CN109749582A - A kind of graphene heat radiation coating and preparation method thereof - Google Patents
A kind of graphene heat radiation coating and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of graphene heat radiation coatings and preparation method thereof, belong to technical field of coatings.Pass through again present invention introduces amino group and modified active agent is added increases interlamellar spacing between graphene, so that heat conduction and heat radiation channel is opened, increases heat conduction rate.The hydrophobic framework having using heat dissipation migration agent can occur absorption behavior by electrostatic interaction, hydrogen bond action etc. and graphene interface, improve dispersibility.Dispersibility of the graphene oxide in epoxy resin-base can be increased by being introduced into imidazole radicals both, simultaneously, imidazole radicals is complexed with transition metal ions, make that there is longer storage period and preferable temperature response performance in epoxy resin, preferable adhesive property is kept in radiation processes, there is phenyl etc. the group of preferable heat resistance to add heat-resistant stability, it is therefore prevented that the heated cracking of coating falls off, and improves the overall performance of coating.The present invention solves the problems, such as that dispersion performance of the current graphene in coating is poor, heat-conducting effect is low.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of graphene heat radiation coating and preparation method thereof.
Background technique
With the high speed development of electronics industry, modern electronic equipment is increasingly becoming the highly integrated system of High Density Packaging
System, this makes the heat flow density of product become larger increasingly.Heat-sinking capability such as fruit product is insufficient, and component and circuit temperature rise, just
It can make equipment thermal deformation and thermal failure, influence performance and the service life of electronic product.In addition, in metallurgy, petrochemical industry, ceramics, medicine
In equal industry fields, the furnace bodies such as various Industrial Boilers, station boiler, flame furnace, peace of the heat dissipation performance to personnel are often related to
Complete and equipment reliability service is most important.Therefore, how to improve electronics industry and the heat dissipation performance of other field devices has become
For the important topic for promoting industrial progress.
Application of the graphene in terms of functional coating at present has been achieved for very big progress, but in addition to anticorrosive paint
Outside, other majority researchs also rest on laboratory stage.Main cause has the following aspects:
(1) coating industry is an industry very sensitive to cost, compared to existing frequently-used paint filler, the valence of graphene
Lattice are relatively higher, therefore limit its application.
(2) graphene surface can be high, is difficult to disperse in the common solvent such as dimethylbenzene of water and coating, butyl acetate, with
This simultaneously, the performance of graphene coating depends critically upon degree of scatter of the graphene in coating, therefore conventional simple dispersion
Means are not suitable for graphene coating.
(3) at present graphene relevant criterion lack, cause in the market graphene product spread in performance it is uneven, to application and development
There is very big misleading.
(4) lack graphene coating application standard at present, cannot be sent out according to present standard in application graphene coating
Shoot the advantage of graphene coating.
(5) in actual application, it usually needs apply layered coating, it is therefore desirable to consider the matching problem of coating,
Graphene coating lacks corresponding verify data, limits its application to a certain extent since development time is short.Utilize graphite
The anti-corrosion of coating, antifouling, flame retardant effect can be improved in the physical barrier performance of alkene；, high thermal conductivity highly conductive using its can be opened
Send out conductive coating, heat radiation coating, electromagnetic screen coating etc..Heat radiation coating not only has the base of decoration as a kind of new coating
This function, while having the function of improving radiating efficiency, it receives extensive attention and studies.However, on the market exhausted big at present
Most heat radiation coatings are using expensive heat transfer medium as filler, and production process is complex and costly, is unfavorable for applying
The mass production and scale application of material.
Graphene is carbon molecules made of one kind is arranged and is connected with each other according to hexagon as carbon atom, and structure is non-
Often stablize, is presently found most thin, maximum intensity, a kind of strongest novel nano-material of electrical and thermal conductivity performance.Graphene is led
Hot coefficient is up to 5000W/mK, can be answered extensively in fields such as coating, electronics, space flight military project, new energy, new materials
With.Therefore, heat radiation coating is prepared as research hotspot using graphene as main heat sink medium.However, existing graphene dissipates
In hot coating, since graphene is easy cohesion, it is caused to disperse in coating unevenly, so that coating is conductive and thermally conductive
Performance is bad.In order to reduce the cohesion between graphene, stability of the graphene in heat radiation coating is improved, it usually needs addition
The chemicals such as polyethylene wax, polyvinyl chloride, polyvinylpyrrolidone add above-mentioned dispersion as dispersing agent or surfactant
Although agent can reduce the cohesion between graphene to a certain extent, volatilized, is endangered in radiation processes using chemicals
Human body and environment.Meanwhile in order to improve coating color, coating adhesion is improved, existing graphene heat radiation coating can also add
Colorant, adhesion promoter with toxic component, these components are very unfavorable to human body and environment in radiation processes.
Summary of the invention
The technical problems to be solved by the invention: the poor, heat-conducting effect for dispersion performance of the current graphene in coating
Low problem provides a kind of graphene heat radiation coating and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of graphene heat radiation coating, including graphene-based raw material, heat dissipation migration agent, component bridging agent, curing additive；
The graphene-based raw material the preparation method comprises the following steps: take graphite alkene monomer 2 ~ 5:30 in mass ratio ~ 50 be added N, N- dimethyl
Formamide, ultrasound are passed through nitrogen protection, and 3 ~ 6 times of graphene monomer mass of modified active agent is added and is stirred, and must stir mixed
Object is closed, takes stirring mixture 40 ~ 50:1 in mass ratio ~ 3 that dibutyl tin dilaurate is added, is passed through carbon dioxide reaction, in 30 ~
It is kept under 35 DEG C of supercriticalities, filters, take filter cake to be dried in vacuo to get graphene-based raw material.
