CN104231633B - A kind of graphene organic siliconresin conducing composite material - Google Patents
A kind of graphene organic siliconresin conducing composite material Download PDFInfo
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- CN104231633B CN104231633B CN201410547858.XA CN201410547858A CN104231633B CN 104231633 B CN104231633 B CN 104231633B CN 201410547858 A CN201410547858 A CN 201410547858A CN 104231633 B CN104231633 B CN 104231633B
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Abstract
The present invention relates to a kind of graphene organic siliconresin conducing composite material, belong to conductive material technical field.Graphene organic siliconresin conducing composite material of the present invention is added to ground and mixed in ball mill by graphene and methyl phenyl silicone resin and is uniformly made, and described graphene and the weight ratio of methyl phenyl silicone resin are 1:20~500.The present invention's causes organic siliconresin to become conductive from insulation, the good electric conductivity of so existing graphene, there are organic siliconresin remarkable weatherability and heat resistance again, and be methyl phenyl silicone resin and specific proportioning present invention employs specific organic siliconresin, further improve weatherability and heat resistance, and it is easy to solidification, it can be used in preparing the conductive materials such as electrically-conducting paint, conducting film.In addition, the graphene organic siliconresin conducing composite material preparation method of the present invention is simple, it is adapted to industrialized production, effectively save energy consumption, reduces cost.
Description
Technical field
The present invention relates to a kind of conducing composite material, it is more particularly related to a kind of graphene organic siliconresin
Conducing composite material, belongs to conductive material technical field.
Background technology
Organic siliconresin is a kind of thermosetting resin with highly cross-linked network structure.Its most prominent performance is excellent
Different thermo oxidative stability and excellent electrical insulation capability.In addition, silicones also there is remarkable moisture resistance, waterproof, it is cold-resistant, resistance to smelly
The weather resistances such as oxygen, but solvent-proof poor-performing.Therefore, organic siliconresin is mainly for the preparation of insulated paint, hydrophobic coating etc..
It is but also most hard nano material that graphene, which is currently world most thin, and it is almost fully transparent, is only absorbed
2.3% light；Thermal conductivity factor is up to 5300W/mK, higher than CNT and diamond, and its electron mobility exceedes under normal temperature
15000cm2/Vs, it is higher than CNT or silicon crystal, and resistivity about 10-6 Ω cm, it is lower than copper or silver, it is current
The minimum material of world resistivity.Just because of its resistivity is extremely low, the speed of electron transfer is exceedingly fast, and graphene is to lead in the world
Electrically best material, according to its excellent electric conductivity, makes it also have huge application potential in microelectronic.Graphene
It is possible to that the substitute of silicon can be turned into, manufactures ultra micro transistor npn npn, for producing the supercomputer in future, carbon is higher
Electron mobility can make the computer in future obtain higher speed.
The coating that organic siliconresin is applied into electronics industry etc. haves the shortcomings that one very big is exactly that electric conductivity is poor, pole
The earth limits it and uses scope.The electric conductivity performance of silicon resin coating is improved by adding conductive filler, the most frequently used fills out
Material is copper, silver etc., but addition is big.
Application No. 201310546799.X Chinese patent discloses a kind of heat resistant and wear resistant graphene and its preparation side
Method；The Chinese patent of Application No. 201310102556.7 discloses high-performance water-based graphene conductive coating and its preparation side
Method；The Chinese patent of Application No. 201210067339.4 discloses a kind of preparation of polyethylene/graphene conductive composite material
Method；The Chinese patent of Application No. 200910200630.2 discloses poly organic polysulfide thing/sulfonated graphene conductive and is combined
The preparation method of material.The conductive material of some graphenes is aforementioned patents disclosed, but does not possess good weather resistance.
