is dried Screen printing mode is used afterwards, graphene-based electric heating slurry is coated in polyamide film surface, using oven drying, dries temperature Spend for 60-70-80 DEG C.Resistivity is 100 Ω cm after electric heating slurry drying.Electric radiant Heating Film covering PET is protected using hot-pressing technique Sheath, thickness are 50 μm.
During the wooden polyamide Electric radiant Heating Film operating voltage 100V, effective operating temperature is 50 DEG C, is heated to temperature operating temperature 90% time is 3min, and thermal power density is 80 W/m2。
Embodiment 9
The graphene powder prepared using electrochemical stripping micro crystal graphite, graphene thickness is 2-4 nm, and lateral dimension is about 0.5-2 μm, crystal structure is complete.10 mass parts graphene powders are taken, add 200 mass parts hydrogenperoxide steam generators, mechanical agitation 60min, by washing, introduce the functional groups such as hydroxyl, carboxyl.5 mass parts 4- propynyloxy base diazobenzene tetrafluoroborates are added, are surpassed Acoustic shock, which is swung, is passed to the grapheme modified microplate of electrostatic interaction, and dispersion liquid concentration is 5 mg/mL.
Adding 2 mass parts 2- chloroethyl isocyanates in the dispersion liquid, 2 mass parts itaconic acids are as reaction emulsion, and totally 3 Mass parts auxiliary agent, include 0.3 mass parts aliphatic amine polyoxyethylene ether（Dispersant）, 0.3 mass parts neopelex（Into Film auxiliary agent）, 0.2 mass parts potassium sorbate（Preservative）, 1 mass parts polyvinylidene fluoride resin（Binding agent）, 0.2 mass parts silicone oil （Defoamer）, 1 mass parts antimony oxide（Fire retardant）.Stirred under 700 r/min rotating speeds, cross 100 eye mesh screens, formed Homogenous disperse liquid.The dispersion liquid is carried out to be heated to 90 DEG C of 90 min of stirring, induction occurs addition esterification, forms graphite Alkenyl electric heating slurry.
It is matrix to select polyphosphazene polymer vinylidene fluoride, using spraying stearoylketene methacrylate and dimethylamino-ethyl Methacrylate（The copolymer of formation）Enhancing base materials/slurry interface adhesion, screen printing mode is used after drying, by graphite Alkenyl electric heating slurry is coated in polyvinylidene difluoride membrane surface, and using oven drying, drying temperature is 60-70-80 DEG C.Electric heating Resistivity is 25 Ω cm after slurry drying.PET protective layers are covered to Electric radiant Heating Film using hot-pressing technique, thickness is 20 μm.
During the wooden polyamide Electric radiant Heating Film operating voltage 150V, effective operating temperature is 85 DEG C, is heated to temperature operating temperature 90% time is 5min, and thermal power density is 180 W/m2。
Embodiment 10
The graphene liquid slurry prepared using electrochemical stripping graphite, graphene thickness is 1-3 nm, and lateral dimension is about 10-20 μm, crystal structure is complete.Take 10（Solid）Mass parts graphene dispersing solution, dispersion liquid concentration are 3 mg/mL, add 2 Mass parts polyvinyl alcohol is as hydrophilizing agent（Physical modification agent）, ultrasonic vibration 60min disperseed.
4 mass parts hydroxyethyl celluloses are added in the dispersion liquid, 4 mass parts N, N- methylene-bisacrylamides are as anti- Emulsion is answered, totally 5 mass parts auxiliary agent, include 0.5 mass parts polyol ester（Dispersant）, 0.5 mass parts propylene glycol methyl ether acetate （Coalescents）, 2 mass parts acrylate quasi-oligomers and activated monomer（Binding agent）, 1 mass parts aluminium hydroxide（Fire retardant）, 1 mass parts zirconium oxide（Functional stuffing）.Stirred under 300 r/min rotating speeds, cross 200 eye mesh screens, form homogenous disperse liquid. The dispersion liquid is carried out to be heated to 80 DEG C of 120 min of stirring, induction occurs esterification, forms graphene-based electric heating slurry.
