CN108559352A - A kind of thermal conductivity functional paint and preparation method - Google Patents
A kind of thermal conductivity functional paint and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention is using graphene oxide cheap and easy to get as raw material; after being restored by hydrazine hydrate; the selection NMP (N methyl pyrrolidones) of innovation is used as functionalized reagent; stable covalent bond is formed using the acylation reaction of NMP and graphene is upper on the surface of graphene; graphene sheet layer is removed, the graphene two-dimensional highly effective conductive and heat-conductive network of single layer large surface is promoted to be formed.On this basis, graphene is introduced coating system by innovation by in-situ polymerization, is improved the compatibility of graphene and resin matrix, is given full play to the outstanding conduction of graphene and thermal conduction characteristic.In addition, to ensure the comprehensive performance of coating, the mixture conduct film forming matrix of the preferred crosslinking alkyds lotion of the present invention, fluorine modified aqueous acrylic emulsion, graphene styrene-acrylic emulsion, improves the deficiency in weatherability, water resistance, adhesive force, film forming etc. when single acrylic resin matrix forms a film.
Description
Technical field
The present invention relates to field of functional coatings more particularly to a kind of thermal conductivity functional paint and preparation methods.
Background technology
The use of coating is the important means of protection materials, and a variety of materials is modified to assign the most simple of new capability
Just method.Nowadays, the decoration of traditional coating and simple protective effect can not meet the development of modern industry, functional paint already
Not only have basis mask or protective effect, also has both other specific functions, such as heat-insulation and heat-preservation, high temperature resistant, resistance to special media
Burn into self-cleaning, highly conductive etc..Graphene be one kind by carbon atom with sp2Hybridized orbit forms hexangle type in honeycomb lattice
Two-dimentional carbon nanomaterial, special performance make it show huge potentiality and application prospect in field of compound material, at present
Have become the hot spot of domestic and international scientific research.
Graphene be one kind by carbon atom with sp2Hybridized orbit forms the Two-dimensional Carbon nanometer material that hexangle type is in honeycomb lattice
Material, (carrier mobility is big for the excellent heat conduction (thermal conductivity 3000W/mK-1) of special structure imparting graphene and conduction
It is approximately 10 times of silicon chip) performance is the functional filler in ideal thermal conductivity coating system, but single-layer graphene is very
It is thin, and there is no any functional group on its surface, the Van der Waals force and under the action of electrostatic force between graphene film, in dispersion liquid
In or to be easy to reunite in the presence of solid phase, lose the characteristic of graphene, to limit graphene composite material lead
The application in domain.
Invention content
The present invention overcomes the disadvantages of the prior art, provides a kind of thermal conductivity functional paint and preparation method, changes
It has been apt to the deficiency in weatherability, water resistance, adhesive force, film forming etc. when single acrylic resin matrix forms a film.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：
The present invention provides a kind of thermal conductivity functional paint, includes each component of following parts by weight：Film-forming resin matrix 20-
60 parts, 5-15 parts of graphene thermal conductivity functional stuffing, 10-35 parts of color stuffing, 10-60 parts of solvent, 3-10 parts of auxiliary agent.
Preferably, the film-forming resin matrix is crosslinking alkyds lotion, fluorine modified aqueous acrylic emulsion, graphite
The mixture of alkene-styrene-acrylic emulsion, and crosslinking alkyds lotion, fluorine modified aqueous acrylic emulsion, graphene-styrene-acrylic emulsion
Mass ratio is 1：1-3：Between 8-15.
Preferably, the graphene thermal conductivity functional stuffing is the graphene dispersing solution of functionalization, the dispersion liquid and its
He is prepared into graphene-styrene-acrylic emulsion by way of in-situ polymerization and is introduced into coating system monomer.
