CN107384026A - A kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink and preparation method - Google Patents
A kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink and preparation method Download PDFInfo
- Publication number
- CN107384026A CN107384026A CN201710724488.6A CN201710724488A CN107384026A CN 107384026 A CN107384026 A CN 107384026A CN 201710724488 A CN201710724488 A CN 201710724488A CN 107384026 A CN107384026 A CN 107384026A
- Authority
- CN
- China
- Prior art keywords
- water
- dispersion
- graphene
- cnt
- watersoluble plumbago
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a kind of preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, comprise the following steps：Graphene microchip, water-based nonionic macromolecule dispersing agent and water are stirred, then disperseed to obtain the first dispersion；One-dimensional carbon nanopowder body is placed in inorganic acid, temperature rising reflux, be ultrasonically treated, washing, be dried to obtain the second dispersion；Second dispersion and carbon black powder, water-based anionic dispersing agent, neopelex, water-based hydroxyl modified Nano acrylic emulsion, dimethylethanolamine are well mixed, then disperse to obtain the 3rd dispersion；First dispersion, the 3rd dispersion, water-base resin are mixed, grinding, add the well mixed watersoluble plumbago alkene/CNT compound electro-thermal that obtains of levelling agent, defoamer, pH adjusting agent, preservative, antiprecipitant and convert ink.The invention also discloses a kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink.
Description
Technical field
The present invention relates to electric heating to convert technical field of ink, more particularly to a kind of watersoluble plumbago alkene/CNT compound electric
Thermal transition ink and preparation method thereof.
Background technology
For winter northern environment based on dry and cold, conventional heating mode, particularly boiler type heating system easily causes air
Pollution, haze take place frequently.In recent years, government has to take a series of compulsory measures, and the coal-burning boiler for removing a large amount of high pollutions is set
It is standby, with the occurring source that reduces environmental pollution, alleviate northern haze phenomenon.Meanwhile to improve the living environment of resident, government puts into effect
Corresponding subsidy policy, such as mounting cost subsidy and electricity charge subsidy, allround promotion and practicable " coal changes electricity ".It is particularly northern,
Under " coal changes electricity " policy support of government, " coal changes electricity " technology is widelyd popularize with product development with using, encourages resident's cleaning to adopt
It is warm, the coal-fired arcola of tradition is progressively banned, slows down the generation of haze disaster, promotes energy-saving and emission-reduction.
By the development of more than ten years, electricity floor heating heating system is progressively received and approved by consumers in general.Early stage electricity floor heating
Product is using carbon crystal material as heater, and using polyester (PET) film as printing carrier, carbon crystal type electricity is produced using gravure application
Hotting mask.The printing-ink that this kind of product uses is oiliness, and various volatile materials are more in the solvent used, and environmental protection pressure is big.
Meanwhile carbon crystal also has that service life is short for the Electric radiant Heating Film of heater, the heating in efficient heat generation area is uneven, far infrared wave
The shortcomings such as long transformation efficiency is low.Develop environmental protection, long lifespan, the Electric radiant Heating Film that heating is uniform, far infrared wavelength transformation efficiency is high and electricity
Thermal transition ink is the emphasis of industry development, and the developing direction of following electric heating product.
At present, environment-friendly type aqueous graphene electric heating conversion ink preparation work is concentrated mainly on graphene dispersion, life-span
Long-actingization, conversion high efficiency, heat uniforming etc..The patent of invention of Application No. 201710211519.8 discloses a kind of graphene
Three-dimensional composite water soluble electric heating ink and preparation method thereof, it is mixed with graphene dispersing solution, carbon nano tube dispersion liquid, carbon black dispersion liquid
Conjunction forms three-dimensional stability structure；Improve back bone network resistance stability.But this method resin liter during dispersion liquid is prepared
Warm too high (70-90 DEG C), it is common resin to be present hot setting fails the deficiencies of；If not high-temperature process, common difference is disperseed
It is low that liquid is manufactured separately solid content, it is difficult to improve solid content, causes water content to rise, material monolithic conductive difference etc.；High temperature concentrates
During, what common carbon material had agglomeration, particularly a flake graphite alkene material becomes graphite in reunion；Meanwhile
Prepare the problems such as cumbersome, power consumption is larger, economic adaptability during dispersion liquid.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes a kind of watersoluble plumbago alkene/CNT compound electric
Thermal transition ink and preparation method thereof, technique is simple, mature and stable, easy to operate, gained watersoluble plumbago alkene/CNT compound electric
Thermal transition ink resistance is controllable, good conductivity, and adhesive force is good.Obtained electric heating conversion film is applied to resident's electric heating, greenhouse
, there is extraordinary application prospect in the fields such as greenhouse gardening, airport ground snow removing.
A kind of preparation method of watersoluble plumbago alkene proposed by the present invention/CNT compound electro-thermal conversion ink, including such as
Lower step：
S1, graphene microchip, water-based nonionic macromolecule dispersing agent and water stirred, then disperseed to obtain
First dispersion；
S2, one-dimensional carbon nanopowder body is placed in inorganic acid, temperature rising reflux, be ultrasonically treated, washing, be dried to obtain second
Dispersion；
S3, by the second dispersion and carbon black powder, water-based anionic dispersing agent, neopelex, water-based hydroxyl
Base modified Nano acrylic emulsion, dimethylethanolamine are well mixed, and then disperse to obtain the 3rd dispersion；
S4, by the first dispersion, the 3rd dispersion, water-base resin mix, grinding, add levelling agent, defoamer, pH adjust
Section agent, preservative, the well mixed watersoluble plumbago alkene/CNT compound electro-thermal that obtains of antiprecipitant convert ink.