The graphite alkene monomer the preparation method comprises the following steps:
(1) it takes graphene oxide 1 ~ 3:40 in mass ratio ~ 50 that dioxane is added, the N, N- of dioxane quality 5 ~ 10% is added
Dimethylformamide is passed through nitrogen protection, and the cinnamoyl chloride for adding dioxane quality 1 ~ 5% is stirred, and centrifugation, it is heavy to take
It forms sediment washed, it is dry, obtain dried object；
(2) take dried object 3 ~ 7:10 in mass ratio ~ 30 that n,N-Dimethylformamide is added, ultrasound obtains ultrasonic liquid, by mass fraction
Meter takes 20 ~ 30 parts of ultrasonic liquid, 1 ~ 3 part of sodium azide, 0.2 ~ 0.5 part of benzyltriethylammoinium chloride, 40 ~ 50 parts of N, N- dimethyl
Formamide is passed through nitrogen protection, is stirred, and filtering takes filter cake to wash through n,N-Dimethylformamide, takes washings by quality
Hydrochloric acid, ultrasound is added than 10 ~ 20:3 ~ 6, filtering takes filter residue washed, dry to get graphite alkene monomer.
The modified active agent are as follows: according to the mass fraction, 5 ~ 15 parts of 1,6- hexamethylene diisocyanates, 3 ~ 7 part 2 are taken,
4- toluene di-isocyanate(TDI), 4 ~ 8 parts of 4,4'- methyl diphenylene diisocyanates, 2 ~ 6 parts of isoflurane chalcone diisocyanate mixing,
To obtain the final product.
Hydrogen-oxygen is added the preparation method comprises the following steps: taking and pre-processing alkali lignin 2 ~ 5:10 in mass ratio ~ 30 in the heat dissipation migration agent
To change sodium solution to be stirred, the potassium iodide for adding pretreatment alkali lignin quality 10 ~ 15% is stirred, stirring mixture is obtained,
It takes stirring mixture 40 ~ 50:2 in mass ratio ~ 7 that Isosorbide-5-Nitrae-butyl sultone is added to be stirred, adds and be stirred amount of substance
30 ~ 40% 1,2- dichloroethanes keeps the temperature in 70 ~ 80 DEG C, obtains mixture, takes mixture 2 ~ 5:10 in mass ratio ~ 15 that petroleum is added
Ether extraction, takes subnatant to dialyse to get thermally conductive migration agent.
The pretreatment alkali lignin are as follows: take alkali lignin 2 ~ 5:10 in mass ratio ~ 20 that Acetic acid-sodium acetate buffer is added
It is stirred, the laccase for adding alkali lignin quality 3 ~ 9% is stirred, enzyme deactivation, and filtering takes filtrate to be freeze-dried to get pre-
Handle alkali lignin.
The component bridging agent are as follows: take acid activity agent 2 ~ 5:10 in mass ratio ~ 15 that methanol is added, add acid activity agent matter
The p-methyl benzenesulfonic acid of amount 1 ~ 3% is stirred, and is evaporated under reduced pressure, and takes vacuum distillation object washed, dry to get component bridging agent.
The acid activity agent are as follows: take phthalic anhydride, carbic anhydride, maleic anhydride, 4- phenylacetylene benzene
Any one in acid anhydride or it is any it is several by any mass ratio mix to get.
The curing additive the preparation method comprises the following steps:
S1. it takes 2-ethyl-4-methylimidazole 3 ~ 7:1 in mass ratio ~ 3:20 ~ 30 that triethylamine, toluene is added, is passed through nitrogen protection,
It is stirred, obtains stirring mixture, take lauroyl chloride 1 ~ 4:5 in mass ratio ~ 10 that stirring mixture is added and be stirred, filter,
Smoke filtrate rotary evaporation is taken, rotary evaporation residue is collected, it is washed, washed product vacuum drying is collected, vacuum drying object is obtained；
S2. it takes vacuum drying object 2 ~ 5:10 in mass ratio ~ 15 that absolute ethyl alcohol and stirring is added to mix, addition vacuum drying amount of substance 5 ~
10% zinc acetate is stirred, and filtering takes filtrate rotary evaporation, collects rotary evaporation residue to get curing additive.
The preparation method includes the following steps:
A. according to the mass fraction, 20 ~ 30 parts of component bridging agents, 2 ~ 7 parts of allyl amines, 40 ~ 60 parts of deionized waters, 0.4 ~ 0.8 are taken
Part Pt/C catalyst, 40 ~ 60 parts of toluene are passed through argon gas protection, are stirred, obtain mixture, take mixture in mass ratio 40 ~
50:3 ~ 6 is added gamma-aminopropyl-triethoxy-silane and is stirred, and is cooled to room temperature, rotary evaporation, and it is remaining to collect rotary evaporation
Object；
B. according to the mass fraction, 20 ~ 50 parts of graphene-based raw materials, 20 ~ 30 parts of thermally conductive migration agents, 3 ~ 9 parts of rotary evaporation residues are taken
Object, 2 ~ 5 parts of curing additives, 200 ~ 300 parts of epoxy resin E-44s, 1 ~ 5 part of polyoxyethylene polyoxypropylene pentaerythrite ether, 2 ~ 6
Part diluent is stirred to get graphene heat radiation coating.
The diluent are as follows: according to the mass fraction, take 2 ~ 5 parts of acrylic glycidol ethers, 1 ~ 3 part of phenyl glycidyl
Ether, 20 ~ 25 parts of acetone, 2 ~ 6 parts of dibutyl phthalates, 20 ~ 40 parts of propylene glycol, the mixing of 10 ~ 15 parts of ethylene glycol to get.