It for the tubing of insulation antiseptic layer is matrix to select macromolecule polyurethane, using spraying silane coupler enhancing base materials/ Slurry interface adhesion, thermal spraying mode is used after drying, graphene-based electric heating slurry is coated in polyurethane heat-insulation layer surface, Dried using UV lamp, drying temperature is 60-70-80 DEG C.Resistivity is 80 Ω cm after electric heating slurry drying.Using thermal spraying PET protective layers are covered to Electric radiant Heating Film, thickness is 100 μm.
During the wooden polyamide Electric radiant Heating Film operating voltage 220V, effective operating temperature is 80 DEG C, is heated to temperature operating temperature 90% time is 7min, and thermal power density is 300 W/m2。
Embodiment 11
Graphene powder is prepared using electrochemical stripping method, graphene thickness is 3-5 nm, and lateral dimension is about 1-10 μm, Crystal structure is complete.The graphene powder of 5 mass parts is taken, is scattered in deionized water, dispersion liquid concentration is 25 mg/mL, is added Lauryl sodium sulfate is as hydrophilizing agent（Physical modification agent）, ultrasonic vibration 60min disperseed.
2 mass parts methylene-bisacrylamides are added in the dispersion liquid, 2 mass parts polyacrylic acid are used as reaction emulsion, Totally 1 mass parts auxiliary agent, include 0.2 mass parts polyethenoxy ether metacrylic acid ester（Dispersant）, 0.2 mass parts lauryl alcohol ester （Coalescents）, 0.1 mass parts potassium sorbate（Preservative）, 0.1 mass parts silicone oil（Defoamer）, 0.3 mass parts magnesium hydroxide （Fire retardant）, 0.1 mass parts AP-3000（Adhesive promoter）.Stirred under 700 r/min rotating speeds, cross 300 mesh sieves Net, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 80 DEG C of stirring 60min, induction crosslinks reaction, forms stone Mertenyl electric heating slurry.
Selection wood substrate is carrier, and using mechanical grinding method, plank is polished, and increases surface roughness, is used Plasma spray technology covers graphene-based electric heating slurry on wood substrates surface, is put into baking oven, program phase property insulation 60-80-90 ℃.Resistivity is 10 Ω cm after electric heating slurry drying.Polyethylene terephthalate is covered to Electric radiant Heating Film using hot-pressing technique Ester protective layer, thickness are 30 μm.
During wood electric heating film operating voltage 40V, effective operating temperature is 45 DEG C, is heated to temperature operating temperature 90% Time is 3min, and thermal power density is 30 W/m2。
Embodiment 12
Graphene powder is prepared using electrochemical stripping method, graphene thickness is 1-3 nm, and lateral dimension is about 10-20 μ M, crystal structure are complete.The graphene powder of 10 mass parts is taken, is scattered in ethanol/water mixed liquor, dispersion liquid concentration 30 Mg/mL, 8 mass parts potassium permanganate are added as oxidant, introduce the functional groups such as hydroxyl, carboxyl.After scrubbed, six methylenes are added Carboxyl or hydroxyl reaction on group diisocyanate, with graphene microchip, form amido link or amino-formate bond activation graphite Alkene, ultrasonic vibration are disperseed.
10 mass parts acrylic acid are added in the dispersion liquid, 10 mass parts polyurethane help totally as reaction emulsion, 5 mass parts Agent, include 0.5 mass parts polyethenoxy ether acrylate（Dispersant）, 0.5 mass parts propylene glycol methyl ether acetate（Film forming helps Agent）, 2 mass parts epoxy resin（Binding agent）, 1 mass parts magnesium hydroxide（Fire retardant）, 1 mass parts aluminum oxide（Functional stuffing）. Stirred under 700 rotating speeds, cross 100 eye mesh screens, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 90 DEG C of stirrings 120 min, induction occur isocyanation esterification reaction, form graphene-based electric heating slurry.
It is carrier to select wood substrate, using dipping chromic anhydride processing, strengthens interface hydrophilicity, uses screen printing technique Graphene-based electric heating slurry is covered on wood substrates surface, is put into baking oven, program phase property is incubated 50-80-100 DEG C.Electric heating is starched Resistivity is 20 Ω cm after material is dried.ABS resin protective layer is covered to Electric radiant Heating Film using hot-pressing technique, thickness is 10 μm.