Preferably, the preparation method of a kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, including following step
Suddenly：
S1, graphene microchip, water-based nonionic macromolecule dispersing agent and water stirred, speed of agitator 50-
300rpm, then disperseed, rate of dispersion 600-1400rpm, obtain the first dispersion；
S2, one-dimensional carbon nanopowder body is placed in inorganic acid, temperature rising reflux, be ultrasonically treated, washing, be dried to obtain second
Dispersion；
S3, by the second dispersion and carbon black powder, water-based anionic dispersing agent, neopelex, water-based hydroxyl
Base modified Nano acrylic emulsion, dimethylethanolamine are well mixed, and speed of agitator 50-300rpm, are then disperseed, and disperse speed
Spend for 600-1400rpm, obtain the 3rd dispersion；
S4, by the first dispersion, the 3rd dispersion, water-base resin mixing 1-60min, mix rotating speed 1-1440rpm, grinding
1-60min, grinding rotating speed are 1-1440rpm, and grinding zirconium spherolite degree is 1.0-2.0mm, add levelling agent, defoamer, pH and adjust
Section agent, preservative, the well mixed watersoluble plumbago alkene/CNT compound electro-thermal that obtains of antiprecipitant convert ink.
Preferably, in S1, the mass ratio of graphene microchip, water-based nonionic macromolecule dispersing agent and water is 0.1-10：
0.1-2：88-99.
Preferably, in S1, graphene microchip is that graphene made from vapor plasma, graphene made from arc process are thin
One or more in piece, redox graphene, graphene nanometer sheet, modified graphene.
Preferably, in S1, the carbon content of graphene microchip is more than 99%, and its lateral dimension is 0.1-20 μm, its piece thickness
Spend for 0.1-3.35nm.
Preferably, in S2, CNT is multi-walled carbon nanotube, single-walled carbon nanotube, gas phase nano carbon fiber, onion shape
One or more in CNT.
Preferably, in S2, CNT is multi-walled carbon nanotube, gas phase nano carbon fiber or onion shape CNT.
Preferably, in S2, the carbon content of CNT is more than 99%, and its caliber is 0.1-50nm, and its draw ratio is 0.1-
50。
Preferably, in S2, inorganic acid is concentrated nitric acid and/or the concentrated sulfuric acid.
Preferably, inorganic acid is that concentrated nitric acid and the concentrated sulfuric acid are 0.1-1 by volume：3, preferably 1：3.
Preferably, in S2, reflux temperature is 100-150 DEG C, ultrasonic power 0.1-300W, drying temperature 60-100
℃。
Preferably, in S2, ultrasonic power 300W.
Preferably, in S2, drying mode is vacuum drying.
Preferably, in S2, drying temperature is 80 DEG C.
Preferably, washing times are 3-10 times.
Preferably, in S3, the second dispersion and carbon black powder, water-based anionic dispersing agent, water-based hydroxyl modified Nano
The mass ratio of acrylic emulsion is 0.1-10：0.1-30：0.1-4：0.1-30.
Preferably, in S3, the granularity of carbon black powder is 50-200nm (D90), preferably 50-100nm.
Preferably, in S3, in addition to dimethylethanolamine.
Preferably, in S3, the second dispersion and carbon black powder, water-based anionic dispersing agent, water-based hydroxyl modified Nano
Acrylic emulsion, the mass ratio of dimethylethanolamine are 5-10：10-30：2-4：0.1-30：0-2.5.
Preferably, in S3, water-based anionic dispersing agent is anion-type water-thinned hyper-dispersant, including anchoring group and molten
Agent chain part.
Preferably, the anchoring group of water-based anionic dispersing agent is COO-、SO3H and/or SO3-。
Preferably, the solvent chain of water-based anionic dispersing agent is acrylic acid, acid anhydrides, hydro carbons, phenyl ring base, carbon oxygen cyclization
One or more in thing.
Preferably, the solvent chain of water-based anionic dispersing agent is made up of acrylic acid, acid anhydrides, carbon oxygen cyclocomplex.
Preferably, the degree of polymerization of the solvent chain of water-based anionic dispersing agent is 1-10000, preferably 1-100.
Preferably, it is the first dispersion, the 3rd dispersion, water-base resin, levelling agent, defoamer, preservative, anti-heavy in S4
The mass ratio of shallow lake agent is 0.1-30：0.1-50：0.1-40：0.01-0.2：0.01-0.2：0.01-0.2：0.01-0.2.
Preferably, in S4, granularity is ground to as 1-20 μm.
Preferably, in modified graphene, epoxidized soybean oil, polyoxypropyleneglycol, catalyst Ti acid esters are mixed, nitrogen
Under gas shielded, in 140-148 DEG C of reaction of temperature, it is warming up to 190-210 DEG C and continues to react, remove nitrogen protection, add oxidation stone
Black alkene, toluene mix, ultrasonic disperse, nitrogen protection under, be added dropwise thionyl chloride, be added dropwise completely after in temperature 85-95 DEG C stir
Mix, distillation removes toluene and unnecessary thionyl chloride, adds pyridine stirring, obtains modified graphene.