Preferably, the functionalized reagent of the functionalization graphene dispersion liquid selects NMP (N-Methyl pyrrolidone), utilizes
After graphene oxide is reduced into the graphene with excellent conductive and heat-conductive characteristic by two hydrazides, innovation passes through functionalized reagent
NMP (N-Methyl pyrrolidone) and the acylation reaction of graphene above form stable covalent bond on the surface of graphene, to graphene
Lamella is removed, and is promoted the graphene two-dimensional highly effective conductive and heat-conductive network of single layer large surface to be formed, is obtained the stone of NMP functionalization
Black alkene dispersion liquid.
Preferably, graphene-styrene-acrylic emulsion by acrylic monomer, function modified monomer, functionalization graphene dispersion
Liquid is prepared by situ aggregation method " pre-emulsification semi-continuous emulsion polymerizing " technique, wherein methyl methacrylate, acrylic acid
Ethyl ester and n-octyl are acrylic monomer；Styrene, N hydroxymethyl acrylamide and acrylonitrile are function modified list
The amount ratio of the substance of body, acrylic monomer and function modified monomer monomer is 1：Between 0.2-0.5, third in function modified monomer
The amount ratio of the substance of alkene nitrile, N hydroxymethyl acrylamide and styrene is 1：1-3：Between 1-3；The graphene dispersing solution of functionalization
As one of monomer, graphene-styrene-acrylic emulsion is prepared by situ polymerization under initiator effect.Initiator is selected water-soluble
Oxidation-reduction trigger system such as ammonium persulfate/sodium thiosulfate, potassium peroxydisulfate/sodium sulfite or water-soluble azo compounds
Object initiator such as azo dicyclohexyl formonitrile HCN hydrochloride (AIBI) (V50, VA-044 etc.) etc. is any, and dosage is monomer
0.2%~2% (mass fraction), emulsifier select pure NaLS (Texapon K-12) or SDS (dodecyl sulphates
Sodium) it is any, dosage be monomer 0.5%~2% (mass fraction).
Preferably, the fluorine modified aqueous acrylic emulsion is passed through by fluorine-containing olefin monomer with acrylic monomer
" monomer dripping method technique " is prepared, and fluorine-containing olefin monomer is hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate
With any one or several combinations of dodecafluoroheptyl methacrylate, acrylic monomer selects methyl methacrylate, third
Any one or several combinations of olefin(e) acid ethyl ester, n-octyl, the object of fluorine-containing olefin monomer and acrylic monomer
The amount ratio of matter is 1：Between 1-2；Initiator selects water soluble oxidized-reduction initiating system such as ammonium persulfate/sodium thiosulfate, mistake
Potassium sulfate/sodium sulfite or water-soluble azoic compound initiator such as azo dicyclohexyl formonitrile HCN hydrochloride (AIBI)
(V50, VA-044 etc.) etc. is any, and dosage is 0.2%~2% (mass fraction) of monomer；Emulsifier is by anionic breast
The compound emulsifying agent of agent and nonionic emulsifier composition, as SDS (anionic)/AEO (nonionic) or DSB are (cloudy
Ionic)/CO436 (nonionic) any combination blended emulsifier, dosage be monomer 0.5%~2% (mass fraction),
Wherein the mass ratio of anionic emulsifier and nonionic emulsifier is 1：Between 1-3；Chain-transferring agent selects IOMP (3- sulfydryls
The different monooctyl ester of propionic acid), dosage is 0.1%~0.5% (mass fraction) of monomer.
Preferably, the color stuffing nano ATO, conductive mica powder, the combination of rutile type titanium white, wherein nanometer
ATO, conductive mica powder, the mass ratio of rutile type titanium white is 1：20-30：Between 20-30.