The present invention is compared with other methods, and advantageous effects are:
(1) graphene-based raw material prepared by the present invention is obtained using graphite alkene monomer as raw material is modified, graphite alkene monomer be with
Graphene oxide and cinnamoyl chloride carry out acyl chloride reaction, add sodium azide progress azido reaction and obtain, with oxidation stone
The carboxyl on black alkene surface reacts to form amination graphene oxide, introduces amino group and passes through addition modified active agent again, wherein
- NCO group access amino can react with it to form urea bond, and improve graphene oxide in coating dispersibility activity,
It is grafted upper isocyanate molecule simultaneously, increases the steric hindrance between coating strand and graphene, hydrogen bond can be formed between the two,
Its glass transition temperature is improved, so heat resistance of coating during heat conduction and heat radiation also gets a promotion, finally by
The processing of supercritical carbon dioxide using the density of lower liquid, while there is the performance for reducing surface tension to handle
Graphene afterwards preferably dissolves, and carries out swelling removing, increases the interlamellar spacing between graphene, so that heat conduction and heat radiation channel is beaten
It opens, increases heat conduction rate；
(2) heat dissipation migration agent prepared by the present invention is to be pre-processed with laccase to alkali lignin, increases the active sites of phenolic hydroxyl group
Point, then carry out necleophilic reaction with Isosorbide-5-Nitrae-butyl sultone, so that alkali lignin phenolic groups and alcoholic OH groups is alkyl etherified,
Under the catalysis for keeping sodium hydroxide, treated, and alkali lignin carries out alkane bridging, is bridging reagent, shape through 1,2- dichloroethanes
At the lignin polymers of the alkane bridging type of high molecular weight, so that alkyl chain is successfully accessed the phenolic hydroxyl group of lignin, lignin
Phenol structure can generate radical cation in oxidation process, along with the transfer process of electronics, with graphene raw material matrix
It is combined to form three-dimensional heat conduction network, is conducive to the transmitting of heat, lignin-base polymer during heat conduction and heat radiation
Hole migration is provided, the heat of importing is subjected to Transport And Transformation, forms the heat conduction and heat radiation channel comparatively fast dispersed, while utilizing heat dissipation
The hydrophobic framework that migration agent has, surface have hydrophilic active group hydroxy, methoxyl group etc. again, can by electrostatic interaction,
With graphene interface absorption behavior occurs for hydrogen bond action etc., and self assembly is then formed in coating using hydrophily, and improves
Dispersibility；
(3) component bridging agent prepared by the present invention carries out polycondensation reaction by acid anhydrides, allyl amine etc. for raw material and forms polyamides Asia
Amine acid, then the imido cyclization of heat is carried out with gamma-aminopropyl-triethoxy-silane, introducing in strand has water repellent
The siloxane chain of waterproof effect, and introduce phenyl etc. and utilize acyl during heat conduction and heat radiation with the group of preferable heat resistance
The thermal stability of imide ring and stronger polarity can be coated matrix to coating and form bonding, on the one hand will applied using siloxane chain
Material each component is attached, and improves component compatibility, on the other hand forms Thermal protection to heat conduction and heat radiation channel, increases Heat-resistant stable
Property, so that coating is still able to maintain excellent performance under heating condition；
(4) curing additive prepared by the present invention with 2-ethyl-4-methylimidazole, lauroyl chloride carry out acyl chloride reaction, then with
Zinc acetate forms the solidification that complexing carries out coating, and graphene oxide can be increased in epoxy resin-base by being introduced into imidazole radicals both
Dispersibility, meanwhile, the presence of imidazoles participates in graphene oxide in the curing reaction of epoxy resin again, plays solidification
The effect of agent, is complexed using metal ion, since the imines nitrogen of imidazoles has a lone pair electrons, easily be free valence orbit
Transition metal atoms form chelation structure, and chelation structure limits the reactivity of imidazole molecule, in the epoxy longer
Storage period, and when heating temperature increases, the fit key of complex compound can be destroyed again, and the imidazole molecule being released can join resin
It is cured reaction, so that coating has preferable temperature response performance, preferable adhesive property is kept in radiation processes, is prevented
Stop the heated cracking of coating, fallen off, improves the overall performance of coating.
Specific embodiment
Graphite alkene monomer the preparation method comprises the following steps:
(1) it takes graphene oxide 1 ~ 3:40 in mass ratio ~ 50 that dioxane is added, the N, N- of dioxane quality 5 ~ 10% is added
Dimethylformamide is passed through nitrogen protection, adds the cinnamoyl chloride of dioxane quality 1 ~ 5%, is stirred in 20 ~ 25 DEG C
10 ~ 12h, centrifugation take precipitating through methylene chloride, acetone washing, and drying obtains dried object；
(2) take dried object 3 ~ 7:10 in mass ratio ~ 30 that n,N-Dimethylformamide is added, 20 ~ 30min of ultrasound obtains ultrasonic liquid, presses
Mass fraction meter takes 20 ~ 30 parts of ultrasonic liquid, 1 ~ 3 part of sodium azide, 0.2 ~ 0.5 part of benzyltriethylammoinium chloride, 40 ~ 50 parts of N,
Dinethylformamide is passed through nitrogen protection, is stirred 8 ~ 12h in 50 ~ 60 DEG C, and filtering takes filter cake through N, N- dimethyl methyl
Amide washing, takes washings 10 ~ 20:3 in mass ratio ~ 6 that the hydrochloric acid that mass fraction is 35%, 1 ~ 3h of ultrasound is added, and filtering takes filter
Slag is washed through deionized water, dry to get graphite alkene monomer.
Modified active agent are as follows: according to the mass fraction, take 5 ~ 15 parts of 1,6- hexamethylene diisocyanates, 3 ~ 7 parts of 2,4- first
Phenylene diisocyanate, 4 ~ 8 parts of 4,4'- methyl diphenylene diisocyanates, the mixing of 2 ~ 6 parts of isoflurane chalcone diisocyanates to get.
Graphene-based raw material the preparation method comprises the following steps: take graphite alkene monomer 2 ~ 5:30 in mass ratio ~ 50 be added N, N- dimethyl
Formamide, 20 ~ 30min of ultrasound are passed through nitrogen protection, and 3 ~ 6 times of graphene monomer mass of modified active agent is added, is warming up to 65
~ 75 DEG C are stirred 30 ~ 50min, obtain stirring mixture, take stirring mixture 40 ~ 50:1 in mass ratio ~ 3 that tin dilaurate is added
Dibutyl tin is passed through carbon dioxide reaction, keep 18 under 30 ~ 35 DEG C of supercriticalities ~ for 24 hours, it filters, takes filter cake vacuum dry
It is dry to get graphene-based raw material.
Pre-process alkali lignin are as follows: the Acetic acid-sodium acetate for taking alkali lignin 2 ~ 5:10 in mass ratio ~ 20 that pH4.9 is added is slow
Fliud flushing is stirred 20 ~ 40min in 20 ~ 25 DEG C, adds the laccase of alkali lignin quality 3 ~ 9%, is stirred in 30 ~ 40 DEG C
3 ~ 6h, enzyme deactivation, filtering take filtrate to be freeze-dried to get pretreatment alkali lignin.