It is further preferred that in modified graphene, by weight by 4-8 parts epoxidized soybean oil, 0.5-1 parts polyoxygenated third
Enediol, the mixing of 0.01-0.02 part catalyst Tis acid esters, under nitrogen protection, in 140-148 DEG C of reaction 30-50min of temperature, rise
Temperature continues to react 40-70min to 190-210 DEG C, removes nitrogen protection, adds 30-50 parts graphene oxide, 100-200 part first
Benzene mixes 5-15min, mixing speed 1600-1800r/min, ultrasonic disperse 20-40min, supersonic frequency 4500-
5000Hz, under nitrogen protection, 2-4 part thionyl chlorides are added dropwise, are gone after being added dropwise completely in 85-95 DEG C of stirring 20-30h of temperature, distillation
Except toluene and unnecessary thionyl chloride, add 0.1-0.2 part pyridines and continue to stir 2-3h, obtain modified graphene.
The present invention also proposes a kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, using above-mentioned watersoluble plumbago
The preparation method of alkene/CNT compound electro-thermal conversion ink is made.
Preferably, the solid content of gained watersoluble plumbago alkene/CNT compound electro-thermal conversion ink is 1-60%, its granularity
For 1-20 μm, viscosity 1-10000mPa.s, sheet resistance is 10-104 Ω/, 0 grade of adhesive force.
Gained watersoluble plumbago alkene of the invention/CNT compound electro-thermal conversion ink has the following technical effect that：
(1) present invention uses one-dimensional wire carbon material (one-dimensional carbon nanopowder body) and zero dimension carbon material (carbon black powder) as resistance
Every agent, the dispersiveness for preventing graphene in graphitization, on the one hand raising graphene is punctured into inside flake graphite alkene, on the other hand
The three-dimensional sponge body conductive structure network that one-dimensional carbon material, zero dimension carbon material and graphene are self-assembled into layer by layer adds composite guide
The electric conductivity of electrical carbon material, improve paint film conduction uniformity.
(2) surface carboxyl groups of one-dimensional wire carbon material and water-based hydroxyl modified Nano propylene yogurt after inorganic acid is handled
Liquid surface hydroxyl carries out chemical bonding processing, obtains dispersed conductive emulsion, then is punctured into graphene sheet layer, by graphite
Alkene piece is wrapped in the three-dimensional cylinder mould emulsion of CNT composition, improves the ability of resin emulsion outer cladding graphene, significantly
Dispersiveness of the graphene in emulsion is improved, also greatly improves conductive carbon material service life.
(3) zero dimension carbon material carries out cladding processing with water-based hydroxyl modified Nano acrylic emulsion, passes through nano carbon particle
Surface great amount of hydroxy group carries out hydrogen bond weak binding power with water-based hydroxyl modified Nano acrylic emulsion surface hydroxyl and acted on, with emulsion bag
Zero dimension carbon material after covering is barrier, interspersed agent reaches graphene film piece bridging effect, coordinates the cylinder mould knot of CNT composition
Structure emulsion, using high-strength nano water-base resin as carrier, prepare that adhesive force is good, and water-fast, the watersoluble plumbago of resistance to alcohol alkene/CNT is multiple
Electric heating conversion ink is closed, is adapted to the levelability of intaglio printing, the excellent rate of product of Electric radiant Heating Film is substantially increased, improves product and go out
Factory's security.
(4) in modified graphene, further high temperature open loop, ring after epoxidized soybean oil, polyoxypropyleneglycol ester exchange
Oxygen key occurs open loop and forms hydroxyl, graphene oxide can it is dispersed wherein, the lower graphene oxide of nitrogen protection completes acyl first
Chlorination, the then acid chloride groups hydroxyl reaction with above-mentioned formation again under the cooperation of pyridine, finally in surface of graphene oxide bag
Layer protecting film is covered, not only bond strength is high difficult for drop-off, and according to similar compatibility principle, can effectively improve and disperse with the 3rd
The compatibility of body, water-base resin, be more convenient for one-dimensional wire carbon material and zero dimension carbon material intert, and will not cause graphene group
Poly- graphitization, mutual degree of scatter is high after grinding, not only can effectively enhanced article adhesive force and hot property, and electricity
The electric conductivity of hotting mask further enhances, and modified graphene combines organic protective film due to surface in addition, is more easy in conductive carbon material
Emulsion is disperseed, and further improves the ability of resin emulsion coated graphite alkene, and substantially increase conductive carbon material uses the longevity
Life, the security of Electric radiant Heating Film is high, and raw material is cheap, and method is simple, easy to operate.
Gained watersoluble plumbago alkene of the invention/CNT compound electro-thermal conversion ink has uniformly dispersed, high conductivity
The advantages that, it is good to prepare adhesive force, water-fast, the watersoluble plumbago of resistance to alcohol alkene/CNT compound electro-thermal conversion ink, is adapted to intaglio process
The levelability of brush, the excellent rate of product of Electric radiant Heating Film is substantially increased, improve product export security.
Electric heating conversion film obtained by it is applied to the fields such as resident's electric heating, warmhouse booth plantation, airport ground snow removing,
There is extraordinary application prospect.
Brief description of the drawings
Fig. 1 is a kind of watersoluble plumbago alkene proposed by the present invention/preparation of CNT compound electro-thermal conversion ink, conductive original
Reason figure.
Embodiment
As shown in figure 1, Fig. 1 is a kind of watersoluble plumbago alkene proposed by the present invention/CNT compound electro-thermal conversion ink
Prepare, conductivity principle figure.