During wood electric heating film operating voltage 100V, effective operating temperature is 50 DEG C, is heated to temperature operating temperature 90% Time is 3min, and thermal power density is 50 W/m2。
Embodiment 13
Graphene powder is prepared using electrochemical stripping method, graphene thickness is 3-5 nm, and lateral dimension is about 0.3-5 μ M, crystal structure are complete.The graphene powder of 10 mass parts is taken, part concentrated nitric acid is added and is pre-oxidized, introduce hydroxyl, carboxyl Deng functional group.After scrubbed, add gamma-methyl allyl acyloxypropyl trimethoxysilane and occur instead with hydroxyl in graphene microchip Should, after be stably dispersed in DMF, dispersion liquid concentration is 10 mg/mL.
5 mass parts acrylic resins are added in the dispersion liquid, 5 mass parts ammoniacal liquor help totally as reaction emulsion, 5 mass parts Agent, include 0.5 mass parts APEO acrylate（Dispersant）, 0.5 mass parts propandiol butyl ether（Coalescents）, 0.5 Mass parts potassium sorbate（Preservative）, the water-based saturated polyester resin of 2.5 mass parts,（Binding agent）, 0.5 mass parts aluminium hydroxide （Fire retardant）, 0.5 mass parts dimethyl silicone polymer（Adhesive promoter）.Stirred under 500 r/min rotating speeds, mistake 200 eye mesh screens, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 120 DEG C of stirring 1h, induction crosslinks reaction, shape Into graphene-based electric heating slurry.
It is matrix to select macromolecule membrane PET resin, and using sided corona treatment, substrate surface is handled, and increase is hydrophilic Property, using screen printing mode, graphene-based electric heating slurry is coated in pet sheet face, dried using volume to volume, drying temperature is 80-100-120℃.Resistivity is 10 Ω cm after electric heating slurry drying.Electric radiant Heating Film is covered using volume to volume film coating technique poly- Ethylene glycol terephthalate protective layer, thickness are 50 μm.
For the PET flexible electrothermal membranes operating voltage in 10V, effective operating temperature is 50 DEG C, refers to and song is heated in accompanying drawing 5 Line, the time for being heated to temperature operating temperature 90% is 3 min, can be limited to using voltage under safe voltage, safe and reliable.
Embodiment 14
Graphene liquid slurry is prepared using electrochemical stripping method, graphene thickness is 0.5-5 nm, and lateral dimension is about 1- 10 μm, crystal structure is complete.Take 10（Solid）Mass parts graphene dispersing solution, add 3 mass parts potassium permanganate powders, microwave 5 min are handled, afterwards with hydrochloric acid, water washing, introduce hydroxyl, carboxyl official rank can be rolled into a ball.Imidazoles is added, by ion exchange by vinyl Benzyl exchanges to the edge of graphene, and dispersion liquid concentration is 15 mg/mL.
2 mass parts trimethylolpropanes are added in the dispersion liquid, 2 mass parts acrylic acid are used as reaction emulsion, totally 2 mass Part auxiliary agent, includes 0.3 mass parts fatty acid polyethylene glycol ester（Dispersant）, 0.1 mass parts propylene glycol methyl ether acetate（Film forming helps Agent）, 0.5 mass parts polyamide（Binding agent）, 0.4 mass parts, two antimony of oxidation（Fire retardant）, 0.5 mass parts titanium dioxide （Functional filler）, 0.2 mass parts acrylic acid DCPA（Adhesive promoter）.Stirred under 500 r/min rotating speeds Uniformly, 100 eye mesh screens are crossed, form homogenous disperse liquid.The dispersion liquid is carried out to be heated to 90 DEG C of stirring 1h, induction occurs esterified Cross-linking reaction, form graphene-based electric heating slurry.
Ceramic substrate is chosen as carrier substrate, using dipping stearoylketene methacrylate and dimethylamino-ethyl isobutyl Olefin(e) acid ester（The copolymer of formation）Enhancing and electric heating slurry adhesion, graphite is covered in ceramic base plate surface using plasma spray technology Alkenyl electric heating slurry, is put into baking oven, and program phase property is incubated 80-100-120 DEG C.Resistivity is 3 Ω after electric heating slurry drying cm.Polyimide resin protective layer is covered to Electric radiant Heating Film using hot-pressing technique, thickness is 30 μm.