Mass fraction is added the preparation method comprises the following steps: taking and pre-processing alkali lignin 2 ~ 5:10 in mass ratio ~ 30 in heat dissipation migration agent
For 20% sodium hydroxide solution, it is stirred 20 ~ 30min in 20 ~ 25 DEG C, adds pretreatment alkali lignin quality 10 ~ 15%
Potassium iodide, be stirred 1 ~ 3h in 70 ~ 80 DEG C, obtain stirring mixture, take stirring mixture 40 ~ 50:2 in mass ratio ~ 7 be added
Isosorbide-5-Nitrae-butyl sultone is stirred 20 ~ 30min in 70 ~ 80 DEG C, adds 1, the 2- dichloro for being stirred amount of substance 30 ~ 40%
Ethane obtains mixture in 70 ~ 80 DEG C of 5 ~ 8h of heat preservation, takes mixture 2 ~ 5:10 in mass ratio ~ 15 that petroleum ether extraction is added, removes
Layer liquid dialysis is to get thermally conductive migration agent.
Acid activity agent are as follows: take phthalic anhydride, carbic anhydride, maleic anhydride, in 4- phenylacetylene benzoic anhydride
Any one or it is any it is several by any mass ratio mix to get.
Component bridging agent are as follows: take acid activity agent 2 ~ 5:10 in mass ratio ~ 15 be added methanol, add acid activity agent quality 1 ~
3% p-methyl benzenesulfonic acid is stirred 1 ~ 3h in 30 ~ 40 DEG C, vacuum distillation, takes vacuum distillation object molten through saturated sodium bicarbonate
Liquid washing, it is dry to get component bridging agent.
Curing additive the preparation method comprises the following steps:
S1. it takes 2-ethyl-4-methylimidazole 3 ~ 7:1 in mass ratio ~ 3:20 ~ 30 that triethylamine, toluene is added, is passed through nitrogen protection,
It is stirred 30 ~ 50min in 20 ~ 25 DEG C, obtains stirring mixture, lauroyl chloride 1 ~ 4:5 in mass ratio ~ 10 addition is taken to be stirred
Object is stirred 4 ~ 6h in 20 ~ 25 DEG C, filters, and takes smoke filtrate rotary evaporation, rotary evaporation residue is collected, through petroleum ether, second
Acetoacetic ester washing collects washed product vacuum drying, obtains vacuum drying object；
S2. it takes vacuum drying object 2 ~ 5:10 in mass ratio ~ 15 that dehydrated alcohol is added, is stirred 20 ~ 30min, it is dry that vacuum is added
The zinc acetate of dry amount of substance 5 ~ 10% is stirred 1 ~ 3h in 40 ~ 50 DEG C, and filtering takes filtrate rotary evaporation, collects rotary evaporation
Residue is to get curing additive.
Diluent are as follows: according to the mass fraction, take 2 ~ 5 parts of acrylic glycidol ethers, 1 ~ 3 part of phenyl glycidyl ether, 20 ~
25 parts of acetone, 2 ~ 6 parts of dibutyl phthalates, 20 ~ 40 parts of propylene glycol, the mixing of 10 ~ 15 parts of ethylene glycol to get.
A kind of preparation method of graphene heat radiation coating, includes the following steps:
A. according to the mass fraction, 20 ~ 30 parts of component bridging agents, 2 ~ 7 parts of allyl amines, 40 ~ 60 parts of deionized waters, 0.4 ~ 0.8 are taken
Part Pt/C catalyst, 40 ~ 60 parts of toluene are passed through argon gas protection, are stirred 20 ~ 40min in 40 ~ 50 DEG C, obtain mixture, take mixed
It closes object 40 ~ 50:3 in mass ratio ~ 6 and gamma-aminopropyl-triethoxy-silane is added, be warming up to 60 ~ 80 DEG C and be stirred 2 ~ 4h, it is cooling
To room temperature, rotary evaporation collects rotary evaporation residue；
B. according to the mass fraction, 20 ~ 50 parts of graphene-based raw materials, 20 ~ 30 parts of thermally conductive migration agents, 3 ~ 9 parts of rotary evaporation residues are taken
Object, 2 ~ 5 parts of curing additives, 200 ~ 300 parts of epoxy resin E-44s, 1 ~ 5 part of polyoxyethylene polyoxypropylene pentaerythrite ether, 2 ~ 6
Part diluent, is stirred 1 ~ 3h in 30 ~ 50 DEG C to get graphene heat radiation coating.
Graphite alkene monomer the preparation method comprises the following steps:
(1) it takes graphene oxide 1:40 in mass ratio that dioxane is added, the N of dioxane quality 5%, N- dimethyl methyl is added
Amide is passed through nitrogen protection, adds the cinnamoyl chloride of dioxane quality 1%, is stirred 10h in 20 DEG C, and centrifugation, it is heavy to take
It forms sediment through methylene chloride, acetone washing, it is dry, obtain dried object；
(2) take dried object 3:10 in mass ratio that n,N-Dimethylformamide is added, ultrasonic 20min obtains ultrasonic liquid, by mass fraction
Meter takes 20 parts of ultrasonic liquid, 1 part of sodium azide, 0.2 part of benzyltriethylammoinium chloride, 40 parts of n,N-Dimethylformamide, is passed through nitrogen
Gas shielded is stirred 8h in 50 DEG C, and filtering takes filter cake to wash through n,N-Dimethylformamide, takes washings in mass ratio 10:
3 are added the hydrochloric acid that mass fraction is 35%, ultrasonic 1h, and filtering takes filter residue to wash through deionized water, dry to get graphene list
Body.
Modified active agent are as follows: according to the mass fraction, take 5 parts of 1,6- hexamethylene diisocyanates, 3 parts of 2,4- toluene two different
Cyanate, 4 parts of 4,4'- methyl diphenylene diisocyanates, the mixing of 2 parts of isoflurane chalcone diisocyanates to get.