State Intellectual Property Office discloses a Publication No. CN102925100A, a kind of entitled " height in 2013.2.13
The patent of invention of heat conductivility conductive silver glue and preparation method thereof ", the patent be related to a kind of High-thermal conductivity conductive silver adhesive and its
Preparation method, the conductive silver glue is made up of the raw material of following percentage by weight：Organic siliconresin or epoxy resin 14~28, solidification
Agent 0.14~1.4, graphene 0.5~1, conductive filler 70~85, diluent 0.15~1.5, reinforcing agent 0.05~1；Preparation side
Method is as follows：(1) organic siliconresin or epoxy resin are mixed with curing agent, matrix resin is made；(2) by graphite and organic solvent
After mixing, centrifugation, distillation obtain graphene solution；(3) conductive filler, graphite weak solution and organic solvent are mixed, centrifuged, done
It is dry, obtain the mixture of conductive filler and graphene；(4) mixture of conductive filler and graphene and matrix resin are passed through three
Roller mill is mixed, and adds diluent, reinforcing agent, produces conductive silver glue.Compared with prior art, the high thermal conductivity of the invention
Conductive silver glue has higher conductance, also with very high thermal conductivity, and the maximum operation (service) temperature of the conductive silver glue of the present invention
300 DEG C can be reached.
State Intellectual Property Office discloses a Publication No. CN102925099A in 2013.2.13, and entitled " one kind changes
The patent of invention of property cupric powder conductive adhesive and preparation method thereof ", the patent is related to conducting resinl technical field, is that prior art is changed
Enter, and in particular to a kind of modified cupric powder conductive adhesive and preparation method thereof, its percentage by weight (%) is：2~8% curing agent, 1.0~
10.0% diluent, 0.05~3.5% accelerator, 0.01~1% plasticizer, 15~45% graphenes are modified copper powder, remaining is organic
Silicones, each Ingredients Weight sum is 100%.Graphene is modified the addition of copper powder and organic siliconresin, makes the invention compared to existing
There is technology, with performances such as more preferable electric conductivity, hygroscopicity, anti-silver migrations, and material cost greatly reduces.Dive in the invention market
Power is big, and practicality is good.
Above-mentioned two pieces patent discloses two kinds of conducting resinls, is a kind of rubber, applies thickness, and quality weight is unsuitable for most of need
Want to apply in the case of frivolous material；And conducting resinl needs addition curing agent and accelerator to reach solidification purpose, uses
It is comparatively laborious；In addition, the heat resistance of above two conducting resinl is still bad.
The content of the invention
It is an object of the invention to overcome the shortcomings of that there is provided a kind of graphene organic siliconresin conduction is compound in prior art
Material, the conducing composite material weather resistance is good, and electric conductivity is excellent, while heat resistance is good, it is easy to solidify, be widely used.
In order to realize foregoing invention purpose, technical scheme is as follows：
A kind of graphene organic siliconresin conducing composite material, it is characterised in that：Described graphene organic siliconresin is led
Composite is added to ground and mixed in ball mill by graphene and methyl phenyl silicone resin and is uniformly made, described graphene
Weight ratio with methyl phenyl silicone resin is 1:20~500.
The time of ground and mixed of the present invention is 3~5 hours.
Methyl phenyl silicone resin of the present invention is made by following methods：
A, 20~40 parts of butyl acetate, 40~60 parts of toluene, 500~780 parts of water, phenyl trichlorine are weighed according to parts by weight
75~95 parts of silane, 50~70 parts of diphenyl dichlorosilane, 10~18 parts of dimethyldichlorosilane, methyl trichlorosilane 10~15
Part, 300~380 parts of dimethylbenzene；
B, the butyl acetate for now weighing step A, toluene and water are added in reactor, are well mixed, are obtained mixture
A；Phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane and dimethylbenzene are mixed equal again
It is even, obtain mixture B；
C, the mixture B in step B is added in the reactor equipped with mixture A, stirring reaction obtains hydrolysate；
Hydrolysate is washed to neutrality, 0.008~0.05% TMAH of hydrolysate quality is added after cooling, polycondensation is anti-
Acid adding is neutralized to neutrality after answering, and redistillation to solid content is 50%（Mass fraction）Transparent methyl phenyl silicone resin solution, cooling
It is 20% to add dimethylbenzene afterwards and be diluted to solid content（Mass fraction）Methyl phenyl silicone resin solution.