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
Reference picture 1, a kind of preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, including following step
Suddenly：
S1, by 5 parts of graphene microchips, (carbon content is more than 99%, and lateral dimension is 10-20 μm, graphene film by weight
Thickness degree is 2.0-3.35nm), 1.25 parts of water-based nonionic oligomerization macromolecule dispersing agents, 93.75 parts of water automatic chargings extremely
In 500L stirred tanks, agitating paddle, speed of agitator 200rpm, mixing time 20min are opened；Open high speed dispersion dish and carry out height
Speed is scattered, rate of dispersion 1200rpm, jitter time 20min, and environment temperature is 25 DEG C in high speed dispersion process；Disperse
The first dispersion is obtained after；
Wherein graphene microchip be graphene made from vapor plasma, graphene platelet, reduction made from arc process
The one or more of graphene oxide, graphene nanometer sheet；
S2, by multi-walled carbon nanotube, (99%) caliber 0.1-50nm, draw ratio 0.1-50, carbon content are more than, are placed in
Concentrated nitric acid and the concentrated sulfuric acid by volume 1：In 3 inorganic acids being mixed to get, under the conditions of 140 DEG C, flow back 6h, is placed at ultrasonic wave
30min is handled under 300w ultrasound intensities in reason device, is washed to neutrality, 80 DEG C of vacuum drying obtain the second dispersion；
S3, by weight by 2 part of second dispersion, 30 parts of water-based hydroxyl modified Nano acrylic emulsions, 0.5 part of dodecane
In base benzene sulfonic acid sodium salt and 43 parts of ultra-pure water automatic charging to stirred tanks, agitating paddle, speed of agitator 200rpm, mixing time are opened
For 20min, carbon black powder, 2 parts of water-based anionic dispersing agents, 2.5 parts of dimethyl ethanols that 20 parts of granularities are 50nm are added
Amine, open agitating paddle, speed of agitator 200rpm, mixing time 20min；Then high speed dispersion dish are opened divide at a high speed
Dissipate, rate of dispersion 1200rpm, jitter time 20min, environment temperature is 25 DEG C in high speed dispersion process；After the completion of scattered,
It is filtrated to get the 3rd dispersion；
S4,20 part of first dispersion, 40 part of the 3rd dispersion, 40 parts of water-base resins are mixed by weight, open stirring,
Speed of agitator is 200rpm, mixing time 20min, is then turned on scattered at a high speed, rate of dispersion 1200rpm, and jitter time is
20min；Then granularity is ground to as 5 μm, and grinding rotating speed is 800rpm；Then add 0.2 part of levelling agent, 0.2 part of defoamer,
0.2 part of pH adjusting agent, 0.2 portion of preservative, 0.2 part of antiprecipitant stirring, speed of agitator 200rpm, mixing time 20min,
It is then turned on high speed dispersion dish disperse at a high speed, rate of dispersion 1200rpm, jitter time 20min, in high speed dispersion process
Environment temperature is 25 DEG C, obtains watersoluble plumbago alkene/CNT compound electro-thermal conversion ink.
Embodiment 2
S1, S2, S4 are same as Example 1, and S3 is changed to：
By weight by 2 part of second dispersion, 30 parts of water-based hydroxyl modified Nano acrylic emulsions, 0.5 part of dodecyl
In benzene sulfonic acid sodium salt and 33 parts of ultra-pure water automatic charging to stirred tanks, agitating paddle, speed of agitator 200rpm are opened, mixing time is
20min, carbon black powder, 2 parts of water-based anionic dispersing agents, 2.5 parts of dimethylethanolamines that 30 parts of granularities are 50nm are added,
Open agitating paddle, speed of agitator 200rpm, mixing time 20min；Then high speed dispersion dish are opened disperse at a high speed, point
It is 1200rpm to dissipate speed, jitter time 20min, and environment temperature is 25 DEG C in high speed dispersion process；After the completion of scattered, filtering
Obtain the 3rd dispersion.
Embodiment 3
S1, S2, S3 are same as Example 1, and S4 is changed to：
20 part of first dispersion, 50 part of the 3rd dispersion, 30 parts of water-base resins are mixed by weight, stirring is opened, stirs
Mix rotating speed is 200rpm, mixing time 20min, is then turned on scattered at a high speed, rate of dispersion 1200rpm, and jitter time is
20min；Then granularity is ground to as 5 μm, and grinding rotating speed is 800rpm；Then add 0.2 part of levelling agent, 0.2 part of defoamer,
0.2 part of pH adjusting agent, 0.2 portion of preservative, 0.2 part of antiprecipitant stirring, speed of agitator 200rpm, mixing time 20min,
It is then turned on high speed dispersion dish disperse at a high speed, rate of dispersion 1200rpm, jitter time 20min, in high speed dispersion process
Environment temperature is 25 DEG C, obtains watersoluble plumbago alkene/CNT compound electro-thermal conversion ink.
Embodiment 4
S1, S2 are same as Example 1, and S3 is same as Example 2, and S4 is same as Example 3.