For the ceramic base Electric radiant Heating Film operating voltage in 40V, effective operating temperature is 38 DEG C, is heated to temperature operating temperature 90% time is 3 min, and thermal power density is 35 W/m2。
Embodiment 15
The graphene liquid slurry prepared using electrochemical stripping micro crystal graphite, graphene thickness is 1-5 nm, and lateral dimension is about For 10-30 μm, crystal structure is complete.Take 5（Solid）Mass parts graphene dispersing solution, add the peroxidating of 100 mass parts 30% Hydrogen, wash after oxidation reaction 3h, introduce the functional groups such as hydroxyl, carboxyl.Doxorubicin hydrochloride is added, ultrasonic vibration is passed to hydrogen bond Grapheme modified microplate, dispersion liquid concentration are 10 mg/mL.
5 mass parts polyethylene glycol are added in the dispersion liquid, 5 mass parts maleic anhydrides are used as reaction emulsion, totally 2 mass parts Auxiliary agent, include 0.2 mass parts aliphatic amine polyoxyethylene ether（Dispersant）, 0.2 mass parts propandiol butyl ether（Coalescents）, 0.3 Mass parts organic siliconresin（Binding agent）, 0.1 mass parts tallow acid amides（Defoamer）, 0.5 mass parts magnesium hydroxide（It is fire-retardant Agent）, 0.5 mass parts zirconium oxide（Functional stuffing）, 0.2 mass parts gum dammar（Adhesive promoter）.In 200 r/min rotating speeds Under stir, cross 100 eye mesh screens, formed homogenous disperse liquid.The dispersion liquid is carried out to be heated to 50 DEG C of stirring 6h, induction hair Raw esterification reaction, forms graphene-based electric heating slurry.
Ceramic substrate is chosen as carrier substrate, using the enhancing of dipping silane coupler and electric heating slurry adhesion, is used Plasma spray technology covers graphene-based electric heating slurry in ceramic base plate surface, is put into baking oven, program phase property insulation 80-100- 120℃.Resistivity is 15 Ω cm after electric heating slurry drying.Using hot-pressing technique to Electric radiant Heating Film covering polyurethane resin protection Layer, thickness are 50 μm.
For the ceramic base Electric radiant Heating Film operating voltage in 100V, effective operating temperature is 50 DEG C, is heated to temperature operating temperature 90% time is 5 min, and thermal power density is 40 W/m2。

Claims (15)

  1. A kind of 1. multifunctional graphite vinyl electric heating slurry, it is characterised in that：It is prepared by the raw material of following weight proportion：
    Graphene：1-10 mass parts,
    Dispersion liquid solvent：20-2000 mass parts,
    Surfactant：0.5-10 mass parts,
    Surface Oxygen agent：10-100 mass parts,
    Esterification, the reaction emulsion of crosslinking：1-20 mass parts,
    Auxiliary agent：0.1-8 mass parts,
    Above-mentioned auxiliary agent includes following several：
    Dispersant：0-0.5 mass parts,
    Coalescents：0-0.5 mass parts,
    Preservative：0-0.5 mass parts,
    Binding agent：0-2.5 mass parts,
    Defoamer：0-0.5 mass parts,
    Fire retardant：0-2 mass parts,
    Functional filler：0-1.5 mass parts,
    Adhesive promoter；0-0.5 mass parts.
  2. 2. multifunctional graphite vinyl electric heating slurry according to claim 1, it is characterised in that：Described graphene is black gray expandable Powder；The nm of graphene thickness ＜ 5,0.3~50 μm of lateral dimension, crystal structure is complete；
    Described surfactant includes APEO, acetylbutyrylcellulose, Tween-80, polyvinyl alcohol, dodecane One kind in base sodium sulphate, neopelex.