The present invention is in step C, and the mixture B in the B by step, which is added in the reactor equipped with mixture A, is
Mixture B in step B was added in the reactor equipped with mixture A by finger in 3~6 hours.
The present invention is in step C, and described stirring reaction obtains hydrolysate and refers to stirring reaction 30~60 minutes, obtains
Hydrolysate.
The present invention is neutralized in step C, after described polycondensation reaction refers to 40~80 points of polycondensation reaction at 30~50 DEG C
Neutralized after clock.
The present invention is in step C, and described distillation refers to distill under the conditions of pressure is -0.05~-0.08MPa.
Graphene organic siliconresin conducing composite material of the present invention answering in conducting film and electrically-conducting paint is prepared
With.
The present invention has advantages below compared with prior art：
1st, a kind of graphene organic siliconresin conducing composite material of the invention is by graphene and methyl phenyl silicone resin knot
Close, graphene resistivity only has about 10~6 Ω cm, it is lower than copper or silver, it is the minimum material of current resistivity so that organic
Silicones becomes conductive from insulation, the good electric conductivity of so existing graphene, there is the remarkable weatherability of organic siliconresin again
And heat resistance, and be methyl phenyl silicone resin and specific proportioning present invention employs specific organic siliconresin, one is entered again
Step improves weatherability and heat resistance, and is easy to solidification, can be used in preparing the conductive materials such as electrically-conducting paint, conducting film.In addition,
The graphene organic siliconresin conducing composite material preparation method of the present invention is simple, suitable industrialized production, effectively save energy consumption,
Reduce cost.
2nd, methyl phenyl silicone resin of the invention is synthesized using specific method, the film forming of the synthesis of methyl phenyl silicones
Property and it is good with the compatibility of filler, so as to improve the film forming and cementability of conducing composite material of the present invention；Tetramethyl hydrogen
Amine-oxides are a kind of cationic catalysts, in the polycondensation process of methyl phenyl silicone resin, due to ion induction effect so that silicon
Silicone hydroxyl in alcohol molecule on the phenyl group substitution Si positions of electronegativity preferentially carries out condensation reaction, is lived so as to remain reaction
The higher silicone hydroxyl of property.By controlling polycondensation reaction temperature, time, with regard to that can obtain being more easy under normal temperature under surface drying, low temperature（70℃）
With regard to curable methyl phenyl silicone resin.
3rd, mixture B of the present invention in step C, the B by step, which is added in the reactor equipped with mixture A, is
Mixture B in step B was added in the reactor equipped with mixture A by finger in 3~6 hours.Pass through the above-mentioned process time
Selection, product configuration and performance can be made to point to the direction of high polymer design.Because reaction can produce a large amount of HCl, put simultaneously
Go out substantial amounts of heat；Simultaneously as reaction materil structure is different, its reaction rate is also differed, the hydrolysis speed of such as methyl trichlorosilane
Degree is more than phenyl trichlorosilane.Therefore, by the selection to the process time, using the specific addition time of the invention, it can make
The reaction of chlorosilane monomer is carried out in atent solvent, is conducive to controlling and making the structure distribution of product equal for reaction temperature
It is even, so that the performance of product is more stablized.
4th, the present invention is in step C, and described stirring reaction obtains hydrolysate and refers to stirring reaction 30~60 minutes, obtains
To hydrolysate.The selection of above-mentioned specific stirring reaction time, is conducive to the regularity of the distribution of product structure.Because with reaction
Progress, the content of various materials is changing in reactor, and therefore, the product of different time sections is also to be not quite similar
's.The selection of above-mentioned specific mixing time, one can make reaction more abundant, secondly also can smoothly complete telomerization
Process.
5th, the present invention is neutralized in step C, after described polycondensation reaction refers to the polycondensation reaction 40~80 at 30~50 DEG C
Neutralized after minute.TMAH is the catalyst of high activity, high selectivity in the present reaction.Too low temperature can not be opened
Dynamic reaction, and too high temperature, can make runaway reaction, the selection of above-mentioned special process parameter both can guarantee that the progress of reaction again,
The extent of reaction can be preferably controlled again.And the specific polycondensation time can either ensure that reaction is complete, ensure that telomerization is abundant again.