Embodiment 5
S2, S3, S4 are same as Example 4, and S1 is changed to：
By weight by 5 parts of modified graphenes, 1.25 parts of water-based nonionic oligomerization macromolecule dispersing agents, 93.75 parts
In water automatic charging to 500L stirred tanks, agitating paddle, speed of agitator 200rpm, mixing time 20min are opened；Open at a high speed
Dispersion impeller carries out scattered at a high speed, rate of dispersion 1200rpm, jitter time 20min, and environment temperature is in high speed dispersion process
25℃；The first dispersion is obtained after the completion of scattered；
In modified graphene, 6 parts of epoxidized soybean oils, 0.68 part of polyoxypropyleneglycol, 0.012 part are urged by weight
Agent titanate esters mix, and under nitrogen protection, in 146 DEG C of reaction 42min of temperature, are warming up to 205 DEG C and continue to react 52min, remove
Nitrogen is protected, and adds 42 parts of graphene oxides, 180 parts of toluene mix 10min, mixing speed 1720r/min, ultrasound point
Dissipate 32min, supersonic frequency 4850Hz, nitrogen protection under, be added dropwise 2.15 parts of thionyl chlorides, be added dropwise completely after in temperature 92 DEG C stir
16h is mixed, distillation removes toluene and unnecessary thionyl chloride, adds 0.14 part of pyridine and continues to stir 2-3h, obtains modified graphene.
Comparative example 1
S1 is same as Example 1, and subsequent step is as follows：
S2, by weight by 20 parts of granularities be 50nm carbon black powder, 30 parts of water-based hydroxyl modified Nano acrylic emulsions,
2 parts of water-based anionic dispersing agents, 45.5 parts of ultra-pure waters, in 2.5 parts of dimethylethanolamine automatic charging to stirred tanks, unlatching is stirred
Mix oar, speed of agitator 200rpm, mixing time 20min；Then high speed dispersion dish are opened and carry out scattered at a high speed, rate of dispersion
For 1200rpm, jitter time 20min, environment temperature is 25 DEG C in high speed dispersion process；After the completion of scattered, thing is filtrated to get
Expect a；
S3,20 part of first dispersion, 50 parts of material a, 30 parts of water-base resins are mixed by weight, open stirring, stirring
Rotating speed is 200rpm, mixing time 20min, is then turned on scattered at a high speed, rate of dispersion 1200rpm, and jitter time is
20min；Then granularity is ground to as 5 μm, and grinding rotating speed is 800rpm；Then add 0.2 part of levelling agent, 0.2 part of defoamer,
0.2 part of pH adjusting agent, 0.2 portion of preservative, 0.2 part of antiprecipitant stirring, speed of agitator 200rpm, mixing time 20min,
It is then turned on high speed dispersion dish disperse at a high speed, rate of dispersion 1200rpm, jitter time 20min, in high speed dispersion process
Environment temperature is 25 DEG C, obtains finished product electric heating conversion ink.
Comparative example 2
S1 is same as Example 1, and subsequent step is as follows：
S2, by weight by 2 parts of CNTs, 30 parts of water-based hydroxyl modified Nano acrylic emulsions, 0.5 part of dodecyl
Benzene sulfonic acid sodium salt, 65 parts of ultra-pure waters, in 2.5 parts of dimethylethanolamine automatic charging to stirred tanks, agitating paddle is opened, speed of agitator is
200rpm, mixing time 20min；Then high speed dispersion dish are opened disperse at a high speed, rate of dispersion 1200rpm, are disperseed
Time is 20min, and environment temperature is 25 DEG C in high speed dispersion process；After the completion of scattered, material b is filtrated to get；
S3,20 part of first dispersion, 50 parts of material b, 30 parts of water-base resins are mixed by weight, open stirring, stirring
Rotating speed is 200rpm, mixing time 20min, is then turned on scattered at a high speed, rate of dispersion 1200rpm, and jitter time is
20min；Then granularity is ground to as 5 μm, and grinding rotating speed is 800rpm；Then add 0.2 part of levelling agent, 0.2 part of defoamer,
0.2 part of pH adjusting agent, 0.2 portion of preservative, 0.2 part of antiprecipitant stirring, speed of agitator 200rpm, mixing time 20min,
It is then turned on high speed dispersion dish disperse at a high speed, rate of dispersion 1200rpm, jitter time 20min, in high speed dispersion process
Environment temperature is 25 DEG C, obtains finished product electric heating conversion ink.
Comparative example 3
S1 is same as Example 1, and subsequent step is as follows：
S2,20 part of first dispersion, 50 parts of water-base resins, 30 parts of ultra-pure waters are mixed by weight, open stirring, stirring
Rotating speed is 200rpm, mixing time 20min, is then turned on scattered at a high speed, rate of dispersion 1200rpm, and jitter time is
20min；Then granularity is ground to as 5 μm, and grinding rotating speed is 800rpm；Then add 0.2 part of levelling agent, 0.2 part of defoamer,
0.2 part of pH adjusting agent, 0.2 portion of preservative, 0.2 part of antiprecipitant stirring, speed of agitator 200rpm, mixing time 20min,
It is then turned on high speed dispersion dish disperse at a high speed, rate of dispersion 1200rpm, jitter time 20min, in high speed dispersion process
Environment temperature is 25 DEG C, obtains finished product electric heating conversion ink.
By watersoluble plumbago alkene obtained by embodiment 1-4/CNT compound electro-thermal conversion ink and electric heating obtained by comparative example 1-3
Convert ink and carry out contrast properties test, its result is as follows：
Zero dimension carbon material (carbon black), one-dimensional carbon material (CNT), the Two-dimensional Carbon of different proportion are used in embodiment 1-5
Material (graphene microchip) is carried out preparing watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, it was demonstrated that different proportion is matched somebody with somebody
The electric conductivity, conductive uniformity, adhesive force for comparing electric heating conversion ink all have an impact.
