CN109824866A - A kind of graphene in-situ polymerization reinforced epoxy and preparation method thereof - Google Patents
A kind of graphene in-situ polymerization reinforced epoxy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to composite material field, more particularly to a kind of graphene in-situ polymerization high-thermal-conductivity epoxy resin and preparation method thereof.The method have the characteristics that by the way that redox graphene@powder of nanometric particles is uniformly dispersed in inside epoxychloropropane in a manner of stirring and is ultrasonic, epoxychloropropane is aqueous liquid at room temperature, viscosity of its viscosity well below polymer epoxy, so the gap in redox graphene@nano particle can be filled up well, gas in powder particle excludes completely also by means such as ultrasounds, to solve the problems, such as that powder cannot be uniformly blended in colloid；The advantage that the present invention is able to batch production is that the combination of thermally conductive powder and epoxychloropropane does not chemically react, the remaining epoxychloropropane of polymerization reaction can pass through circulating collection after vacuum distillation, it is reacted again, also the appearance that environmental pollution has been prevented while cost can be saved is a kind of environmentally friendly production method.
Description
Technical field
The invention belongs to composite material field, more particularly to arriving a kind of graphene in-situ polymerization high thermal conductivity epoxy
Resin and preparation method thereof.
Background technique
Graphene is a kind of two-dimension single layer flake nano material being made of carbon atom with hybrid form close-packed arrays, because of it
Excellent conductive, thermally conductive, mechanical property is received significant attention with optical transmission in new material and special material field.Single layer stone
The thermal conductivity theoretical value of black alkene up to 5300W m-1 K-1 is that be currently known thermal conductivity in substance highest, thus the present invention tightly around
The good heat conductive property of graphene researched and developed, it is known that chemical method is most simple from several graphene preparation methods known
Single method, but the graphene of single layer is hardly resulted in, so being born by adding nano particle in graphene oxide state
Load, which restores, can solve the problems, such as that pure graphene is easy to reunite.
Aluminium nitride aluminium nitride is a kind of substance being connected with covalent bond, it has hex crystal structure, with zinc sulphide, fiber zinc
Mine similar shape possesses good thermal conductivity, and thermal coefficient reaches 320W m-1 K-1, and the thermal conductivity than metals such as fine copper, iron is also high,
So be widely used in various electronic instruments, above the instruments such as heat transfer heat dissipation, aluminium nitride is also as thermal stability is good, impact resistance ability
The advantages that strong and route of synthesis is simple is even more to be widely used in the various aspects such as military affairs of living.
Boron nitride is the crystal being made of nitrogen-atoms and boron atom.Chemical composition be 43.6% boron and 56.4% nitrogen,
There are four types of different variants for tool: hexagonal boron nitride (HBN), water chestnut side's boron nitride (RBN), cubic boron nitride (CBN) and buergerite nitrogen
Change boron (WBN), BN material thermal stability is good, and not decomposing under high temperature is the most excellent third generation semiconductor material of performance, not only
It can be used to prepare the electronic device to work under the extreme conditions such as high temperature, high frequency, high-power, and in deep-UV light-emitting and detection
Have a wide range of applications in terms of device, furthermore boron nitride because its heating conduction it is good, equally can also be thermally conductive again, heat dissipation aspect
It is widely used.
Oxidation alumina is a kind of compound of high rigidity, and fusing point is 2054 DEG C, at high temperature ionizable ionic crystals, often
For manufacturing refractory material, aluminium oxide is because the cost of itself is cheap and heating conduction is good, so, heat dissipation thermally conductive doing
Aspect also has good application prospect.
The thermal conductivity of the low-density epoxy resin heat-conducting glue of mainstream all maintains 0.2-1.0W m-1 K-1 currently on the market
Between, once the resin that thermal coefficient is more than 1W m-1 K-1 is all density, viscosity is all very big, is difficult drip to pour encapsulating, institute
To be a problem that current industry is faced, the present invention by heat conductive graphite powder and epoxy source material epoxychloropropane into
In-situ polymerization effective solution epoxy resin large viscosity is difficult and the well-mixed problem of powder again after the mixing of row presoma.
Summary of the invention
In order to solve the shortcomings of the prior art, the present invention provides a kind of graphene for being uniformly dispersed, reuniting few is former
Position polymerization reinforced epoxy and preparation method thereof.
To realize that graphene can be uniformly dispersed well and occur the phenomenon that reunion less, the present invention provides with nanometer
Grain is by the graphene film layer material uniform load of the state of oxidation, by aluminium nitride, aluminium oxide, the nano particles such as boron nitride and oxidation stone
Black alkene control mass ratio, by the collective effect of coupling agent and ultrasound, keeps nano particle particle fine between 1:1-1:5
Ground is supported on surface of graphene oxide, and because play the role of coupling agent than the active force of traditional direct physical load also than
It is strong very much, the method effective solution graphene film layer material itself problem easy to reunite, so that finally obtained compound
The property for saving nanoscale of material maximum dynamics.