6th, the present invention is in step C, and described distillation refers to distill under the conditions of pressure is -0.05~-0.08MPa.Subtract
The purpose of pressure distillation is thoroughly to steam the water produced by reaction, solid content is controlled, too low pressure can not make distillation
Complete；Too high pressure is then easily caused product and is carried over, or solvent is brought into surge tank even vavuum pump, so that not only unfavorable
In control solid content, equipment can be also damaged.The selection of above-mentioned specific distillation pressure is balanced very much, is conducive to controlling the yield of product
And solid content.
Embodiment
Embodiment 1
A kind of graphene organic siliconresin conducing composite material, described graphene organic siliconresin conducing composite material by
Graphene and methyl phenyl silicone resin are added to that ball mill is well mixed to be made, described graphene and methyl phenyl silicone resin
Weight ratio is 1:20.
On the basis of above-mentioned basic technical scheme, it is preferred that the time of described ground and mixed is 3 hours.
Embodiment 2
A kind of graphene organic siliconresin conducing composite material, described graphene organic siliconresin conducing composite material by
Graphene and methyl phenyl silicone resin are added to that ball mill is well mixed to be made, described graphene and methyl phenyl silicone resin
Weight ratio is 1:500.
On the basis of above-mentioned basic technical scheme, it is preferred that the time of described ground and mixed is 5 hours.
Embodiment 3
A kind of graphene organic siliconresin conducing composite material, described graphene organic siliconresin conducing composite material by
Graphene and methyl phenyl silicone resin are added to that ball mill is well mixed to be made, described graphene and methyl phenyl silicone resin
Weight ratio is 1:260.
On the basis of above-mentioned basic technical scheme, it is preferred that the time of described ground and mixed is 4 hours.
Embodiment 4
A kind of graphene organic siliconresin conducing composite material, described graphene organic siliconresin conducing composite material by
Graphene and methyl phenyl silicone resin are added to that ball mill is well mixed to be made, described graphene and methyl phenyl silicone resin
Weight ratio is 1:320.
On the basis of above-mentioned basic technical scheme, it is preferred that the time of described ground and mixed is 4.5 hours.
Embodiment 5
On the basis of embodiment 1-4：
Described methyl phenyl silicone resin is made by following methods：
A, 20 parts of butyl acetate, 40 parts of toluene, 500 parts of water, 75 parts of phenyl trichlorosilane, hexichol are weighed according to parts by weight
50 parts of base dichlorosilane, 10 parts of dimethyldichlorosilane, 10 parts of methyl trichlorosilane, 300 parts of dimethylbenzene；
B, the butyl acetate for now weighing step A, toluene and water are added in reactor, are well mixed, are obtained mixture
A；Phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane and dimethylbenzene are mixed equal again
It is even, obtain mixture B；
C, the mixture B in step B is added in the reactor equipped with mixture A, stirring reaction obtains hydrolysate；
Hydrolysate is washed to neutrality, 0.008% TMAH of hydrolysate quality is added after cooling, is added after polycondensation reaction
Acid is neutralized to neutrality, and redistillation to solid content is 50%（Mass fraction）Transparent methyl phenyl silicone resin solution, after cooling add
It is 20% that dimethylbenzene, which is diluted to solid content,（Mass fraction）Methyl phenyl silicone resin solution.
Embodiment 6
On the basis of embodiment 1-4：
Described methyl phenyl silicone resin is made by following methods：
A, 40 parts of butyl acetate, toluene 60,780 parts of water, 95 parts of phenyl trichlorosilane, diphenyl are weighed according to parts by weight
70 parts of dichlorosilane, 18 parts of dimethyldichlorosilane, 15 parts of methyl trichlorosilane, 380 parts of dimethylbenzene；
B, the butyl acetate for now weighing step A, toluene and water are added in reactor, are well mixed, are obtained mixture
A；Phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane and dimethylbenzene are mixed equal again
It is even, obtain mixture B；
C, the mixture B in step B is added in the reactor equipped with mixture A, stirring reaction obtains hydrolysate；
Hydrolysate is washed to neutrality, 0.05% TMAH of hydrolysate quality, acid adding after polycondensation reaction are added after cooling
Neutrality is neutralized to, redistillation to solid content is 50%（Mass fraction）Transparent methyl phenyl silicone resin solution, add two after cooling
Dilution with toluene to solid content is 20%（Mass fraction）Methyl phenyl silicone resin solution.