  3. 3. multifunctional graphite vinyl electric heating slurry according to claim 1, it is characterised in that：In the reaction emulsion, including Hydroxyl class emulsion, the emulsion of class containing carboxyl, the emulsion of carboxyl acylation reaction or the emulsion of cross-linking reaction；
    Hydroxyl class emulsion include polyvinyl alcohol, melamine resin, polyethylene glycol, neopentyl glycol, trimethylolpropane, One kind in hydroxyethyl cellulose, polyurethane；
    The emulsion of class containing carboxyl includes sodium carboxymethylcellulose, polyacrylic acid, aliphatic acid, N,N methylene bis acrylamide, clothing health One kind in acid, methacrylic acid, maleic anhydride, terephthalic acid (TPA), 2- chloroethyl isocyanates, adipic acid；
    In described carboxyl acylation reaction, reaction emulsion includes 2- (7- azepine -1-H- BTA -1- bases) -1,1,3,3- tetra- One kind in MU hexafluorophosphoric acid, propargyl alcohol, polyethyleneimine；
    The emulsion of cross-linking reaction includes polyamide fat, polyvinyl alcohol, dimethylbenzene, formic acid, glutaraldehyde, ethene-vinyl acetate copolymerization One kind in thing, silane coupler.
  4. 4. multifunctional graphite vinyl electric heating slurry according to claim 1, it is characterised in that：Described dispersant includes polyoxy Ethene ether metacrylic acid ester, APEO acrylate, polyethenoxy ether acrylate, fatty acid polyethylene glycol ester are more One kind in first alcohol ester, aliphatic amine polyoxyethylene ether；
    Described coalescents are included in lauryl alcohol ester, neopelex, propandiol butyl ether, propylene glycol methyl ether acetate One or more mixing；
    Described preservative is potassium sorbate；
    Described binding agent includes aqueous polyurethane, water-based chlorine vinegar, water-based saturated polyester resin, epoxy resin, phenolic resin, has Machine silicones, fluorocarbon resin, acrylate quasi-oligomer, acrylic ester monomer, alkyd resin, vinylite, synthesis are fine Tie up one kind in element, polyamide, polyvinylidene fluoride resin, synthetic rubber；
    Described defoamer includes one kind in silicone oil, tallow acid amides, aluminum stearate；
    Described fire retardant includes one kind in antimony oxide, magnesium hydroxide, aluminium hydroxide；
    Described functional filler includes titanium dioxide, zirconium oxide, one kind in zinc oxide or aluminum oxide；
    Described adhesive promoter is AP-3000, dimethyl silicone polymer, gum dammar, acrylic acid DCPA list One kind in body.
  5. A kind of 5. preparation method of the multifunctional graphite vinyl electric heating slurry described in any one of claim 1 ~ 4, it is characterised in that：Bag Include following steps：
    （1）Different sizes, the graphene powder of thickness or dispersions in liquids are chosen, is carried out pre-dispersed；
    （2）Physical modification or chemical modification are carried out to the graphene after pre-dispersed；
    The physical modification, addition surfactant is used graphene microchip surface tension is approached with solvent surface tension to change Kind solution dispersion；The chemical modification is to introduce the modified method of chemical bonding, i.e., carries out controllable oxidization to graphenic surface, Optimization introduces carboxyl, hydroxyl or epoxy radicals active group, is drawn afterwards using the chemical reaction between above-mentioned group and other bioactive molecules Enter covalent bond or ion exchange carries out chemical modification；
    （3）By different size graphite alkene after modification and the reaction emulsion that in situ can induce esterified crosslinking, each analog assistant mutually mixes Close, be dispersed with stirring；
    （4）The pre-dispersed mixed liquor of above-mentioned graphene is heated to 60 ~ 150 DEG C of uniform stirrings, esterification, cross-linking reaction occur for induction Form graphene-based homogeneous electric heating slurry.
  6. 6. the preparation method of multifunctional graphite vinyl electric heating slurry according to claim 5, it is characterised in that：Step（1）Institute The graphene dispersions in liquids solvent stated includes water, fat hydrocarbon solvent, aromatic hydrocarbon solvent, alcohols solvent, ketones solvent, alcohol One kind in ether solvent；The concentration of described graphene dispersions in liquids is 0.5 mg/mL -50 mg/mL.