The method have the characteristics that by the way that redox graphene@powder of nanometric particles is equal in a manner of stirring and is ultrasonic
Even is dispersed in inside epoxychloropropane, and epoxychloropropane is aqueous liquid at room temperature, and viscosity is well below polymer ring
The viscosity of oxygen resin, so can well fill up the gap in redox graphene@nano particle, in powder particle
Gas excludes completely also by means such as ultrasounds, to solve the problems, such as that powder cannot be uniformly blended in colloid；This hair
The bright advantage for being able to batch production is that the combination of thermally conductive powder and epoxychloropropane does not chemically react, and polymerization reaction is remaining
Epoxychloropropane then can be reacted by circulating collection after vacuum distillation, also prevent environment while cost can be saved
The appearance of pollution is a kind of environmentally friendly production method.
A kind of graphene in-situ polymerization reinforced epoxy, which is characterized in that including with redox graphene, nitridation
Aluminium, epoxychloropropane and bisphenol-A are raw material, obtain the E51 type that epoxide number is 46-55 after in-situ polymerization after being evaporated under reduced pressure and lead
Hot epoxy resin.
A kind of preparation method that graphene in-situ polymerization reinforced epoxy is thermally conductive, comprising the following steps:
S1: with 325 mesh graphite powders in suitable P2O5And K2S2O8Under the action of to be pre-oxidized, after washing is dry
Graphene oxide is prepared with hummer method again, and is saved inside dehydrated alcohol, acetone and other organic solvent；
S2: the step S1 is obtained into graphene oxide solution and suitable aluminium nitride, aluminium oxide, boron nitride carries out at ultrasound
Several hours are managed, until beaker bottom stops ultrasound without solid particle, obtain nano particle@GO dispersion liquid；
S3: the nano particle GO dispersion liquid that the step S2 is obtained is placed in flask, is with appropriate hydrazine hydrate after heating
Reducing agent restores nano particle@GO dispersion liquid, and solution can become palm fibre from ecru within half a minute after hydrazine hydrate is added
Color or black, juvenescence is obvious, obtains the compound of redox graphene@nano particle after sufficiently restoring a period of time；
S4: the nano particle@RGO dispersion liquid that the step S3 is obtained is filtered with pressure-reduction filter device, after suction filtration
Composite material ethyl alcohol, the low boiling point solvents such as acetone carry out displacement washing after be dried in the vacuum drying oven of thermophilic low pressure
Processing obtains the conductive powder needed for us, using wall-breaking machine, pulverizer, the devices such as ball mill by the powder after drying carry out into
One step is smashed；
S5: the nano particle@RGO powder that the step S4 is obtained being stirred with epoxychloropropane and is mixed, and is added after heating
Enter bisphenol-A and NaOH initiation reaction is added, finally obtains the mixture of epoxy resin and epoxychloropropane, and pass through vacuum distillation
Unreacted epoxychloropropane is recycled, the high-thermal-conductivity epoxy resin needed for us is finally obtained；
S6: the thermally conductive system of measurement after the in-situ polymerization heat-conduction epoxy resin and curing agent that the step S5 is obtained are mixing cured
Number.
Preferably, by the graphite powder processing method in S1 step: when being vigorously stirred, by 2.5 g potassium peroxydisulfates,
2.5 g phosphorus pentoxides, which sequentially add, obtains clear solution in the 7.5 mL concentrated sulfuric acids, it is natural to weigh 5.0 g to 80 DEG C for oil bath heating
Graphite, which is carefully added into react 3 hours in mixed liquor, obtains blackish green mixture, cools down 6 hours at room temperature；Slowly secondary water is added
Enter in said mixture and dilute, filter, and to be washed to filtrate be neutral with secondary；It is dried overnight in drier at room temperature, it obtains
Graphite pre-oxidizes object.
Preferably, by the hummer method concrete operations in S1 step: weighing the above-mentioned graphite pre-oxidation object of 1.0 g and carefully add
Enter into the 1000 mL beakers for filling the 23 mL concentrated sulfuric acids and (operated under ice-water bath), then weighs 3.0 g potassium permanganate, it is small under stirring
The heart is added slowly in above-mentioned mixed liquor (this process temperature centainly controls 20 DEG C or less), removes ice bath, and mixed liquor is transferred to 250
In mL round-bottomed flask, using oil bath control system temperature at 35 DEG C, then it is stirred to react 2 hours；There is bubbling existing in reaction process
As with the progress of reaction, mixture gradually thickens, this is because bubbling process is exactly the process of a concentration, system color
Green become taupe by black.It is carefully added into 46 mL secondary waters after 2 hours and obtains yellowish-brown dirty solution, the mixed liquor after dilution is in
Existing brown, adds 140 mL secondary waters, is then slowly added into 2.5 mL hydrogen peroxide (30 %), generates a large amount of gas after 15 minutes
Bubble, after reaction, mixed liquor becomes glassy yellow dirty solution；It filters after cooling and is washed with 250 mL(1:10) hydrochloric acid, and
It is stored in ethanol solution stand-by.