Graphene-based raw material the preparation method comprises the following steps: take graphite alkene monomer 2:30 in mass ratio be added N, N- dimethyl formyl
Amine, ultrasonic 20min are passed through nitrogen protection, and 3 times of graphene monomer mass of modified active agent is added, and it is mixed to be warming up to 65 DEG C of stirrings
30min is closed, stirring mixture is obtained, takes stirring mixture 40:1 in mass ratio that dibutyl tin dilaurate is added, is passed through titanium dioxide
Carbon reaction, keeps 18h under 30 DEG C of supercriticalities, filters, takes filter cake to be dried in vacuo to get graphene-based raw material.
Pre-process alkali lignin are as follows: take alkali lignin 2:10 in mass ratio that the Acetic acid-sodium acetate buffer of pH4.9 is added,
It is stirred 20min in 20 DEG C, adds the laccase of alkali lignin quality 3%, 3h, enzyme deactivation are stirred in 30 DEG C, filtering takes
Filtrate freeze-drying is to get pretreatment alkali lignin.
Heat dissipation migration agent the preparation method comprises the following steps: take pretreatment alkali lignin 2:10 in mass ratio be added mass fraction be 20%
Sodium hydroxide solution, be stirred 20min in 20 DEG C, add pretreatment alkali lignin quality 10% potassium iodide, in 70 DEG C
It is stirred 1h, obtains stirring mixture, takes stirring mixture 40:2 in mass ratio that Isosorbide-5-Nitrae-butyl sultone is added, is stirred in 70 DEG C
20min is mixed, 1, the 2- dichloroethanes for being stirred amount of substance 30% is added, in 70 DEG C of heat preservation 5h, obtains mixture, take mixing
Petroleum ether extraction is added in object 2:10 in mass ratio, takes subnatant to dialyse to get thermally conductive migration agent.
Acid activity agent are as follows: take phthalic anhydride, carbic anhydride by any mass ratio mix to get.
Component bridging agent are as follows: take acid activity agent 2:10 in mass ratio that methanol is added, add pair of acid activity agent quality 1%
Toluenesulfonic acid is stirred 1h in 30 DEG C, vacuum distillation, and vacuum distillation object is taken to wash through saturated sodium bicarbonate solution, dry,
Up to component bridging agent.
Curing additive the preparation method comprises the following steps:
S1. it takes 2-ethyl-4-methylimidazole 3:1:20 in mass ratio that triethylamine, toluene is added, is passed through nitrogen protection, is stirred in 20 DEG C
Mixing 30min is mixed, stirring mixture is obtained, takes lauroyl chloride 1:5 in mass ratio that stirring mixture is added, is stirred in 20 DEG C
4h is filtered, and takes smoke filtrate rotary evaporation, collects rotary evaporation residue, is washed through petroleum ether, ethyl acetate, is collected washing and is produced
Object vacuum drying, obtains vacuum drying object；
S2. it takes vacuum drying object 2:10 in mass ratio that dehydrated alcohol is added, is stirred 20min, vacuum drying amount of substance is added
5% zinc acetate is stirred 1h in 40 DEG C, and filtering takes filtrate rotary evaporation, collects rotary evaporation residue and adds to get solidification
Add agent.
Diluent are as follows: according to the mass fraction, take 2 parts of acrylic glycidol ethers, 1 part of phenyl glycidyl ether, 20 part third
Ketone, 2 parts of dibutyl phthalates, 20 parts of propylene glycol, the mixing of 10 parts of ethylene glycol to get.
A kind of preparation method of graphene heat radiation coating, includes the following steps:
A. according to the mass fraction, take 20 parts of component bridging agents, 2 parts of allyl amines, 40 parts of deionized waters, 0.4 part of Pt/C catalyst,
40 parts of toluene are passed through argon gas protection, are stirred 20min in 40 DEG C, obtain mixture, mixture 40:3 in mass ratio is taken to be added
Gamma-aminopropyl-triethoxy-silane is warming up to 60 DEG C and is stirred 2h, is cooled to room temperature, rotary evaporation, and it is surplus to collect rotary evaporation
Excess；
B. according to the mass fraction, take 20 parts of graphene-based raw materials, 20 parts of thermally conductive migration agents, 3 parts of rotary evaporation residues, 2 parts it is solid
Change additive, 200 parts of epoxy resin E-44s, 1 part of polyoxyethylene polyoxypropylene pentaerythrite ether, 2 parts of diluents, is stirred in 30 DEG C
1h is mixed to get graphene heat radiation coating.
Graphite alkene monomer the preparation method comprises the following steps:
(1) it takes graphene oxide 2:45 in mass ratio that dioxane is added, the N of dioxane quality 8%, N- dimethyl methyl is added
Amide is passed through nitrogen protection, adds the cinnamoyl chloride of dioxane quality 3%, is stirred 11h in 22 DEG C, and centrifugation, it is heavy to take
It forms sediment through methylene chloride, acetone washing, it is dry, obtain dried object；
(2) take dried object 5:20 in mass ratio that n,N-Dimethylformamide is added, ultrasonic 25min obtains ultrasonic liquid, by mass fraction
Meter takes 25 parts of ultrasonic liquid, 2 parts of sodium azide, 0.3 part of benzyltriethylammoinium chloride, 45 parts of n,N-Dimethylformamide, is passed through nitrogen
Gas shielded is stirred 10h in 55 DEG C, and filtering takes filter cake to wash through n,N-Dimethylformamide, takes washings in mass ratio
The hydrochloric acid that mass fraction is 35%, ultrasonic 2h is added in 15:5, and filtering takes filter residue to wash through deionized water, dry to get graphene
Monomer.
Modified active agent are as follows: according to the mass fraction, take 10 parts of 1,6- hexamethylene diisocyanates, 5 parts of 2,4- toluene two
Isocyanates, 6 parts of 4,4'- methyl diphenylene diisocyanates, the mixing of 4 parts of isoflurane chalcone diisocyanates to get.