Embodiment 7
On the basis of embodiment 1-4：
Described methyl phenyl silicone resin is made by following methods：
A, 30 parts of butyl acetate, 50 parts of toluene, 640 parts of water, 85 parts of phenyl trichlorosilane, hexichol are weighed according to parts by weight
60 parts of base dichlorosilane, 14 parts of dimethyldichlorosilane, 13 parts of methyl trichlorosilane, 340 parts of dimethylbenzene；
B, the butyl acetate for now weighing step A, toluene and water are added in reactor, are well mixed, are obtained mixture
A；Phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane and dimethylbenzene are mixed equal again
It is even, obtain mixture B；
C, the mixture B in step B is added in the reactor equipped with mixture A, stirring reaction obtains hydrolysate；
Hydrolysate is washed to neutrality, 0.029% TMAH of hydrolysate quality is added after cooling, is added after polycondensation reaction
Acid is neutralized to neutrality, and redistillation to solid content is 50%（Mass fraction）Transparent methyl phenyl silicone resin solution, after cooling add
It is 20% that dimethylbenzene, which is diluted to solid content,（Mass fraction）Methyl phenyl silicone resin solution.
Embodiment 8
On the basis of embodiment 1-4：
Described methyl phenyl silicone resin is made by following methods：
A, 21 parts of butyl acetate, toluene 55,715 parts of water, 82 parts of phenyl trichlorosilane, diphenyl are weighed according to parts by weight
66 parts of dichlorosilane, 13 parts of dimethyldichlorosilane, 11 parts of methyl trichlorosilane, 365 parts of dimethylbenzene；
B, the butyl acetate for now weighing step A, toluene and water are added in reactor, are well mixed, are obtained mixture
A；Phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane and dimethylbenzene are mixed equal again
It is even, obtain mixture B；
C, the mixture B in step B is added in the reactor equipped with mixture A, stirring reaction obtains hydrolysate；
Hydrolysate is washed to neutrality, 0.001% TMAH of hydrolysate quality is added after cooling, is added after polycondensation reaction
Acid is neutralized to neutrality, and redistillation to solid content is 50%（Mass fraction）Transparent methyl phenyl silicone resin solution, after cooling add
It is 20% that dimethylbenzene, which is diluted to solid content,（Mass fraction）Methyl phenyl silicone resin solution.
Embodiment 9
On the basis of embodiment 5-8：
It is preferred that, in step C, the mixture B in the B by step is added in the reactor equipped with mixture A
Refer to the mixture B in step B being added in 3 hours in the reactor equipped with mixture A.
It is preferred that, in step C, described stirring reaction obtains hydrolysate and refers to stirring reaction 30 minutes, hydrolyzed
Thing.
It is preferred that, neutralized in step C, after described polycondensation reaction in referring at 30 DEG C after polycondensation reaction 40 minutes
With.
It is preferred that, in step C, described distillation refers to distill under the conditions of pressure is -0.08MPa.
Embodiment 10
On the basis of embodiment 5-8：
It is preferred that, in step C, the mixture B in the B by step is added in the reactor equipped with mixture A
Refer to the mixture B in step B being added in 6 hours in the reactor equipped with mixture A.
It is preferred that, in step C, described stirring reaction obtains hydrolysate and refers to stirring reaction 60 minutes, hydrolyzed
Thing.
It is preferred that, neutralized in step C, after described polycondensation reaction in referring at 50 DEG C after polycondensation reaction 80 minutes
With.
It is preferred that, in step C, described distillation refers to distill under the conditions of pressure is -0.05MPa.