Preferably, by the ethyl alcohol of the nano particles and graphene oxide such as aluminium nitride, aluminium oxide, boron nitride in S2 step
Solution is according to graphene: the mass ratio of nano particle is the 1-10% for adding about gross mass after the ratio of 1:5-1:1 is mixed again
KH550 coupling agent carry out ultrasonic treatment 2-4 hours, enable nano particle completely to load and mix with graphene oxide
It closes, just obtains nano particle@GO solution after ultrasound.
Preferably, it is 1g that the graphene oxide@nanoparticles solution in S3 step, which is configured to graphene oxide content,
The solution of/L, and the hydrazine hydrate of 10-20 times of graphene oxide quality of addition is restored in 80 DEG C of environment, juvenescence is
Solution becomes pitch-dark completely in 1-5 minutes, and it is molten to obtain redox graphene@nano particle after restoring two hours at 80 DEG C
Liquid.
Preferably, by the redox graphene@nanoparticles solution in S4 step through decompression filtering and washing into
Property, obtained filter cake uses acetone again, and the low boiling point solvents such as ethyl alcohol are replaced, and obtains new filter cake, and new filter cake is placed in vacuum and is dried
It is 24 hours dry at 30-60 DEG C in case, redox graphene@nano particle filter cake is obtained, then pass through ball mill, pulverizer
Filter cake is crushed to after several micron levels for use by equal devices.
Preferably, the epoxychloropropane in S5 step is stirred with graphene complex, mixed mass ratio is
Graphene complex: theoretical epoxy is warming up to after stirring by mixing after 90 DEG C and gradually adds in batches again between 1:3-1:1
Enter NaOH and carries out initiated polymerization, it, will be more to which dark brown solution to be passed through to vacuum distillation again after mixing evenly after reaction
Remaining epoxychloropropane distillation is walked, and is recycled, and the epoxide number for obtaining brown or black is the epoxy resin of 46-55.
Preferably, by in-situ polymerization heat-conduction epoxy resin obtained in S5 step and curing agent according to quality than resin:
Curing agent be 10:1 or 8:1 ratio be added, 20 minutes degassing process are carried out after curing agent is added, after pour into
Sample after solidification is carried out thermally conductive measurement by mold cured.
Preferably, including: ethylenediamine, diethylenetriamine, triethylene tetramine, the rouge such as cyanamide class by curing agent in S5 step
Fat amine curing agent is also possible to aromatic amine curing agent；Wherein test equipment includes the plate stable state of the DRP major class of stable state class
Method test also includes HOT-Disk, the thermally conductive instrument of the transient tests such as infrared method.
Requirement according to the invention, the present invention provides the preparation sides of another graphene in-situ polymerization reinforced epoxy
Method, epoxy resin synthesis in remaining epoxychloropropane it is recyclable, graphite powder, epoxychloropropane, bisphenol-A original cost valence
Lattice are cheap, and having into tonne raw material can provide, specifically includes the following steps:
S1: 30 μm of graphite powder and the concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide, potassium permanganate etc. are aoxidized by hummer method
Graphene acid solution；
S2: the graphene oxide acid solution in step S1 is subjected to static layering and removes upper part acidic liquid, is left
Substance finally carries out solvent replacement with dehydrated alcohol to neutrality by centrifuge centrifuge washing under 8000 r/min revolving speed
To obtain the ethanol solution of graphene oxide；
S3: by step S2 graphene oxide ethanol solution and the nano particles such as aluminium nitride according to mass ratio be 5:1-1:1
Ratio column mixed, along with quality accounting 1% -10% KH550 coupling agent carry out ultrasound two hours, restored
Graphene oxide@nanoparticles solution；
S4: the molten liquid of matching of the graphene oxide@nano particle in step S3 is configured to graphene oxide mass concentration as 1 g/L
Solution, and restored under conditions of 80 DEG C with the hydrazine hydrate of 10 times of graphene oxide quality, after reduction two hours
To redox graphene@nanoparticles solution；And by resulting redox graphene@nanoparticles solution washed to
Ethyl alcohol is used after neutrality again, the low boiling point solvents such as acetone replace former solvent, and the filter cake washed passes through again under conditions of vacuum drying oven
It is dried, finally obtains dry redox graphene@nano particle filter cake, retell filter cake pulverizer, ball mill etc.