  7. 7. the preparation method of multifunctional graphite vinyl electric heating slurry according to claim 5, it is characterised in that：Step（2）Institute Controllable oxidization in the chemical modification stated, the oxidant of use include the concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide, and one in potassium permanganate Kind；In described chemical modification, with graphenic surface contained by carboxyl, hydroxyl and epoxy radicals active group chemical bonding occurs and is modified Bioactive molecule include：Gamma-methyl allyl acyloxypropyl trimethoxysilane, hexamethylene diisocyanate, methacrylic acid Methyl esters, cyclopenta methoxypolyethylene glycol, polylysine, polyethylene glycol, doxorubicin hydrochloride, 4- propynyloxy base diazobenzene tetrafluoro boric acids One kind in salt, nitrogen base polyethylene carboxylic acid.
  8. 8. the preparation method of multifunctional graphite vinyl electric heating slurry according to claim 5, it is characterised in that：Step（4）In, Stirring at low speed, stir speed (S.S.) 200-700 r/min are taken, until forming homogenous disperse liquid；The homogenous disperse liquid is sieved Processing, reunion graphene and undissolved auxiliary agent are removed, screen cloth number is 100-300 mesh；Whipping temp is 60-150 DEG C；Instead It is 30 min -12 h between seasonable, until graphene forms homogenous disperse liquid with emulsion, auxiliary agent slurry after all kinds of reactions.
  9. 9. one kind Multifunctional electrothermic film made of the multifunctional graphite vinyl electric heating slurry described in any one of claim 1 ~ 4, its It is characterised by：The preparation process of Multifunctional electrothermic film is as follows：
    （1）Modification is modified to base material；
    Base material use is physically or chemically modified；
    （2）Graphene electric heating slurry and carrier substrate are carried out to be compounded to form graphene conductive heating layer, more work(are obtained after drying Can Electric radiant Heating Film.
  10. 10. Multifunctional electrothermic film made of multifunctional graphite vinyl electric heating slurry according to claim 9, it is characterised in that： Step（1）Described base material includes wood materials, macromolecule resin base material, pottery matrix material；Substrate shapes include sheet material, Wire rod, tubing, fabric or irregular odd-shaped substrates；
    Substrate material physical, which is modified, to be referred to：Using mechanical grinding, plasma technique, irradiation, ultrasonic immersing, sided corona treatment or ultralow temperature The method of processing improves substrate surface tension, strengthening slurry and basal body binding force；
    Base material chemical modification makes graphene slurry and base material formationization using liquid impregnation, spraying method pretreating substrates surface Learn bonding.
  11. 11. Multifunctional electrothermic film made of multifunctional graphite vinyl electric heating slurry according to claim 10, it is characterised in that： The modifying agent that chemical modification uses includes stearoylketene methacrylate and dimethylamino-ethyl ethylmethacrylate copolymer, chromic anhydride Or coupling agent；
    The coupling agent includes one kind in silane coupler, titanate coupling agent, aluminate coupling agent, zircoaluminate coupling agent It is or several.
  12. 12. Multifunctional electrothermic film made of multifunctional graphite vinyl electric heating slurry according to claim 9, it is characterised in that： Step（2）Described graphene conductive heating layer thickness is 0.001- 0.5mm；Resistivity value is 0.2-200 Ω cm；
    Should cover insulating protective layer when making Electric radiant Heating Film, outside graphene conductive heating layer, the insulating protective layer by coating, Spraying method is combined on the outside of heating layer, and thickness is 0.01-0.5 mm, and protective layer material is polyurethane, ABS resins, polyamides One kind in amine, polysulfones, polyimides or PEI.
  13. 13. Multifunctional electrothermic film made of multifunctional graphite vinyl electric heating slurry according to claim 9, it is characterised in that： Step（2）Described electric heating slurry and the compound method of base material include thermal spraying, silk-screen printing, infusion process, spread method, roll printing method In one kind；Described graphene electrothermal layer, which is dried, takes the stage to be incubated, and drying temperature is 60-150 DEG C；Drying means includes One kind during closed oven drying, infrared light irradiation are dry, volume to volume is dry, UV is dried.