Embodiment 11
On the basis of embodiment 5-8：
It is preferred that, in step C, the mixture B in the B by step is added in the reactor equipped with mixture A
Refer to the mixture B in step B being added in 4.5 hours in the reactor equipped with mixture A.
It is preferred that, in step C, described stirring reaction obtains hydrolysate and refers to stirring reaction 45 minutes, hydrolyzed
Thing.
It is preferred that, neutralized in step C, after described polycondensation reaction in referring at 40 DEG C after polycondensation reaction 60 minutes
With.
It is preferred that, in step C, described distillation refers to distill under the conditions of pressure is -0.065MPa.
Embodiment 12
On the basis of embodiment 5-8：
It is preferred that, in step C, the mixture B in the B by step is added in the reactor equipped with mixture A
Refer to the mixture B in step B being added in 5.5 hours in the reactor equipped with mixture A.
It is preferred that, in step C, described stirring reaction obtains hydrolysate and refers to stirring reaction 35 minutes, hydrolyzed
Thing.
It is preferred that, neutralized in step C, after described polycondensation reaction in referring at 48 DEG C after polycondensation reaction 50 minutes
With.
It is preferred that, in step C, described distillation refers to distill under the conditions of pressure is -0.07MPa.
Embodiment 13
In the prior art, usual organic siliconresin is mainly used as insullac and coating.Coating product mainly has heat-resisting
Coating, weather-resistant coating, water-repellent paint, hardening be wear-resisting and decorative paint etc..
In the prior art, to more than the research of graphene at conductive, heat-resisting two aspect, it is but multiple to graphene/organic siliconresin
The research of condensation material still belongs to blank.From technical background as can be seen that the excellent electric insulation of organic siliconresin is exactly itself preparation
One big barrier of electrically-insulating paint.Therefore, prepare that a kind of heat resistance, weather resistance are good, the excellent organosilicon tree of electric conductivity
Grease coating material is a conflicting technical barrier.
Graphene provided by the present invention/organic siliconresin conducing composite material, the conducing composite material include graphene,
Organic siliconresin, wherein organic siliconresin are methyl phenyl silicone resin, and the weight ratio of graphene and methyl phenyl silicone resin is 1:
20~500.
Graphene of the present invention/organic siliconresin conducing composite material is that graphene and methyl phenyl silicone resin are added into ball
Ground 3~5 hours in grinding machine, it is ensured that graphene is uniformly dispersed in methyl phenyl silicone resin, then packs.Above steps is equal
Carry out at normal temperatures and pressures.
Method of preparing methyl phenyl polysiloxane provided by the present invention is as follows：
A, by butyl acetate, toluene, water by weight 20~40：40~60：500~780 add in reactor, and mixing is equal
It is even；
B, by phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane, dimethylbenzene, press
Weight is than 75~95：50~70：10~18：10~15：300~380 are well mixed；
C, the mixture of gained in step B added into reactor reaction 30~60 minutes in 3~6 hours；
D, the static split-phase of hydrolysate by gained in step C, remove water layer, then are washed to neutrality, and cooling adds tetramethyl
Ammonium hydroxide, polycondensation reaction is neutralized after 40~80 minutes at 30~50 DEG C, then under the conditions of pressure is -0.05~-0.08MPa
Distillation to solid content is 50%（Mass fraction）Transparent methyl phenyl silicone resin solution, added after cooling dimethylbenzene be diluted to it is solid
Content is 20%（Mass fraction）Methyl phenyl silicone resin solution.
Graphene/the organic siliconresin provided by the present invention being somebody's turn to do is applied to the conducting film of high heat-resisting, weather-proof condition, conductive painting
Material, conducing composite material etc..
The present invention is when preparing methyl phenyl silicone resin, the R/Si values of use（The organic radix averagely connected on silicon atom）
And Ph/（Me+Ph）×100（Phenyl content）It is the basis for preparing methyl phenyl silicone resin.Aminomethyl phenyl silicon tree in the present invention
The R/Si values of fat are designed in 1.2~1.7, and when R/Si changes are small, the drying property of silicones improves, and hardness increase, thermal weight loss becomes
Small and thermoelasticity is deteriorated；And phenyl content is higher, condensation speed is slower, and epithelium is harder, but thermoplasticity is bigger.With regard to heat resistance
Speech, phenyl content is preferred with 20~60%.