It crushes, finally obtains redox graphene-aluminium nitride nanometer, micron-sized powder particle；
S5: by the thermally conductive powder of graphene in step S4 according to the mass ratio of epoxychloropropane be 1:3-1:1 proportion into
Row is stirred, and is carried out ultrasound again after mixing and is removed interpore micro-bubble, and is added 0.1 times after being warming up to 90 DEG C and is rubbed
Sodium hydroxide initiation reaction is added after the bisphenol-A and a small amount of water of your ratio by several times, polymerize city epoxy resin, leads to again after the completion of polymerization
Crossing vacuum distillation removing, extra epoxychloropropane obtains final epoxy resin heat-conducting glue.
As another scheme of the invention, the advantages of this scheme, is to reduce the pre-treatment step of graphene, saves people
Work cost and time cost；The disadvantage is that, the degree of oxidation of graphene oxide is inadequate, well-proportioned cannot disperse long in a solvent
Coagulation phenomenon can be occurred by putting, and Gu needs now-making-now-using, there is certain limitation.
Contemplated above technical scheme through the invention, compared with prior art, emphasis of the present invention solve two compared with
Intractable problem:
First, the present invention by when the state of graphene oxide be all nano particle aluminium oxide, aluminium nitride, nitridation
The problem of boron carries out ultrasonic load, and the pure graphene reduction-state itself of effective solution is easy to reunite, Yi Juchen, simultaneously as by very
It scatter well, when being restored with reducing agents such as hydrazine hydrates, the phenomenon that reduction is also more obvious, and the speed being reduced also becomes
It is fast very much；
Second, the effectively thorny problem for solving nano-powder and can not being mixed into gel of the present invention, the especially present invention will
When finely dispersed nano heat-conductive powder obtained in the step S1 is added in epoxy chloropropionate alkane solvents by stirring, nano powder
Body can be infiltrated well, and the method that the latter passes through ultrasound again will also remain in powder and also arrange with the minute gas in solvent
It removes, to thoroughly solve the problems, such as air thermal resistance.
The to sum up low-gravity high-thermal-conductivity epoxy resin that the present invention is prepared by in-situ polymerization, it is relatively new in technical aspect,
It is operationally easy, in environmental-friendly aspect less pollution, it is conducive to environmentally friendly production.
Detailed description of the invention
Fig. 1 is to implement aluminium nitride load stereoscan photograph of the graphene oxide through hydrazine hydrate reduction, the lower right corner in example 1
Having a size of 1 micron.
Fig. 2 is after the different proportion for implementing to prepare in example 1 adds the epoxy resin cure that graphene in-situ polymerization obtains
Thermally conductive datagram.
Fig. 3 is that different nanometer powders load graphene fabricated in situ epoxy resin heat-conducting effect compares.
Fig. 4 is to implement to prepare the round pie sample after solidifying in example 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Specific implementation method is divided into two parts in the present invention, and first part is the preparation of graphene-heat-conducting type nanometer powder；
Second part is that in-situ polymerization forms heat-conduction epoxy resin after heat-conducting type nanometer powder is mixed with epoxy source material.
Graphene oxide in the present invention is prepared by improving hummer and routine hummer method method, needs to use
Instrument has: three mouthfuls of glass flasks, water-bath, reflux condensing tubes, mechanical stirring, supercentrifuge, and baking oven and Conventional glass are real
Test instrument etc.；The drug for needing to use has: analyzing potassium permanganate, the concentrated sulfuric acid, concentrated nitric acid, the hydrogen peroxide and 99.5% of pure rank
The different-grain diameter graphite powder of purity.Graphene oxide is obtained by chemistry redox method to be aoxidized through means such as centrifugations again
Graphene.
Nanoparticle size in the present invention is the thermally conductive powder within the scope of 60-600 nm, graphene oxide and nanometer
Grain obtains graphene complex conductive powder after reduction washing is dry after ultrasound, then after being mixed with epoxychloropropane with bisphenol-A hydrogen
The in-situ polymerizations such as sodium oxide molybdena obtain final epoxy heat-conducting resin；The instrument that need to be used has: ultrasonic washing instrument, vacuum drying oven,
Pressure-reduction filter device, pulverizer, vacuum distillation apparatus, thermally conductive DATA REASONING instrument and Conventional glass instrument etc..
The following are specific implementation examples
Implement example 1
A kind of preparation and method of graphene in-situ polymerization reinforced epoxy heat-conductive composite material, which is characterized in that this is compound
Material includes with redox graphene, aluminium nitride, epoxychloropropane, and bisphenol-A is raw material, after in-situ polymerization after being evaporated under reduced pressure
Obtain epoxide number be 46-55 E51 type heat-conduction epoxy resin, it is thermally conductive can be by 0.2 Wm-1·K-1It is increased to 2.6 Wm-1·K-1, and additive amount is only 40wt%.