Preferably, the auxiliary agent includes dispersant, thickener, levelling agent, preservative, mildew and algae agent, pH adjusting agent.Its
In, dispersant is anionic Sodium Polyacrylate the saline solution such as Flosperse3000A55 or DC35 etc. of low molecular weight, with
0.5-3 parts of weight meter；Thickener is the hydroxyethyl cellulose class compound in cellulose ether and its derivative (such as Natrosol
The QP100000 etc. of 250H4R or Cellosize), 0.05-2 parts by weight；Levelling agent is the acrylic resin of fluorine richness
Conjunction object, such as EFKA-3777 or ADL151,0.05-1.5 parts by weight；Preservative selects BIT (2-benzisothiazoles-
3- ketone) class, if Promex Na20TS or BIOBAN P-1487 are any, 0.02-0.1 parts by weight；Mildew and algae agent is selected
With Compositional type system such as Rocima350 (- 4 isothiazoline -3- ketone (DCOIT) of 4,5 two chloro- 2- n-octyls and iodo- 2 propargyls of 3-
The compounding of butyl carbamate (IPBC)) or Rocima361 (benzimidazole methyl carbamate (BCM) and N '-(3,4 dichloros
Phenyl)-N, the compounding of N- dimethyl ureas) it is any, 0.02-0.2 parts by weight；What pH adjusting agent was selected is ethanolamines
Neutralizer, 0.01-5 parts by weight.
Preferably, the solvent includes deionized water, ethyl alcohol and 3,5,5- trimethyl -2- cyclohexene -1- ketone.
Preferably, a kind of thermal conductivity functional paint, which is characterized in that include the following steps：
(1) prepared by the graphene solution of functionalization：
NMP (N-Methyl pyrrolidone) modified graphene the specific steps are：Add graphene oxide into deionized water
In, it is configured to the graphene oxide water solution of 1mg/mL, the surfactant of 1% (mass fraction) is added such as into the aqueous solution
SDBS's or SDS is any, 30min is ultrasonically treated, after the pH value of system is adjusted to 9.5-10 using diethanol amine, then up
The hydrazine hydrate that about 1/10 volume is added in graphene oxide dispersion is stated, heating systems to 80 DEG C, react for 24 hours by stirring at low speed, will
Graphene oxide is reduced to graphene, and the graphene aqueous solution of 1mg/mL is obtained after filtering.To the 1mg/ obtained as stated above
Appropriate NMP (graphene aqueous solution of 1mL adds NMP0.3-0.5mmol), stirring at low speed reaction are added in the graphene aqueous solution of mL
1-2h obtains NMP (N-Methyl pyrrolidone) modified graphene aqueous dispersions.
(2) preparation of graphene-styrene-acrylic emulsion：
Weighed the graphene solution, acrylic monomers and function modified monomer of functionalization in advance by formula, emulsifier and
Deionized water is added in round-bottomed flask, high speed pre-emulsification 30min, and pre-emulsion is made；Then equipped with agitating device, dropping liquid
In the four-hole boiling flask of funnel, condenser pipe and thermometer, 1/3 pre-emulsion, 1/3 initiator solution, speed appropriate are sequentially added
Stirring, it is 30-45min that heating, which reaches 80 DEG C or so to be allowed to polymerization time, after there is blue-fluorescence, is added dropwise with funnel remaining
2/3 pre-emulsion and 1/3 initiator solution are warming up to 85 DEG C of heat preservation about 45min to get to stone after being added dropwise in 1-1.5h
Black alkene-styrene-acrylic emulsion.
(3) preparation of fluorine modified aqueous acrylic emulsion：
Under N2 atmosphere, it is added and causes into the four-hole boiling flask equipped with agitating device, dropping funel, condenser pipe and thermometer
Agent, fluorine-containing olefin monomer and emulsifier, stir evenly (solution is 1.)；By acrylic monomer and mixed solvent (3,5,5-
Trimethyl -2- cyclohexene -1- ketone：Ethyl alcohol：Deionized water presses 1：2-5：The volume ratio of 10-15 mixes) stir evenly (solution
2.) and be heated to 60 DEG C；Under stiring, in 1. 2. 1/2 solution being added drop-wise to solution in 30-45min, continue to be heated to
It is stirred to react 1.5-2h (solution is 3.) at 70-80 DEG C, then 1. 3. remaining solution is added drop-wise to solution in 30-45min, after
It is continuous to be stirred to react 2.5-3h, it is stirred evenly after chain-transferring agent is added, removes N2 atmosphere, cool, obtain fluorine modified aqueous third
Olefin(e) acid lotion.