And comparative example 1-5 prepares electric heating conversion ink using inhomogeneity dimension carbon material, it was demonstrated that zero dimension, one-dimensional carbon material
As the effect of intercalation, barrier, while water-based hydroxyl modified Nano acrylic emulsion is cross-linked into cylinder mould shape with one-dimensional carbon material
Good dispersed graphite alkene microplate, prevent graphene microchip from graphitization occurs in agglomeration, have enhancing to the adhesive force of ink
Effect.
Watersoluble plumbago alkene/good conductive uniformity of CNT compound electro-thermal conversion ink has the electric heating for preventing preparing
Film produces hot-spot and causes the safety problem such as on fire because printed resistor is uneven.Meanwhile one-dimensional carbon material, zero dimension carbon materials
The three-dimensional sponge body conductive structure network that material and graphene are self-assembled into layer by layer adds the conductive life-span of composite conducting carbon material,
Substantially increase the service life of Electric radiant Heating Film.
Present invention process is simple, mature and stable, easy to operate, gained watersoluble plumbago alkene/CNT compound electro-thermal conversion oil
Black resistance is controllable, and adhesive force is good, water-fast, alcohol resistance is good, has that environmental protection, long lifespan, heating be uniform, far infrared wavelength transformation efficiency
The features such as high, the electric heating conversion film obtained by it are applied to the necks such as resident's electric heating, warmhouse booth plantation, airport ground snow removing
Domain, there is extraordinary application prospect.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. the preparation method of a kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, it is characterised in that including following step
Suddenly：
S1, graphene microchip, water-based nonionic macromolecule dispersing agent and water is uniformly mixing to obtain the first dispersion；
S2, one-dimensional carbon nanopowder body is placed in inorganic acid, temperature rising reflux, be ultrasonically treated, washing, it is scattered to be dried to obtain second
Body；
S3, the second dispersion and carbon black powder, water-based anionic dispersing agent, neopelex, water-based hydroxyl changed
Property nanometer acrylic emulsion is well mixed obtains the 3rd dispersion；
S4, by the first dispersion, the 3rd dispersion, water-base resin mix, grinding, add levelling agent, defoamer, pH regulation
Agent, preservative, the well mixed watersoluble plumbago alkene/CNT compound electro-thermal that obtains of antiprecipitant convert ink.
2. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In in S1, the mass ratio of graphene microchip, water-based nonionic macromolecule dispersing agent and water is 0.1-10：0.1-2：88-99.
3. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In in S1, graphene microchip is graphene made from vapor plasma, graphene platelet, reduction-oxidation made from arc process
One or more in graphene, graphene nanometer sheet, modified graphene；Preferably, in S1, the carbon content of graphene microchip
More than 99%, its lateral dimension is 0.1-20 μm, and its lamellar spacing is 0.1-3.35nm.
4. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In in S2, CNT is in multi-walled carbon nanotube, single-walled carbon nanotube, gas phase nano carbon fiber, onion shape CNT
It is one or more kinds of；Preferably, in S2, CNT is multi-walled carbon nanotube, gas phase nano carbon fiber or onion shape carbon nanometer
Pipe；Preferably, in S2, the carbon content of CNT is more than 99%, and its caliber is 0.1-50nm, and its draw ratio is 0.1-50.
5. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In in S2, inorganic acid is concentrated nitric acid and/or the concentrated sulfuric acid；Preferably, inorganic acid is concentrated nitric acid and the concentrated sulfuric acid is by volume
0.1-1：3, preferably 1：3.
6. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In in S2, reflux temperature is 100-150 DEG C, ultrasonic power 0.1-300W, and drying temperature is 60-100 DEG C；Preferably, water
Number is washed as 3-10 times.
7. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In, in S3, the second dispersion and carbon black powder, water-based anionic dispersing agent, water-based hydroxyl modified Nano acrylic emulsion
Mass ratio is 0.1-10：0.1-30：0.1-4：0.1-30；
Preferably, water-based anionic dispersing agent is anion-type water-thinned hyper-dispersant, including anchoring group and solvent chain portion
Point；Preferably, anchoring group COO-, SO3H and/or SO3-；
It is further preferred that the solvent chain be acrylic acid, acid anhydrides, hydro carbons, phenyl ring base, one kind in carbon oxygen cyclocomplex or
It is a variety of；
It is further preferred that solvent chain is made up of acrylic acid, acid anhydrides, carbon oxygen cyclocomplex；
It is further preferred that the degree of polymerization of solvent chain is 1-10000, preferably 1-100.
8. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 1
In, in S4, the first dispersion, the 3rd dispersion, water-base resin, levelling agent, defoamer, preservative, the mass ratio of antiprecipitant
For 0.1-30：0.1-50：0.1-40：0.01-0.2：0.01-0.2：0.01-0.2：0.01-0.2.
9. the preparation method of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, its feature exist according to claim 3
In, in modified graphene, epoxidized soybean oil, polyoxypropyleneglycol, catalyst Ti acid esters are mixed, under nitrogen protection,
140-148 DEG C of reaction of temperature, is warming up to 190-210 DEG C and continues to react, and removes nitrogen protection, adds graphene oxide, toluene mixes
Stirring is closed, ultrasonic disperse, nitrogen protection is lower to be added dropwise thionyl chloride, and first is removed in 85-95 DEG C of stirring of temperature, distillation after being added dropwise completely
Benzene and unnecessary thionyl chloride, pyridine stirring is added, obtains modified graphene.