A kind of preparation method that graphene in-situ polymerization reinforced epoxy is thermally conductive, follows the steps below:
S1: when being vigorously stirred, 5.0 g potassium peroxydisulfates, 5.0 g phosphorus pentoxides are sequentially added into the dense sulphur of 15.0 mL
In acid clear solution, oil bath heating weigh 10.0 g natural graphites and are carefully added into react 3 hours in mixed liquor and obtain to 80 DEG C
Blackish green mixture cools down 6 hours at room temperature；Slowly secondary water is added in said mixture and is diluted, is filtered, and use secondary water
Filtrate is washed till as neutrality；It is dried overnight in drier at room temperature, obtain graphite pre-oxidation object；
S2: it weighs the above-mentioned graphite pre-oxidation object of 10.0 g and is carefully added into the 1000 mL beakers for filling the 230 mL concentrated sulfuric acids
(being operated under ice-water bath), then 30.0 g potassium permanganate are weighed, (this process temperature is carefully added slowly in above-mentioned mixed liquor under stirring
Certain 20 DEG C of control or less), ice bath is removed, mixed liquor is transferred in 3000mL round-bottomed flask, utilizes oil bath control system temperature
At 35 DEG C, then it is stirred to react 2 hours；There is bubbling phenomenon in reaction process, with the progress of reaction, mixture gradually thickens,
This is because bubbling process is exactly the process of a concentration, system color green becomes taupe by black.It is carefully added into after 2 hours
460 mL secondary waters obtain yellowish-brown dirty solution, and brown is presented in the mixed liquor after dilution, 1400 mL are added after 15 minutes bis- times
Water is then slowly added into 25 mL hydrogen peroxide (30 %), generates a large amount of bubbles, and after reaction, mixed liquor becomes glassy yellow muddiness
Liquid；It filters after cooling and is washed with 2500 mL(1:10) hydrochloric acid, and be stored in ethanol solution stand-by；
S3: by the ethanol solution of graphene oxide according to graphene: the mass ratio of aluminium nitride is that the ratio of 3:1-1:1 is mixed
The coupling agent for adding the KH550 of the 1-10% of aluminium nitride and graphene gross mass after conjunction again carries out ultrasonic treatment 2-4 hours, so that
Aluminium nitride can be loaded completely and be mixed with graphene oxide, just obtain AlN-GO solution after ultrasound；
S4: the solution for being 1g/L at graphene oxide content by AlN-GO solution allocation, and 10- is added in 80 DEG C of environment
The hydrazine hydrate of 20 times of graphene oxide quality is restored, and juvenescence is that solution becomes pitch-dark completely in 1-5 minutes, at 80 DEG C
Lower reduction obtains AlN-RGO solution after two hours, and by decompression filtering and washing to neutrality, obtained filter cake uses acetone, second again
The low boiling point solvents such as alcohol are replaced, and new filter cake is obtained, and new filter cake is placed in vacuum drying oven at 30-60 DEG C, 0.08 negative big
It is 24 hours dry under air pressure, AlN-RGO filter cake is obtained, then by ball mill, filter cake is crushed to several microns by the devices such as pulverizer
It is stand-by after rank；
S5: taking epoxychloropropane to be stirred with AlN-RGO, and mixed mass ratio is AlN-RGO: theoretical epoxy is 1:3-1:
Between 2, after the bisphenol-A dissolution of 10wt% epoxychloropropane is added after being warming up to 90 DEG C again after stirring by mixing, gradually divide
It criticizes and NaOH progress initiated polymerization is added, to which dark brown solution to be passed through to vacuum distillation again after mixing evenly after reaction,
Extra epoxychloropropane distillation is walked, and is recycled, the epoxide number for obtaining brown or black is the epoxy resin of 46-55；
S6: taking out the heat-conduction epoxy resin of black and the curing agent of 10wt% is added, and stirs evenly after adding curing agent, after degassing
Mold is poured into, is solidified 24 hours at room temperature, the sample after being solidified takes sample in TC3000E transient heat conduct test equipment
On tested.
Graphene oxide in step S4 be reduced after electromicroscopic photograph, as shown in Fig. 1, particle as we can see from the figure
It is evenly distributed in inside netted graphene, has effectively obstructed the reunion of graphene itself, restored to ensure that
Graphene is in nanoscale, is conducive to subsequent reactions.
Cured dose of solidification rear surface of round pie sample in step S6 is flat and smooth, and internal almost bubble-free exists, tool
Body is as shown in figure 3, be clear that surface is smooth.
Sample after solidifying in step S6 has obtained Different adding amount graphene in-situ polymerization after conductivity instrument is tested
Heat-conduction epoxy resin afterwards obtains thermal conductivity from original 0.2Wm-1·K-1It has been increased to highest 2.6Wm-1·K-1, specifically
Variation as shown in Fig. 2, Cong Tuzhong it may be seen that with graphene addition, it is evident that improve leading for epoxy resin
Heating rate greatly increases application of the epoxy resin in terms of electron pouring sealant.