(4) preparation of thermal conductivity functional paint：
By formula by thermal conductivity functional stuffing, color stuffing, solvent, container is added in auxiliary agent, first with 1000-2000rpm's
Speed stirs, and stirs 20-30min with 2500-3000rpm after 10min, mill base is made；Under stiring, into above-mentioned mill base by matching
Crosslinking alkyds lotion, fluorine modified aqueous acrylic emulsion is added in side, and graphene-styrene-acrylic emulsion is stirred at 1000r/min
PH adjusting agent, regulation system pH to 7-8 is added in 20min；Then thickener regulation system viscosity is added, with 1500-
The speed of 2000rpm stirs 30-45min to get a kind of thermal conductivity functional paint finished product.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is using graphene oxide cheap and easy to get as raw material, after being restored by hydrazine hydrate, the selection NMP of innovation
(N-Methyl pyrrolidone) is used as functionalized reagent, is formed surely using the acylation reaction of NMP and graphene is upper on the surface of graphene
Fixed covalent bond, removes graphene sheet layer, promotes the graphene two-dimensional highly effective conductive and heat-conductive network shape of single layer large surface
At.On this basis, graphene by in-situ polymerization is introduced coating system by innovation, improves graphene and resin matrix
Compatibility gives full play to the outstanding conduction of graphene and thermal conduction characteristic.In addition, to ensure that the comprehensive performance of coating, the present invention are excellent
The mixture of crosslinking alkyds lotion, fluorine modified aqueous acrylic emulsion, graphene-styrene-acrylic emulsion is selected to be used as film forming matrix,
Improve the deficiency in weatherability, water resistance, adhesive force, film forming etc. when single acrylic resin matrix forms a film.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
(1) prepared by the graphene solution of functionalization：
NMP (N-Methyl pyrrolidone) modified graphene the specific steps are：Add graphene oxide into deionized water
In, it is configured to the graphene oxide water solution of 1mg/mL, the surfactant of 1% (mass fraction) is added into the aqueous solution
SDBS, be ultrasonically treated 30min, after the pH value of system is adjusted to 9.5 using diethanol amine, then toward above-mentioned graphene oxide disperse
The hydrazine hydrate of about 1/10 volume is added in liquid, heating systems to 80 DEG C, react for 24 hours, and graphene oxide is reduced to by stirring at low speed
Graphene obtains the graphene aqueous solution of 1mg/mL after filtering.Take the 1mg/mL graphene aqueous solutions that 100mL is prepared to appearance
In device, appropriate 30mmolNMP is added, stirring at low speed reacts 1.5h, obtains NMP modified graphene aqueous dispersions.
(2) preparation of graphene-styrene-acrylic emulsion：
Weigh the NMP modified graphene aqueous dispersions being prepared in 20mL (1), ethyl acrylate 60.07g, acrylic acid
N-octyl 110.56g, acrylonitrile 4.24g, N hydroxymethyl acrylamide 8.1g and styrene 8.33g, initiator ammonium persulfate 1g,
Sodium thiosulfate 1g (is both added in 20mL deionized waters, be configured to initiator solution), emulsifier Texapon K-12
1.2g, deionized water 100mL.By NMP modified graphene aqueous dispersions, acrylic monomers and function modified monomer, emulsifier and
Deionized water is added in round-bottomed flask, and pre-emulsion is made in high speed (1500-2000r/min) pre-emulsification 30min；Then exist
In four-hole boiling flask equipped with agitating device, dropping funel, condenser pipe and thermometer, 1/3 pre-emulsion, 1/3 initiator are sequentially added
Aqueous solution, speed stirring appropriate, it is 45min that heating, which reaches 80 DEG C or so to be allowed to polymerization time, after there is blue-fluorescence, is used
Remaining 2/3 pre-emulsion and 1/3 initiator solution is added dropwise in funnel, and 85 DEG C of heat preservations are warming up to after being added dropwise in 1.5h about
45min is to get to graphene-styrene-acrylic emulsion.