Graphene-based raw material the preparation method comprises the following steps: take graphite alkene monomer 4:40 in mass ratio be added N, N- dimethyl formyl
Amine, ultrasonic 25min are passed through nitrogen protection, and 5 times of graphene monomer mass of modified active agent is added, and it is mixed to be warming up to 70 DEG C of stirrings
40min is closed, stirring mixture is obtained, takes stirring mixture 45:2 in mass ratio that dibutyl tin dilaurate is added, is passed through titanium dioxide
Carbon reaction, keeps 21h under 32 DEG C of supercriticalities, filters, takes filter cake to be dried in vacuo to get graphene-based raw material.
Pre-process alkali lignin are as follows: take alkali lignin 3:15 in mass ratio that the Acetic acid-sodium acetate buffer of pH4.9 is added,
It is stirred 30min in 22 DEG C, adds the laccase of alkali lignin quality 6%, 5h, enzyme deactivation are stirred in 35 DEG C, filtering takes
Filtrate freeze-drying is to get pretreatment alkali lignin.
Heat dissipation migration agent the preparation method comprises the following steps: take pretreatment alkali lignin 3:20 in mass ratio be added mass fraction be 20%
Sodium hydroxide solution, be stirred 25min in 22 DEG C, add pretreatment alkali lignin quality 12% potassium iodide, in 75 DEG C
It is stirred 2h, obtains stirring mixture, takes stirring mixture 45:5 in mass ratio that Isosorbide-5-Nitrae-butyl sultone is added, is stirred in 75 DEG C
25min is mixed, 1, the 2- dichloroethanes for being stirred amount of substance 35% is added, in 75 DEG C of heat preservation 7h, obtains mixture, take mixing
Petroleum ether extraction is added in object 4:12 in mass ratio, takes subnatant to dialyse to get thermally conductive migration agent.
Acid activity agent are as follows: take carbic anhydride, maleic anhydride by any mass ratio mix to get.
Component bridging agent are as follows: take acid activity agent 4:12 in mass ratio that methanol is added, add pair of acid activity agent quality 2%
Toluenesulfonic acid is stirred 2h in 35 DEG C, vacuum distillation, and vacuum distillation object is taken to wash through saturated sodium bicarbonate solution, dry,
Up to component bridging agent.
Curing additive the preparation method comprises the following steps:
S1. it takes 2-ethyl-4-methylimidazole 5:2:25 in mass ratio that triethylamine, toluene is added, is passed through nitrogen protection, is stirred in 22 DEG C
Mixing 40min is mixed, stirring mixture is obtained, takes lauroyl chloride 3:8 in mass ratio that stirring mixture is added, is stirred in 23 DEG C
5h is filtered, and takes smoke filtrate rotary evaporation, collects rotary evaporation residue, is washed through petroleum ether, ethyl acetate, is collected washing and is produced
Object vacuum drying, obtains vacuum drying object；
S2. it takes vacuum drying object 4:13 in mass ratio that dehydrated alcohol is added, is stirred 25min, vacuum drying amount of substance is added
7% zinc acetate is stirred 2h in 45 DEG C, and filtering takes filtrate rotary evaporation, collects rotary evaporation residue and adds to get solidification
Add agent.
Diluent are as follows: according to the mass fraction, take 3 parts of acrylic glycidol ethers, 2 parts of phenyl glycidyl ethers, 23 part third
Ketone, 4 parts of dibutyl phthalates, 30 parts of propylene glycol, the mixing of 13 parts of ethylene glycol to get.
A kind of preparation method of graphene heat radiation coating, includes the following steps:
A. according to the mass fraction, take 25 parts of component bridging agents, 5 parts of allyl amines, 50 parts of deionized waters, 0.6 part of Pt/C catalyst,
50 parts of toluene are passed through argon gas protection, are stirred 30min in 45 DEG C, obtain mixture, mixture 45:5 in mass ratio is taken to be added
Gamma-aminopropyl-triethoxy-silane is warming up to 70 DEG C and is stirred 3h, is cooled to room temperature, rotary evaporation, and it is surplus to collect rotary evaporation
Excess；
B. according to the mass fraction, take 35 parts of graphene-based raw materials, 25 parts of thermally conductive migration agents, 6 parts of rotary evaporation residues, 3 parts it is solid
Change additive, 250 parts of epoxy resin E-44s, 3 parts of polyoxyethylene polyoxypropylene pentaerythrite ethers, 4 parts of diluents, is stirred in 40 DEG C
2h is mixed to get graphene heat radiation coating.
Graphite alkene monomer the preparation method comprises the following steps:
(1) it takes graphene oxide 3:50 in mass ratio that dioxane is added, the N of dioxane quality 10%, N- dimethyl methyl is added
Amide is passed through nitrogen protection, adds the cinnamoyl chloride of dioxane quality 5%, is stirred 12h in 25 DEG C, and centrifugation, it is heavy to take
It forms sediment through methylene chloride, acetone washing, it is dry, obtain dried object；
(2) take dried object 7:30 in mass ratio that n,N-Dimethylformamide is added, ultrasonic 30min obtains ultrasonic liquid, by mass fraction
Meter takes 30 parts of ultrasonic liquid, 3 parts of sodium azide, 0.5 part of benzyltriethylammoinium chloride, 50 parts of n,N-Dimethylformamide, is passed through nitrogen
Gas shielded is stirred 12h in 60 DEG C, and filtering takes filter cake to wash through n,N-Dimethylformamide, takes washings in mass ratio
The hydrochloric acid that mass fraction is 35%, ultrasonic 3h is added in 20:6, and filtering takes filter residue to wash through deionized water, dry to get graphene
Monomer.
Modified active agent are as follows: according to the mass fraction, take 15 parts of 1,6- hexamethylene diisocyanates, 7 parts of 2,4- toluene two
Isocyanates, 8 parts of 4,4'- methyl diphenylene diisocyanates, the mixing of 6 parts of isoflurane chalcone diisocyanates to get.
Graphene-based raw material the preparation method comprises the following steps: take graphite alkene monomer 5:50 in mass ratio be added N, N- dimethyl formyl
Amine, ultrasonic 30min are passed through nitrogen protection, and 6 times of graphene monomer mass of modified active agent is added, and it is mixed to be warming up to 75 DEG C of stirrings
50min is closed, stirring mixture is obtained, takes stirring mixture 50:3 in mass ratio that dibutyl tin dilaurate is added, is passed through titanium dioxide
Carbon reaction keeps for 24 hours, filtering, taking filter cake to be dried in vacuo to get graphene-based raw material under 35 DEG C of supercriticalities.