10. a kind of watersoluble plumbago alkene/CNT compound electro-thermal conversion ink, it is characterised in that appointed using such as claim 1-9
The preparation method of the one watersoluble plumbago alkene/CNT compound electro-thermal conversion ink is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710724488.6A CN107384026B (en) | 2017-08-22 | 2017-08-22 | A kind of watersoluble plumbago alkene/carbon nanotube compound electro-thermal conversion ink and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710724488.6A CN107384026B (en) | 2017-08-22 | 2017-08-22 | A kind of watersoluble plumbago alkene/carbon nanotube compound electro-thermal conversion ink and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107384026A true CN107384026A (en) | 2017-11-24 |
| CN107384026B CN107384026B (en) | 2018-10-09 |
Family
ID=60353912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710724488.6A Expired - Fee Related CN107384026B (en) | 2017-08-22 | 2017-08-22 | A kind of watersoluble plumbago alkene/carbon nanotube compound electro-thermal conversion ink and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107384026B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108550856A (en) * | 2018-05-23 | 2018-09-18 | 山东希诚新材料科技有限公司 | Carbon nano tube/graphene composite conducting slurry and preparation method thereof |
| CN109068412A (en) * | 2018-07-11 | 2018-12-21 | 安徽宝利乐暖环保科技有限公司 | A kind of containing graphene and the water nano heating film of carbon nanotube and preparation method thereof |
| CN109306209A (en) * | 2018-08-31 | 2019-02-05 | 江苏天创新材料科技有限公司 | A kind of preparation method of preparation method and cylinder the printing Electric radiant Heating Film of the black compound electro-thermal ink of graphene/carbon |
| CN109666339A (en) * | 2019-02-26 | 2019-04-23 | 新奥石墨烯技术有限公司 | Electric heating ink and preparation method thereof |
| CN110294960A (en) * | 2019-07-30 | 2019-10-01 | 高碑店市隆泰丰博石墨烯有限公司 | Freezing point is starched and preparation method in -20 DEG C or less anti-freeze type watersoluble plumbago alkene electric heating |
| CN110591485A (en) * | 2019-09-27 | 2019-12-20 | 安徽省聚科石墨烯科技股份公司 | Graphene plastic for packaging box and preparation method |
| CN110769528A (en) * | 2019-10-11 | 2020-02-07 | 深圳天元羲王材料科技有限公司 | Graphene aqueous heating film conductive paste |
| CN111334121A (en) * | 2020-04-17 | 2020-06-26 | 宁波石墨烯创新中心有限公司 | Water-based graphene PTC ink and preparation method thereof |
| CN111363413A (en) * | 2020-04-17 | 2020-07-03 | 宁波石墨烯创新中心有限公司 | Graphene-based PTC ink, electric heating device and preparation method of graphene-based PTC ink |
| CN112759980A (en) * | 2021-03-02 | 2021-05-07 | 梁贻波 | Environment-friendly anti-counterfeiting ink and preparation method thereof |
| CN114437604A (en) * | 2022-03-10 | 2022-05-06 | 信和新材料（苏州）有限公司 | Nanoparticle modified water-based white wood sealing primer and preparation method and application 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 |
| CN114957761A (en) * | 2022-04-12 | 2022-08-30 | 扬州大学 | Green preparation process of PET heating film |
| CN117025024A (en) * | 2023-10-09 | 2023-11-10 | 山东概念印刷有限公司 | Water-based ink composition for flexographic printing and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693897A (en) * | 2015-02-28 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Conductive ink based on graphene composite material and preparation method thereof |
| KR20150080370A (en) * | 2013-12-31 | 2015-07-09 | 삼성정밀화학 주식회사 | Metal ink for transparent electrodes and method of manufacturing the same |
| US20160177111A1 (en) * | 2014-12-17 | 2016-06-23 | Xerox Corporation | Nanosilver Ink Compositions Comprising Clay Additives |
| CN106883684A (en) * | 2017-04-01 | 2017-06-23 | 北京创新爱尚家科技股份有限公司 | Graphene three-dimensional composite water soluble electric heating ink and preparation method thereof |
-
2017
- 2017-08-22 CN CN201710724488.6A patent/CN107384026B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150080370A (en) * | 2013-12-31 | 2015-07-09 | 삼성정밀화학 주식회사 | Metal ink for transparent electrodes and method of manufacturing the same |
| US20160177111A1 (en) * | 2014-12-17 | 2016-06-23 | Xerox Corporation | Nanosilver Ink Compositions Comprising Clay Additives |
| CN104693897A (en) * | 2015-02-28 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Conductive ink based on graphene composite material and preparation method thereof |
| CN106883684A (en) * | 2017-04-01 | 2017-06-23 | 北京创新爱尚家科技股份有限公司 | Graphene three-dimensional composite water soluble electric heating ink and preparation method thereof |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108550856A (en) * | 2018-05-23 | 2018-09-18 | 山东希诚新材料科技有限公司 | Carbon nano tube/graphene composite conducting slurry and preparation method thereof |
| CN109068412A (en) * | 2018-07-11 | 2018-12-21 | 安徽宝利乐暖环保科技有限公司 | A kind of containing graphene and the water nano heating film of carbon nanotube and preparation method thereof |
| CN109306209A (en) * | 2018-08-31 | 2019-02-05 | 江苏天创新材料科技有限公司 | A kind of preparation method of preparation method and cylinder the printing Electric radiant Heating Film of the black compound electro-thermal ink of graphene/carbon |