(3) preparation of fluorine modified aqueous acrylic emulsion：
Weigh initiator ammonium persulfate 0.5g/ sodium thiosulfate 0.5g, emulsifier SDS0.3g/AEO0.3g, chain-transferring agent
IOMP 0.3g, ethyl acrylate 17.6g, n-octyl 32.4g, Hexafluorobutyl mathacrylate 43.8g, mixed solvent
(including 3,5,5- trimethyl -2- cyclohexene -1- ketone 5mL, 95% ethyl alcohol 10mL and deionized water 35mL).In N2Under atmosphere, press
Initiator, fluorine-containing alkene is added in the above-mentioned four-hole boiling flask equipped with agitating device, dropping funel, condenser pipe and thermometer with direction
Hydrocarbon monomer and emulsifier stir evenly (solution is 1.)；Acrylic monomer and mixed solvent are stirred evenly into (solution is 2.) simultaneously
It is heated to 60 DEG C；Under stiring, in 1. 2. 1/2 solution being added drop-wise to solution in 30-45min, continue to be heated to 70-80 DEG C
Under be stirred to react 1.5-2h (solution is 3.), then 1. 3. remaining solution is added drop-wise to solution in 30-45min, continues to stir
2.5-3h is reacted, is stirred evenly after chain-transferring agent is added, removes N2Atmosphere cools, and obtains fluorine modified aqueous propylene yogurt
Liquid.
(4) preparation of thermal conductivity functional paint：
Crosslinking alkyds lotion 20g is weighed, the fluorine modified aqueous acrylic emulsion 20g being prepared in (3), in (2)
The graphene being prepared-styrene-acrylic emulsion 160g, nano ATO 1g, conductive mica powder 25g, rutile type titanium white 20g, go from
Sub- water 20g, dispersant Flosperse3000A55 2g, thickener QP100000 1.5g, levelling agent ADL151 1.5g, anti-corrosion
Agent Promex Na20TS 0.3g, mildew and algae agent Rocima350 0.5g, pH adjusting agent diethanol amine 5g.
By above-mentioned formula by color stuffing, solvent, container is added in auxiliary agent, first with the stirring of the speed of 1000-2000rpm, 10min
20-30min is stirred with 2500-3000rpm afterwards, mill base is made；Under stiring, crosslinking alkyd is added by formula into above-mentioned mill base
Resin emulsion, fluorine modified aqueous acrylic emulsion, graphene-styrene-acrylic emulsion stir 20min at 1000r/min, and pH tune is added
Save agent, regulation system pH to 8；Then thickener regulation system viscosity is added, 30- is stirred with the speed of 1500-2000rpm
45min is to get a kind of thermal conductivity functional paint finished product.
Embodiment 2
The present embodiment is substantially same as Example 1, and difference is the preparation of step (4) thermal conductivity functional paint
When, each component is weighed according to the following formulation：
Crosslinking alkyds lotion 20g is weighed, the fluorine modified aqueous acrylic emulsion 60g being prepared in (3), in (2)
The graphene being prepared-styrene-acrylic emulsion 300g, nano ATO 2g, conductive mica powder 30g, rutile type titanium white 30g, go from
Sub- water 30g, dispersant Flosperse3000A55 3g, thickener QP100000 2g, levelling agent ADL151 2g, preservative
Promex Na20TS 0.5g, mildew and algae agent Rocima350 0.5g, pH adjusting agent diethanol amine 5g.