Pre-process alkali lignin are as follows: take alkali lignin 5:20 in mass ratio that the Acetic acid-sodium acetate buffer of pH4.9 is added,
It is stirred 40min in 25 DEG C, adds the laccase of alkali lignin quality 9%, 6h, enzyme deactivation are stirred in 40 DEG C, filtering takes
Filtrate freeze-drying is to get pretreatment alkali lignin.
Heat dissipation migration agent the preparation method comprises the following steps: take pretreatment alkali lignin 5:30 in mass ratio be added mass fraction be 20%
Sodium hydroxide solution, be stirred 30min in 25 DEG C, add pretreatment alkali lignin quality 15% potassium iodide, in 80 DEG C
It is stirred 3h, obtains stirring mixture, takes stirring mixture 50:7 in mass ratio that Isosorbide-5-Nitrae-butyl sultone is added, is stirred in 80 DEG C
30min is mixed, 1, the 2- dichloroethanes for being stirred amount of substance 40% is added, in 80 DEG C of heat preservation 8h, obtains mixture, take mixing
Petroleum ether extraction is added in object 5:15 in mass ratio, takes subnatant to dialyse to get thermally conductive migration agent.
Acid activity agent are as follows: take maleic anhydride, 4- phenylacetylene benzoic anhydride by any mass ratio mix to get.
Component bridging agent are as follows: take acid activity agent 5:15 in mass ratio that methanol is added, add pair of acid activity agent quality 3%
Toluenesulfonic acid is stirred 3h in 40 DEG C, vacuum distillation, and vacuum distillation object is taken to wash through saturated sodium bicarbonate solution, dry,
Up to component bridging agent.
Curing additive the preparation method comprises the following steps:
S1. it takes 2-ethyl-4-methylimidazole 7:3:30 in mass ratio that triethylamine, toluene is added, is passed through nitrogen protection, is stirred in 25 DEG C
Mixing 50min is mixed, stirring mixture is obtained, takes lauroyl chloride 4:10 in mass ratio that stirring mixture is added, is stirred in 25 DEG C
6h is filtered, and takes smoke filtrate rotary evaporation, collects rotary evaporation residue, is washed through petroleum ether, ethyl acetate, is collected washing and is produced
Object vacuum drying, obtains vacuum drying object；
S2. it takes vacuum drying object 5:15 in mass ratio that dehydrated alcohol is added, is stirred 30min, vacuum drying amount of substance is added
10% zinc acetate is stirred 3h in 50 DEG C, and filtering takes filtrate rotary evaporation, collects rotary evaporation residue to get solidification
Additive.
Diluent are as follows: according to the mass fraction, take 5 parts of acrylic glycidol ethers, 3 parts of phenyl glycidyl ethers, 25 part third
Ketone, 6 parts of dibutyl phthalates, 40 parts of propylene glycol, the mixing of 15 parts of ethylene glycol to get.
A kind of preparation method of graphene heat radiation coating, includes the following steps:
A. according to the mass fraction, take 30 parts of component bridging agents, 7 parts of allyl amines, 60 parts of deionized waters, 0.8 part of Pt/C catalyst,
60 parts of toluene are passed through argon gas protection, are stirred 40min in 50 DEG C, obtain mixture, mixture 50:6 in mass ratio is taken to be added
Gamma-aminopropyl-triethoxy-silane is warming up to 80 DEG C and is stirred 4h, is cooled to room temperature, rotary evaporation, and it is surplus to collect rotary evaporation
Excess；
B. according to the mass fraction, take 50 parts of graphene-based raw materials, 30 parts of thermally conductive migration agents, 9 parts of rotary evaporation residues, 5 parts it is solid
Change additive, 300 parts of epoxy resin E-44s, 5 parts of polyoxyethylene polyoxypropylene pentaerythrite ethers, 6 parts of diluents, is stirred in 50 DEG C
3h is mixed to get graphene heat radiation coating.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking graphene-based raw material.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking heat dissipation migration agent.
Comparative example 3: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking component bridging agent.
Comparative example 4: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking curing additive.
Comparative example 5: the graphene heat radiation coating of Xi'an company production.
Graphene heat radiation coating obtained by embodiment and comparative example is carried out according to GB/T3651-2008, GB/T6739-1996
Test, test result are as shown in table 1:
Table 1:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Thermal conductivity (W/mk) | 1268 | 1206 | 1250 | 1125 | 1052 | 1084 | 968 | 825 |
| Infrared emittance (%) | 0.97 | 0.96 | 0.96 | 0.94 | 0.95 | 0.92 | 0.90 | 0.85 |
| Dispersibility | Preferably | Preferably | Preferably | Preferably | Preferably | Generally | Generally | It is poor |
In summary, the resulting graphene heat radiation coating thermal conductivity of the present invention is higher, and heat-conducting effect is preferable, compared to commercial product
Effect is more preferable, is worth promoting.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of graphene heat radiation coating, which is characterized in that including graphene-based raw material, heat dissipation migration agent, component bridging agent, consolidate
Change additive；
The graphene-based raw material the preparation method comprises the following steps: take graphite alkene monomer 2 ~ 5:30 in mass ratio ~ 50 be added N, N- dimethyl
Formamide, ultrasound are passed through nitrogen protection, and 3 ~ 6 times of graphene monomer mass of modified active agent is added and is stirred, and must stir mixed
Object is closed, takes stirring mixture 40 ~ 50:1 in mass ratio ~ 3 that dibutyl tin dilaurate is added, is passed through carbon dioxide reaction, in 30 ~
It is kept under 35 DEG C of supercriticalities, filters, take filter cake to be dried in vacuo to get graphene-based raw material.