Implement example 2
A kind of preparation and method of graphene in-situ polymerization reinforced epoxy heat-conductive composite material, which is characterized in that this is compound
Material includes with redox graphene, boron nitride, epoxychloropropane, and bisphenol-A is raw material, after in-situ polymerization after being evaporated under reduced pressure
The E51 type heat-conduction epoxy resin that epoxide number is 46-55 is obtained, when the additive amount of heat conductive graphite powder accounts for gross mass 30%, thermal conductivity
1.8 Wm can be reached-1·K-1。
A kind of preparation and method of graphene in-situ polymerization reinforced epoxy heat-conductive composite material, according to the following steps:
S1: 1000mL beaker is put into mixture of ice and water, and the concentrated sulfuric acid of 110mL is added into beaker, and is put in beaker
Enter magneton, open agitating device, controlling the temperature in beaker is 0 DEG C or so, and the 30 μm of expanded graphites and 2.5g nitric acid of 5g are added
Sodium, after stirring 8min, stirring while be slowly added to the potassium permanganate of 15g, continue to stir, react 30min, at this time solution
Color purple green will be presented, temperature is raised to 45 DEG C, after reacting 60min, the distilled water of 250mL is slowly added into, is warming up to 95
DEG C, it is stirred continuously hydrolysis 1h, the color reacted at this time is in glassy yellow, and the H of 8mL is slowly added in stirring2O2(30%) it handles, instead
Mixed processing is carried out after answering and with 5% hydrochloric acid volume 1:1, then several times with distilled water centrifuge washing, until pH is in
It is saved backup after property with ethanol replacement；
S2: the ethanol solution of graphene oxide is according to graphene: the mass ratio of boron nitride is that the ratio of 3:1-1:1 is mixed
The coupling agent for adding the KH550 of the 1-10% of boron nitride and graphene gross mass again afterwards carries out ultrasonic treatment 2-4 hours, so that nitrogen
Changing boron can completely load and mix with graphene oxide, just obtain BN-GO solution after ultrasound；
S3: the solution for being 1g/L at graphene oxide content by BN-GO solution allocation, and 10- is added in 80 DEG C of environment
The hydrazine hydrate of 15 times of graphene oxide quality is restored, and obtains BN-RGO solution after restoring two hours at 80 DEG C, and pass through
Filtering and washing is depressurized to neutrality, obtained filter cake uses acetone again, and the low boiling point solvents such as ethyl alcohol are replaced, and obtains new filter cake, will
New filter cake is placed in vacuum drying oven drying 24 hours at 30-60 DEG C, obtains BN-RGO filter cake, then will by devices such as pulverizers
Filter cake is crushed to after several micron levels for use；
S4: BN-RGO powder and theoretical epoxy resin quality are added in epoxychloropropane than the ratio for 1:2-1:3 and passed through
Ultrasound removes excessive gas again after being uniformly mixed, then the bisphenol-A of 10wt% epoxychloropropane is added after being warming up to 90 DEG C, complete
NaOH is gradually added portionwise after fully dissolved and carries out initiated polymerization, to after reaction by dark brown solution after mixing evenly again
By vacuum distillation, extra epoxychloropropane distillation is walked, and is recycled, the epoxide number for obtaining brown or black is 46-55
Epoxy resin；
S5: taking out the heat-conduction epoxy resin of black and the curing agent of 10wt% is added, and stirs evenly after adding curing agent, after degassing
Mold is poured into, is solidified 24 hours at room temperature, the sample after being solidified takes sample in TC3000E transient heat conduct test equipment
On tested.