Embodiment 3
The present embodiment is substantially same as Example 1, and difference is：When preparing graphene-styrene-acrylic emulsion, by matching as follows
Side weighs each component：Weigh the NMP modified graphene aqueous dispersions being prepared in 30mL (1), methyl methacrylate
56.07g, n-octyl 103.19g, acrylonitrile 4.24g, N hydroxymethyl acrylamide 24.26g and styrene 25.00g；
When preparing fluorine modified aqueous acrylic emulsion, each component is weighed according to the following formulation：Weigh initiator azo dicyclohexyl formonitrile HCN
Hydrochloride (AIBI) (V50) 1g, emulsifier SDS0.3g/AEO0.3g, chain-transferring agent IOMP 0.3g, methyl methacrylate
17.6g, n-octyl 32.4g, dodecafluoroheptyl methacrylate 88.05g, 3,5,5- trimethyl -2- cyclohexene -1- ketone
15mL, 95% ethyl alcohol 35mL, deionized water 35mL.
Performance detection data：Performance detection is carried out to the thermal conductivity functional paint of embodiment 1-3, testing result see the table below
1。
1 thermal conductivity functional paint the performance test results of table
By testing result it is found that environmentally friendly Waterproof corrosion high-performance coating provided by the invention, innovation with silk peptide
Modified graphene oxide is functional additive, is film forming with Ludox, aqueous crosslinking alkyds lotion and waterborne styrene-acrylic emulsion
Object, preferably specific color stuffing and auxiliary agent compound by a certain percentage, and test result shows：The environmentally friendly Waterproof corrosion
High-performance coating antiseptic property is excellent, and water resistance is good, and adhesive force is good, environmental-friendly, overcomes common water borne acrylic coating body
The shortcomings that being, technology have significant novelty, have good social and economic benefit.
Finally it should be noted that：It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, although
With reference to embodiment, invention is explained in detail, for those skilled in the art, still can be to aforementioned
Technical solution recorded in each embodiment is modified or equivalent replacement of some of the technical features, but it is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of thermal conductivity functional paint and preparation method thereof, which is characterized in that include each component of following parts by weight：Film forming
20-60 parts of resin matrix, 5-15 parts of graphene thermal conductivity functional stuffing, 10-35 parts of color stuffing, 10-60 parts of solvent, auxiliary agent 3-
10 parts.
2. a kind of thermal conductivity functional paint according to claim 1, which is characterized in that the film-forming resin matrix is to hand over
Join the mixture of alkide resin emulsion, fluorine modified aqueous acrylic emulsion, graphene-styrene-acrylic emulsion, and crosslinking alkyds breast
Liquid, fluorine modified aqueous acrylic emulsion, graphene-styrene-acrylic emulsion mass ratio 1：1-3：Between 8-15.
3. a kind of thermal conductivity functional paint according to claim 2, which is characterized in that the graphene thermal conductivity work(
Energy filler is the graphene dispersing solution of functionalization, which is prepared into graphite with other monomers by way of in-situ polymerization
Alkene-styrene-acrylic emulsion and be introduced into coating system.
4. a kind of thermal conductivity functional paint according to claim 3, which is characterized in that the functionalization graphene dispersion
The functionalized reagent of liquid selects N-Methyl pyrrolidone.
5. a kind of thermal conductivity functional paint according to claim 3, which is characterized in that the graphene-styrene-acrylic emulsion
Situ aggregation method " the semicontinuous breast of pre-emulsification is passed through by the graphene dispersing solution of acrylic monomer, function modified monomer, functionalization
Liquid polymerization " technique is prepared, wherein methyl methacrylate, ethyl acrylate and n-octyl are acrylic compounds list
Body；Styrene, N hydroxymethyl acrylamide and acrylonitrile are function modified monomer, acrylic monomer and function modified monomer list
The amount ratio of the substance of body is 1：Between 0.2-0.5, acrylonitrile in function modified monomer, N hydroxymethyl acrylamide and styrene
The amount ratio of substance is 1：1-3：Between 1-3；The graphene dispersing solution of functionalization passes through as one of monomer under initiator effect
Situ polymerization prepares graphene-styrene-acrylic emulsion, and initiator selects water soluble oxidized-reduction initiating system or water-soluble idol
Nitrogen compound initiator, dosage are 0.2%~2% (mass fraction) of monomer, and emulsifier selects pure NaLS or ten
Sodium dialkyl sulfate it is any, dosage be monomer 0.5%~2% (mass fraction).