  14. A kind of 14. application of the Multifunctional electrothermic film described in any one of claim 9 ~ 13 in electrothermal device.
  15. 15. application according to claim 14, it is characterised in that：Multifunctional electrothermic film is by graphene under different operating voltage Conductive heating layer is formed with base material；Described operating voltage is 3-220 V；
    Effective operating temperature section of Multifunctional electrothermic film is 30-120 DEG C；It is adjustable from room temperature electrified regulation to the stable time Control is in 1-10 mim；Its power density is in 30-500W/m2。
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CN108273478A (en) * 2018-03-09 2018-07-13 李怀玉 A kind of formaldehyde removing composition and product
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CN112566290A (en) * 2020-12-31 2021-03-26 深圳市德龙电器有限公司 Flexible electric heating film heating layer and preparation method thereof
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CN113801534A (en) * 2021-06-24 2021-12-17 浙江理工大学 Preparation method of graphene electrothermal film
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103108923A (en) * 2010-07-12 2013-05-15 韩华石油化学株式会社 Conductive coating composition and method for manufacturing a conductive layer using same
CN104277198A (en) * 2014-10-25 2015-01-14 朱蕾 Preparation method of graphene-based conductive flame-retardant water-based polyurethane coating and adhesive
CN105898906A (en) * 2016-05-16 2016-08-24 德阳烯碳科技有限公司 Method for preparing electrothermal film by graphene aqueous slurry
CN105906832A (en) * 2016-06-29 2016-08-31 德阳烯碳科技有限公司 Preparation method of graphene-containing water-based electrothermal film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103108923A (en) * 2010-07-12 2013-05-15 韩华石油化学株式会社 Conductive coating composition and method for manufacturing a conductive layer using same
CN104277198A (en) * 2014-10-25 2015-01-14 朱蕾 Preparation method of graphene-based conductive flame-retardant water-based polyurethane coating and adhesive
CN105898906A (en) * 2016-05-16 2016-08-24 德阳烯碳科技有限公司 Method for preparing electrothermal film by graphene aqueous slurry
CN105906832A (en) * 2016-06-29 2016-08-31 德阳烯碳科技有限公司 Preparation method of graphene-containing water-based electrothermal film

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CN108273478B (en) * 2018-03-09 2021-03-02 李怀玉 Formaldehyde removal composition and product
CN108273478A (en) * 2018-03-09 2018-07-13 李怀玉 A kind of formaldehyde removing composition and product
CN108559359A (en) * 2018-04-25 2018-09-21 中南林业科技大学 A kind of fire-resistant coating for steel structure and preparation method thereof of decalescence, expandable flame retardant
CN110611964A (en) * 2018-06-14 2019-12-24 苏州汉纳材料科技有限公司 Heating film material with PTC effect and preparation method thereof
CN109068413A (en) * 2018-07-20 2018-12-21 江苏三六石墨烯科技有限公司 The preparation method of graphite composite film, the graphite composite film being obtained by this method and its application
CN109233597A (en) * 2018-08-23 2019-01-18 中国科学院福建物质结构研究所 A kind of high throughput prepare graphite it is dilute/method of Waterborne PU Composite
CN109575872A (en) * 2018-11-08 2019-04-05 佛山市真由美化工建材有限公司 A kind of mould proof silicone sealant of high temperature resistant and preparation method thereof
CN109587842A (en) * 2018-11-08 2019-04-05 中国科学院山西煤炭化学研究所 A kind of graphene-based self limiting temperature electric heating slurry and preparation method thereof and the application in electric heating floor system
CN109536142B (en) * 2019-01-15 2020-07-31 苏州世华新材料科技股份有限公司 Preparation method of graphene film heat conduction material
CN109536142A (en) * 2019-01-15 2019-03-29 苏州世华新材料科技股份有限公司 A kind of preparation method of graphene film Heat Conduction Material
CN110437509A (en) * 2019-02-18 2019-11-12 杭州电子科技大学 A kind of preparation method of conduction enhanced functional rubber