2. graphene heat radiation coating according to claim 1, which is characterized in that the preparation method of the graphite alkene monomer
Are as follows:
(1) it takes graphene oxide 1 ~ 3:40 in mass ratio ~ 50 that dioxane is added, the N, N- of dioxane quality 5 ~ 10% is added
Dimethylformamide is passed through nitrogen protection, and the cinnamoyl chloride for adding dioxane quality 1 ~ 5% is stirred, and centrifugation, it is heavy to take
It forms sediment washed, it is dry, obtain dried object；
(2) take dried object 3 ~ 7:10 in mass ratio ~ 30 that n,N-Dimethylformamide is added, ultrasound obtains ultrasonic liquid, by mass fraction
Meter takes 20 ~ 30 parts of ultrasonic liquid, 1 ~ 3 part of sodium azide, 0.2 ~ 0.5 part of benzyltriethylammoinium chloride, 40 ~ 50 parts of N, N- dimethyl
Formamide is passed through nitrogen protection, is stirred, and filtering takes filter cake to wash through n,N-Dimethylformamide, takes washings by quality
Hydrochloric acid, ultrasound is added than 10 ~ 20:3 ~ 6, filtering takes filter residue washed, dry to get graphite alkene monomer.
3. graphene heat radiation coating according to claim 1, which is characterized in that the modified active agent are as follows: press mass parts
Number meter, takes 5 ~ 15 parts of 1,6- hexamethylene diisocyanates, 3 ~ 7 parts of 2,4- toluene di-isocyanate(TDI)s, 4 ~ 8 parts of 4,4'- diphenyl
Methane diisocyanate, the mixing of 2 ~ 6 parts of isoflurane chalcone diisocyanates to get.
4. graphene heat radiation coating according to claim 1, which is characterized in that the preparation method of the heat dissipation migration agent
Are as follows: it takes pretreatment alkali lignin 2 ~ 5:10 in mass ratio ~ 30 that sodium hydroxide solution is added and is stirred, add pretreatment alkali wood
The potassium iodide of quality quality 10 ~ 15% is stirred, and obtains stirring mixture, and stirring mixture 40 ~ 50:2 in mass ratio ~ 7 is taken to be added
Isosorbide-5-Nitrae-butyl sultone is stirred, and adds 1, the 2- dichloroethanes for being stirred amount of substance 30 ~ 40%, is protected in 70 ~ 80 DEG C
Temperature obtains mixture, takes mixture 2 ~ 5:10 in mass ratio ~ 15 that petroleum ether extraction is added, takes subnatant to dialyse to get thermally conductive migration
Agent.
5. graphene heat radiation coating according to claim 4, which is characterized in that the pretreatment alkali lignin are as follows: take alkali
Lignin 2 ~ 5:10 in mass ratio ~ 20 is added Acetic acid-sodium acetate buffer and is stirred, and adds alkali lignin quality 3 ~ 9%
Laccase is stirred, enzyme deactivation, filtering, takes filtrate to be freeze-dried to get pretreatment alkali lignin.
6. graphene heat radiation coating according to claim 1, which is characterized in that the component bridging agent are as follows: take acid activity
Methanol is added in agent 2 ~ 5:10 in mass ratio ~ 15, and the p-methyl benzenesulfonic acid for adding acid activity agent quality 1 ~ 3% is stirred, and depressurizes
Distillation takes vacuum distillation object washed, dry to get component bridging agent.
7. graphene heat radiation coating according to claim 6, which is characterized in that the acid activity agent are as follows: take O-phthalic
Acid anhydrides, carbic anhydride, maleic anhydride, any one in 4- phenylacetylene benzoic anhydride any several press any mass ratio
Mixing to get.
8. graphene heat radiation coating according to claim 1, which is characterized in that the preparation method of the curing additive
Are as follows:
S1. it takes 2-ethyl-4-methylimidazole 3 ~ 7:1 in mass ratio ~ 3:20 ~ 30 that triethylamine, toluene is added, is passed through nitrogen protection,
It is stirred, obtains stirring mixture, take lauroyl chloride 1 ~ 4:5 in mass ratio ~ 10 that stirring mixture is added and be stirred, filter,
Smoke filtrate rotary evaporation is taken, rotary evaporation residue is collected, it is washed, washed product vacuum drying is collected, vacuum drying object is obtained；
S2. it takes vacuum drying object 2 ~ 5:10 in mass ratio ~ 15 that absolute ethyl alcohol and stirring is added to mix, addition vacuum drying amount of substance 5 ~
10% zinc acetate is stirred, and filtering takes filtrate rotary evaporation, collects rotary evaporation residue to get curing additive.
9. a kind of preparation method of the graphene heat radiation coating as described in claim 1 ~ 8 any one, which is characterized in that the system
Preparation Method includes the following steps:
A. according to the mass fraction, 20 ~ 30 parts of component bridging agents, 2 ~ 7 parts of allyl amines, 40 ~ 60 parts of deionized waters, 0.4 ~ 0.8 are taken
Part Pt/C catalyst, 40 ~ 60 parts of toluene are passed through argon gas protection, are stirred, obtain mixture, take mixture in mass ratio 40 ~
50:3 ~ 6 is added gamma-aminopropyl-triethoxy-silane and is stirred, and is cooled to room temperature, rotary evaporation, and it is remaining to collect rotary evaporation
Object；
B. according to the mass fraction, 20 ~ 50 parts of graphene-based raw materials, 20 ~ 30 parts of thermally conductive migration agents, 3 ~ 9 parts of rotary evaporation residues are taken
Object, 2 ~ 5 parts of curing additives, 200 ~ 300 parts of epoxy resin E-44s, 1 ~ 5 part of polyoxyethylene polyoxypropylene pentaerythrite ether, 2 ~ 6
Part diluent is stirred to get graphene heat radiation coating.
10. the preparation method of graphene heat radiation coating according to claim 9, which is characterized in that dilute in the step B
Release agent are as follows: according to the mass fraction, take 2 ~ 5 parts of acrylic glycidol ethers, 1 ~ 3 part of phenyl glycidyl ether, 20 ~ 25 parts of acetone, 2
~ 6 parts of dibutyl phthalates, 20 ~ 40 parts of propylene glycol, the mixing of 10 ~ 15 parts of ethylene glycol to get.
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