6. a kind of thermal conductivity functional paint according to claim 3, which is characterized in that the fluorine modified aqueous acrylic acid
Lotion is prepared with acrylic monomer by " monomer dripping method technique " by fluorine-containing olefin monomer, fluorine-containing olefines
Monomer is any one or several of hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate and dodecafluoroheptyl methacrylate
Combination, acrylic monomer select any one or several groups of methyl methacrylate, ethyl acrylate, n-octyl
It closes, the amount ratio of the substance of fluorine-containing olefin monomer and acrylic monomer is 1：Between 1-2；Initiator selects water-soluble oxygen
Change-reduction initiating system or water-soluble azoic compound initiator, dosage are 0.2%~2% (mass fraction) of monomer；
Emulsifier is the compound emulsifying agent being made of anionic emulsifier and nonionic emulsifier, dosage be monomer 0.5%~
2% (mass fraction), wherein the mass ratio of anionic emulsifier and nonionic emulsifier is 1：Between 1-3；Chain-transferring agent
It is 0.1%~0.5% (mass fraction) of monomer to select 3- isooctyl mercaptopropionates, dosage.
7. a kind of thermal conductivity functional paint according to claim 1, which is characterized in that the color stuffing is nano ATO,
Conductive mica powder, the combination of rutile type titanium white, wherein nano ATO, conductive mica powder, the quality of rutile type titanium white
Than 1：20-30：Between 20-30.
8. a kind of thermal conductivity functional paint according to claim 1, which is characterized in that the auxiliary agent include dispersant,
Thickener, levelling agent, preservative, mildew and algae agent, pH adjusting agent, wherein dispersant is the anionic poly- third of low molecular weight
Olefin(e) acid sodium-salt aqueous solution, 0.5-3 parts by weight；Thickener is the hydroxyethyl cellulose class in cellulose ether and its derivative
Conjunction object, 0.05-2 parts by weight；Levelling agent be fluorine richness acrylic resin compound, 0.05-1.5 parts by weight；It is anti-
2-benzisothiazole-3-ketone classes of rotten agent selection, 0.02-0.1 parts by weight；Mildew and algae agent select Compositional type system with
0.02-0.2 parts of weight meter；What pH adjusting agent was selected is ethanolamines neutralizer, 0.01-5 parts by weight.
9. a kind of thermal conductivity functional paint according to claim 1, which is characterized in that the solvent includes deionization
Water, ethyl alcohol and 3,5,5- trimethyl -2- cyclohexene -1- ketone.