CN110437509B (en) * 2019-02-18 2021-06-25 杭州电子科技大学 Preparation method of conductive enhanced functional rubber
CN110167217A (en) * 2019-06-11 2019-08-23 郑州新世纪材料基因组工程研究院有限公司 A kind of infrared pyrogenicity body of electricity and preparation method thereof
CN110167217B (en) * 2019-06-11 2022-04-01 郑州新世纪材料基因组工程研究院有限公司 Electric infrared heating body and preparation method thereof
CN110415859A (en) * 2019-07-04 2019-11-05 东莞福哥电子有限公司 A kind of wear-resisting long-life conductive carbon paste
CN111154349B (en) * 2020-01-16 2021-11-16 上海立邦长润发涂料有限公司 PU (polyurethane) water-based refinishing paint and preparation method thereof
CN111154349A (en) * 2020-01-16 2020-05-15 上海立邦长润发涂料有限公司 PU (polyurethane) water-based refinishing paint and preparation method thereof
CN111269463A (en) * 2020-04-02 2020-06-12 中国科学技术大学 Ultrathin low-voltage electric heating film material in low-temperature environment and preparation method thereof
CN111432508A (en) * 2020-04-15 2020-07-17 威海无缝新材料有限公司 Graphene fast heating film and preparation method thereof
CN111556598B (en) * 2020-05-27 2022-05-27 佛山(华南)新材料研究院 Flexible low-voltage infrared electrothermal film and preparation method thereof
CN111556598A (en) * 2020-05-27 2020-08-18 佛山(华南)新材料研究院 Flexible low-voltage infrared electrothermal film and preparation method thereof
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CN112291868A (en) * 2020-09-14 2021-01-29 兰州大学 Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof
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CN112457758A (en) * 2020-11-26 2021-03-09 杭州白熊科技有限公司 Graphene slurry, electrothermal coating and electrothermal film prepared from graphene slurry, and application of electrothermal coating and electrothermal film in electrothermal heating
CN112656276A (en) * 2020-12-28 2021-04-16 深圳科利电器有限公司 Toilet seat ring based on graphene heating, temperature control system and electronic toilet
CN112566290A (en) * 2020-12-31 2021-03-26 深圳市德龙电器有限公司 Flexible electric heating film heating layer and preparation method thereof
CN112920364A (en) * 2021-01-28 2021-06-08 江苏威久科技发展有限公司 Polyurethane foam based on graphene modification and preparation method thereof
CN112954836A (en) * 2021-02-07 2021-06-11 张标 Electrothermal film based on graphene electrothermal and preparation method thereof
CN112954836B (en) * 2021-02-07 2023-09-29 张标 Electrothermal film based on graphene electrothermal and preparation method thereof
CN112909097B (en) * 2021-02-27 2023-04-18 贵溪穿越光电科技有限公司 Graphene/black phosphorus alkene composite thin film transistor and preparation method thereof
CN112909097A (en) * 2021-02-27 2021-06-04 成都市水泷头化工科技有限公司 Graphene/black phosphorus alkene composite thin film transistor and preparation method thereof
CN113801534A (en) * 2021-06-24 2021-12-17 浙江理工大学 Preparation method of graphene electrothermal film
CN114350000A (en) * 2022-01-17 2022-04-15 归壹生命科技(东莞)有限公司 Manufacturing process of graphene electric heating silica gel sheet
CN114656879A (en) * 2022-03-22 2022-06-24 河北志盛威华特种涂料有限公司 Permeable anti-oxidation coating and preparation method thereof
CN114621611A (en) * 2022-04-02 2022-06-14 北京斯年智驾科技有限公司 Heating material with graphene sprayed on ceramic surface
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CN115785740B (en) * 2022-10-11 2023-09-01 浙江省海洋开发研究院 Graphene-based high-conductivity acid-containing ink and preparation method thereof
CN115538158A (en) * 2022-11-11 2022-12-30 东莞市鸿亿导热材料有限公司 Preparation method of flexible graphene composite material and product thereof
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CN115770623A (en) * 2022-12-09 2023-03-10 梧州黄埔化工药业有限公司 Preparation method of ion exchange membrane for camphor esterification reaction
CN115770623B (en) * 2022-12-09 2024-03-29 梧州黄埔化工药业有限公司 Preparation method of ion exchange membrane for camphoresterification reaction
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