S6: it obtains the thermally conductive powder of sample graphene to account for 30wt% to measure thermal coefficient after forming a film being 1.8Wm-1·K-1。
Implement example 3
A kind of preparation and method of graphene in-situ polymerization reinforced epoxy heat-conductive composite material, which is characterized in that this is compound
Material includes with redox graphene, aluminium oxide, epoxychloropropane, and bisphenol-A is raw material, after in-situ polymerization after being evaporated under reduced pressure
The E51 type heat-conduction epoxy resin that epoxide number is 46-55 is obtained, when the additive amount of heat conductive graphite powder accounts for gross mass 30%, thermal conductivity
1.6 Wm can be reached-1·K-1。
A kind of preparation and method of graphene in-situ polymerization reinforced epoxy heat-conductive composite material, according to the following steps:
S1: 1000mL beaker is put into mixture of ice and water, and the concentrated sulfuric acid of 110mL is added into beaker, and is put in beaker
Enter magneton, open agitating device, controlling the temperature in beaker is 0 DEG C or so, and the 30 μm of expanded graphites and 2.5g nitric acid of 5g are added
Sodium, after stirring 8min, stirring while be slowly added to the potassium permanganate of 15g, continue to stir, react 30min, at this time solution
Color purple green will be presented, temperature is raised to 45 DEG C, after reacting 60min, the distilled water of 250mL is slowly added into, is warming up to 95
DEG C, it is stirred continuously hydrolysis 1h, the color reacted at this time is in glassy yellow, and the H of 8mL is slowly added in stirring2O2(30%) it handles, instead
Mixed processing is carried out after answering and with 5% hydrochloric acid volume 1:1, then several times with distilled water centrifuge washing, until pH is in
It is saved backup after property with ethanol replacement；
S2: the ethanol solution of graphene oxide is according to graphene: the mass ratio of aluminium oxide is that the ratio of 3:1-1:1 is mixed
The coupling agent for adding the KH550 of the 1-10% of aluminium oxide and graphene gross mass again afterwards carries out ultrasonic treatment 2-4 hours, so that oxygen
Changing aluminium can completely load and mix with graphene oxide, just obtain Al after ultrasound2O3- GO solution；
S3: by Al2O3The solution that-GO solution allocation is 1g/L at graphene oxide content, and be added in 80 DEG C of environment
The hydrazine hydrate of 10-15 times of graphene oxide quality is restored, and obtains Al after restoring two hours at 80 DEG C2O3- RGO solution, and
By decompression filtering and washing to neutrality, obtained filter cake uses acetone again, and the low boiling point solvents such as ethyl alcohol are replaced, newly filtered
New filter cake is placed in vacuum drying oven drying 24 hours at 30-60 DEG C, obtains Al by cake2O3- RGO filter cake, then pass through pulverizer
Filter cake is crushed to after several micron levels for use by equal devices；
S4: by Al2O3- RGO powder and theoretical epoxy resin quality are added in epoxychloropropane than the ratio for 1:2-1:3 to be led to
Ultrasound removing excessive gas again is crossed after being uniformly mixed, then the bisphenol-A of 10wt% epoxychloropropane is added after being warming up to 90 DEG C,
Gradually be added portionwise after being completely dissolved NaOH carry out initiated polymerization, to after reaction by dark brown solution after mixing evenly
Again by vacuum distillation, extra epoxychloropropane distillation is walked, and is recycled, the epoxide number for obtaining brown or black is 46-
55 epoxy resin；
S5: taking out the heat-conduction epoxy resin of black and the curing agent of 10wt% is added, and stirs evenly after adding curing agent, after degassing
Mold is poured into, is solidified 24 hours at room temperature, the sample after being solidified takes sample in TC3000E transient heat conduct test equipment
On tested.
S6: it obtains the thermally conductive powder of sample graphene to account for 30wt% to measure thermal coefficient after forming a film being 1.6Wm-1·K-1。
Claims (10)
1. a kind of graphene in-situ polymerization reinforced epoxy, which is characterized in that including with redox graphene, aluminium nitride,
Epoxychloropropane and bisphenol-A are raw material, obtain the E51 type heat conduction ring that epoxide number is 46-55 after in-situ polymerization after being evaporated under reduced pressure
Oxygen resin.
2. a kind of preparation method of graphene in-situ polymerization reinforced epoxy, includes the following steps:
S1: with 325 mesh graphite powders in P2O5And K2S2O8Under the action of be pre-oxidized, again with hummer method after washing is dry
Graphene oxide is prepared, and is saved in dehydrated alcohol or acetone；
S2: the step S1 is obtained into graphene oxide solution and is ultrasonically treated with aluminium nitride, aluminium oxide and boron nitride, directly
Stop ultrasound without solid particle to beaker bottom, obtains nano particle@GO dispersion liquid；
S3: the nano particle@GO dispersion liquid that the step S2 is obtained is placed in flask, after heating with hydrazine hydrate be reduction
Agent restores nano particle@GO dispersion liquid, be added hydrazine hydrate after solution can within half a minute from ecru become brown or
Black, juvenescence is obvious, sufficiently obtains the compound of redox graphene@nano particle after reduction；
S4: the nano particle@RGO dispersion liquid that the step S3 is obtained is filtered with pressure-reduction filter device, after suction filtration
Composite material ethyl alcohol or acetone in carry out displacement washing after be dried to obtain in the vacuum drying oven of thermophilic low pressure
Conductive powder is further smashed the powder after drying using wall-breaking machine, pulverizer and ball mill；
S5: the nano particle@RGO powder that the step S4 is obtained being stirred with epoxychloropropane and is mixed, and is added after heating
Enter bisphenol-A and NaOH initiation reaction is added, finally obtains the mixture of epoxy resin and epoxychloropropane, and pass through vacuum distillation
Unreacted epoxychloropropane is recycled, high thermal conductivity in-situ polymerization heat-conduction epoxy resin is obtained.
3. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that S1
Graphite powder processing method in step: 2.5g potassium peroxydisulfate, 2.5g phosphorus pentoxide are sequentially added into 7.mL in whipping process
In the concentrated sulfuric acid clear solution, oil bath heating weigh 5 5.g natural graphites and are added in mixed liquor and react 3 hours and obtain to 80 DEG C
Blackish green mixture cools down 6 hours at room temperature；Slowly secondary water is added in said mixture and is diluted, is filtered, and use secondary water
Filtrate is washed till as neutrality；It is dried overnight in drier at room temperature, obtain graphite pre-oxidation object.
4. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that
Hummer method in S1 step includes the following steps: to weigh the above-mentioned graphite pre-oxidation object of 1.0 g and is carefully added into that fill 23 mL dense
It is operated under ice-water bath in 1000 mL beakers of sulfuric acid, then weighs 3.g potassium permanganate, be carefully added slowly under stirring above-mentioned mixed
It closes in liquid (this process temperature centainly controls 20 DEG C or less), removes ice bath, mixed liquor is transferred in 250 mL round-bottomed flasks, utilize
Then oil bath control system temperature is stirred to react 2 hours at 35 DEG C；There is bubbling phenomenon in reaction process, with the progress of reaction,
Mixture gradually thickens, this is because bubbling process is exactly the process of a concentration, system color green becomes taupe by black；
It is carefully added into 46 mL secondary waters after 2 hours and obtains yellowish-brown dirty solution, the mixed liquor presentation brown after dilution, 15 minutes
After add 140 mL secondary waters, be then slowly added into 2.mL(1 mL hydrogen peroxide (30 %), generate a large amount of bubbles, reaction terminates
Afterwards, mixed liquor becomes glassy yellow dirty solution；It filters after cooling and is washed with 250 5:10) hydrochloric acid, and be stored in ethanol solution
In it is stand-by.
5. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that S2
The ethanol solution of aluminium nitride, aluminium oxide and boron nitride nanometer particle and graphene oxide in step is according to graphene: nanometer
The mass ratio of grain adds the KH550 of the 1-10% of quality accounting again coupling agent after being mixed for the ratio of 1:5-1:1 is surpassed
Sonication 2-4 hours, nano particle is enabled completely to load and mix with graphene oxide, is just received after ultrasound
Rice grain@GO solution.
6. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that S3
Graphene oxide@nanoparticles solution in step is configured to the solution that graphene oxide content is 1g/L, and in 80 DEG C of ring
The hydrazine hydrate that 10-20 times of graphene oxide quality is added in border is restored, and juvenescence is that solution becomes completely in 1-5 minutes
It is pitch-dark, redox graphene@nanoparticles solution is obtained after restoring two hours at 80 DEG C.
7. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that S4
For redox graphene@nanoparticles solution in step by decompression filtering and washing to neutrality, obtained filter cake uses acetone again
Or ethyl alcohol is replaced, and new filter cake is obtained, and new filter cake is placed in vacuum drying oven drying 24 hours at 30-60 DEG C, is gone back
Former graphene oxide@nano particle filter cake, then be crushed to filter cake after micron order for use by ball mill, pulverizer.
8. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that S5
Epoxychloropropane in step is stirred with graphene complex, and mixed mass ratio is graphene complex: epoxy chloropropionate
Alkane is warming up to after 90 DEG C again after stirring by mixing and NaOH initiated polymerization is gradually added portionwise between 1:3-1:1,
To which after reaction by dark brown solution after mixing evenly again by vacuum distillation, extra epoxychloropropane distillation is walked, and
Recycling, the epoxide number for obtaining brown or black is the epoxy resin of 46-55.
9. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that S5
In-situ polymerization heat-conduction epoxy resin and curing agent obtained in step are according to quality than resin: curing agent is 10:1's or 8:1
Ratio is added, and 20 minutes degassing process are carried out after curing agent is added, after pour into mold cured.
10. as right 2 requires a kind of preparation method of graphene in-situ polymerization reinforced epoxy, which is characterized in that
Curing agent is ethylenediamine, diethylenetriamine, triethylene tetramine, cyanamide class or aromatic amine curing agent in S5 step.
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| CN110527406A (en) * | 2019-10-11 | 2019-12-03 | 深圳天元羲王材料科技有限公司 | Graphene water-based anticorrosive paint and preparation method thereof |
| CN114425269A (en) * | 2022-01-26 | 2022-05-03 | 武汉纺织大学 | Efficient oil-water separation composite foam based on surface engineering and preparation method thereof |
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| CN114214057B (en) * | 2022-02-22 | 2022-05-31 | 中国石油大学(华东) | Preparation method of self-phase-change propping agent based on emulsified toughened bio-based epoxy resin |
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