10. a kind of preparation method of thermal conductivity functional paint according to claim 1, which is characterized in that including
Following steps：
(1) prepared by the graphene solution of functionalization：
NMP (N-Methyl pyrrolidone) modified graphene the specific steps are：It adds graphene oxide into deionized water, matches
The graphene oxide water solution of 1mg/mL is made, the surfactant such as SDBS of 1% (mass fraction) is added into the aqueous solution
Or SDS's is any, is ultrasonically treated 30min, after the pH value of system is adjusted to 9.5-10 using diethanol amine, then toward above-mentioned oxygen
The hydrazine hydrate of about 1/10 volume is added in graphite alkene dispersion liquid, heating systems to 80 DEG C, react for 24 hours, will aoxidize by stirring at low speed
Graphene is reduced to graphene, and the graphene aqueous solution of 1mg/mL is obtained after filtering, to the 1mg/mL's obtained as stated above
Appropriate NMP (graphene aqueous solution of 1mL adds NMP0.3-0.5mmol) is added in graphene aqueous solution, stirring at low speed reacts 1-
2h obtains NMP (N-Methyl pyrrolidone) modified graphene aqueous dispersions；
(2) preparation of graphene-styrene-acrylic emulsion：
Weighed the graphene solution, acrylic monomers and function modified monomer of functionalization in advance by formula, emulsifier and go from
Sub- water is added in round-bottomed flask, high speed pre-emulsification 30min, and pre-emulsion is made；Then equipped with agitating device, dropping liquid leakage
In the four-hole boiling flask of bucket, condenser pipe and thermometer, 1/3 pre-emulsion, 1/3 initiator solution are sequentially added, is stirred, heating reaches
It is 30-45min that 80 DEG C or so, which are allowed to polymerization time, and after there is blue-fluorescence, remaining 2/3 pre-emulsion and 1/ is added dropwise with funnel
3 initiator solutions are warming up to 85 DEG C of heat preservation about 45min to get newborn to graphene-phenylpropyl alcohol after being added dropwise in 1-1.5h
Liquid；
(3) preparation of fluorine modified aqueous acrylic emulsion：
In N2Under atmosphere, initiator is added into the four-hole boiling flask equipped with agitating device, dropping funel, condenser pipe and thermometer, contains
The olefin monomer and emulsifier of fluorine stir evenly (solution is 1.)；By acrylic monomer and mixed solvent (3,5,5- front threes
Base -2- cyclohexene -1- ketone：Ethyl alcohol：Deionized water presses 1：2-5：The volume ratio of 10-15 mixes) it stirs evenly (solution is 2.)
And it is heated to 60 DEG C；Under stiring, in 1. 2. 1/2 solution being added drop-wise to solution in 30-45min, continue to be heated to 70-80
It is stirred to react 1.5-2h (solution is 3.) at DEG C, then 1. 3. remaining solution is added drop-wise to solution in 30-45min, continue to stir
Reaction 2.5-3h is mixed, is stirred evenly after chain-transferring agent is added, removes N2Atmosphere cools, and obtains fluorine modified aqueous acrylic acid
Lotion；
(4) preparation of thermal conductivity functional paint：
By formula by thermal conductivity functional stuffing, color stuffing, solvent, container is added in auxiliary agent, first with the speed of 1000-2000rpm
It stirs, 20-30min is stirred with 2500-3000rpm after 10min, mill base is made；Under stiring, add into above-mentioned mill base by formula
Enter crosslinking alkyds lotion, fluorine modified aqueous acrylic emulsion, graphene-styrene-acrylic emulsion is stirred at 1000r/min
PH adjusting agent, regulation system pH to 7-8 is added in 20min；Then thickener regulation system viscosity is added, with 1500-
The speed of 2000rpm stirs 30-45min to get a kind of thermal conductivity functional paint finished product.
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| CN111592844A (en) * | 2020-05-19 | 2020-08-28 | 上海嘉好胶粘制品有限公司 | Hot-melt pressure-sensitive adhesive for high-temperature adhesive tape and preparation method thereof |
| GB2583503A (en) * | 2019-04-30 | 2020-11-04 | !Obac Ltd | Heated floor or wall coating system |
| CN113308157A (en) * | 2021-04-16 | 2021-08-27 | 宁波瑞凌新能源科技有限公司 | Radiation refrigeration self-cleaning coating |
| CN114276728A (en) * | 2021-12-31 | 2022-04-05 | 广东美涂士建材股份有限公司 | Modified acrylic acid corrosion-resistant water-based paint and preparation method thereof |
| CN115491115A (en) * | 2022-10-13 | 2022-12-20 | 上海展辰涂料有限公司 | Water-based bi-component graphene solid-color paint for electrostatic coating |
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