| CN109666339A (en) * | 2019-02-26 | 2019-04-23 | 新奥石墨烯技术有限公司 | Electric heating ink and preparation method thereof |
| CN110294960A (en) * | 2019-07-30 | 2019-10-01 | 高碑店市隆泰丰博石墨烯有限公司 | Freezing point is starched and preparation method in -20 DEG C or less anti-freeze type watersoluble plumbago alkene electric heating |
| CN110294960B (en) * | 2019-07-30 | 2022-01-28 | 高碑店市隆泰丰博石墨烯有限公司 | Anti-freezing water-based graphene electrothermal slurry with freezing point below-20 ℃ and preparation method thereof |
| CN110591485A (en) * | 2019-09-27 | 2019-12-20 | 安徽省聚科石墨烯科技股份公司 | Graphene plastic for packaging box and preparation method |
| CN110769528A (en) * | 2019-10-11 | 2020-02-07 | 深圳天元羲王材料科技有限公司 | Graphene aqueous heating film conductive paste |
| CN111363413A (en) * | 2020-04-17 | 2020-07-03 | 宁波石墨烯创新中心有限公司 | Graphene-based PTC ink, electric heating device and preparation method of graphene-based PTC ink |
| CN111334121A (en) * | 2020-04-17 | 2020-06-26 | 宁波石墨烯创新中心有限公司 | Water-based graphene PTC ink and preparation method thereof |
| CN111334121B (en) * | 2020-04-17 | 2022-09-23 | 宁波石墨烯创新中心有限公司 | Water-based graphene PTC ink and preparation method thereof |
| CN112759980A (en) * | 2021-03-02 | 2021-05-07 | 梁贻波 | Environment-friendly anti-counterfeiting ink and preparation method thereof |
| CN114437604A (en) * | 2022-03-10 | 2022-05-06 | 信和新材料（苏州）有限公司 | Nanoparticle modified water-based white wood sealing primer and preparation method and application thereof |
| CN114437604B (en) * | 2022-03-10 | 2022-09-30 | 信和新材料（苏州）有限公司 | Nanoparticle modified water-based white wood sealing primer and preparation method and application 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 |
| CN114957761A (en) * | 2022-04-12 | 2022-08-30 | 扬州大学 | Green preparation process of PET heating film |
| CN114957761B (en) * | 2022-04-12 | 2023-09-29 | 扬州大学 | Green preparation process of PET heating film |
| CN117025024A (en) * | 2023-10-09 | 2023-11-10 | 山东概念印刷有限公司 | Water-based ink composition for flexographic printing and preparation method thereof |
| CN117025024B (en) * | 2023-10-09 | 2024-01-02 | 山东概念印刷有限公司 | Water-based ink composition for flexographic printing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107384026B (en) | 2018-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107384026B (en) | A kind of watersoluble plumbago alkene/carbon nanotube compound electro-thermal conversion ink and preparation method | |
| CN107141726A (en) | Graphene conductive polymer composite, its preparation method and Electric radiant Heating Film therefrom | |
| CN107682943B (en) | Multifunctional graphene electric heating slurry, multifunctional electric heating film prepared from multifunctional graphene electric heating slurry, preparation method and application | |
| WO2016029527A1 (en) | Method for preparing paraffin microcapsule phase-change material modified by graphene oxide | |
| CN103275524B (en) | Preparation method of graphene kaolin composite nanometer rubber fillers | |
| CN1325556C (en) | Large hole nano-composite resin material and its preparation method | |
| CN105017831A (en) | Composition for water-based electric heating nano paint, water-based electric heating nano paint as well as preparation method and application of water-based electric heating nano paint | |
| CN105321592A (en) | CNT (carbon nanotube)-polymer laminated composite flexible transparent electrode and preparation method thereof | |
| CN102614918B (en) | Preparation method of dispersant modified iron nanoparticles | |
| CN106117400A (en) | CNT graphene oxide strengthens the preparation method of polymer matrix composite | |
| CN105778608A (en) | Graphene composite coating and preparation method thereof | |
| CN106609098A (en) | Super-weather-resistance powder coating for electrostatic spraying and preparation method thereof | |
| CN107129752A (en) | A kind of graphene nano silver wire composite mortar and preparation method thereof | |
| CN109207029A (en) | Conductive coating with strong attachment fastness | |
| CN110527402B (en) | Water-based epoxy floor paint and preparation method thereof | |
| CN107021522A (en) | A kind of single dispersing TiO based on microemulsion2The synthetic method of microballoon | |
| CN104592946A (en) | Preparation method of nano-capsule composite phase change material | |
| CN108977081A (en) | A kind of efficient energy-saving coating for building and preparation method thereof | |
| CN104464880A (en) | Heat-resistant flexible transparent conductive film and preparation method thereof | |
| CN104559511A (en) | Organic-inorganic compound water based paint and preparation method thereof | |
| CN104927401A (en) | Modified calcium carbonate and preparation method thereof | |
| CN103599806A (en) | Photocatalyst used for synthesis of aromatic aldehyde chemical and preparation method thereof | |
| CN105038369A (en) | Modified calcium carbonate filler for paint and preparation method thereof | |
| CN102921458A (en) | Polythiophene nanometer photocatalyst and preparation and regeneration method thereof | |
| CN105038318A (en) | Modified calcium carbonate filler with favorable sound absorption and sound insulation effects and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181009 Termination date: 20200822 |