TMAH is a kind of cationic catalyst, in the polycondensation process of methyl phenyl silicone resin, due to from
Sub- inductive effect so that the silicone hydroxyl in silanol molecule on the phenyl group substitution Si positions of electronegativity preferentially carries out being condensed instead
Should, so as to remain the higher silicone hydroxyl of reactivity.By controlling polycondensation reaction temperature, time, it is more easy to regard to normal temperature can be obtained
Surface drying, the conduction of graphene/methyl phenyl silicone resin of film forming, heat-resisting paint.
The present invention solves the consistency problem of graphene and organic siliconresin using ball-milling method, without using solvent
Method, Mechanical Method, ultrasonic method, are because compared to rear three kinds of methods, ball-milling method is low without VOC discharge, cost is further increased
And good dispersion effect can be reached, product has lower conductive threshold values, is more suitable for industrialized production.
Embodiment 14
By butyl acetate, toluene, water by weight 40：45：600 add in hydrolytic reaction pot, are well mixed；Again by phenyl
Trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane, dimethylbenzene, by weight 75：70：12：
12：After 380 is well mixed, the solution that was slowly added to turn one's coat in 4 hours is answered in kettle, stirring reaction 39 minutes；By the water obtained by reaction
The static split-phase of thing is solved, water layer is removed, then is washed to neutrality, cooling adds TMAH, and polycondensation reaction 1 is small at 40 DEG C
When after neutralize, then distill out under the conditions of pressure is -0.06MPa the mixed solvents such as toluene, further polycondensation to solid content is 50%
（Mass fraction）Transparent silicon resin solution, dimethylbenzene is added after cooling and is diluted to solid content for 20%（Mass fraction）Silicon tree
Lipoprotein solution.
Graphene, organic siliconresin are pressed 5：500 weight ratio adds grinding 3.5 hours in ball mill, then spout bag
Dress, is made graphene/organic siliconresin electrically-conducting paint.
Graphene/organic siliconresin electrically-conducting paint is brushed into the stainless steel substrates, aluminium flake, copper sheet in 120mm × 50mm respectively
On, placed 30 minutes under normal temperature, place into after being dried 2 hours at baking oven, 100 DEG C and take out.It is determined according to GB/T 1720-1979
Adhesive force is 1 grade, 1 grade, 1 grade respectively.
Graphene/organic siliconresin electrically-conducting paint is brushed into the epoxy sheet in three pieces of 50mm × 15mm × 2mm respectively
（Make tender by oneself）On, placed 30 minutes under normal temperature, place into after being dried 3 hours at baking oven, 70 DEG C and take out.With its electricity of multitester measuring
Resistance is 523 Ω, 518 Ω, 535 Ω respectively.
Embodiment 15
By butyl acetate, toluene, water by weight 25：60：650 add in hydrolytic reaction pot, are well mixed；Again by phenyl
Trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane, dimethylbenzene, by weight 90：60：12：
10：After 350 is well mixed, the solution that was slowly added to turn one's coat in 6 hours is answered in kettle, stirring reaction 30 minutes；By the water obtained by reaction
The static split-phase of thing is solved, water layer is removed, then is washed to neutrality, cooling adds TMAH, the polycondensation reaction 40 at 60 DEG C
Neutralized after minute, then distill out under the conditions of pressure is -0.05MPa the mixed solvents such as toluene, further polycondensation to solid content is
50%（Mass fraction）Transparent silicon resin solution, dimethylbenzene is added after cooling and is diluted to solid content for 20%（Mass fraction）Silicon
Resin solution.
Graphene, organic siliconresin are pressed 10：500 weight ratio adds grinding 5 hours in ball mill, then spout bag
Dress, is made graphene/organic siliconresin electrically-conducting paint.
Graphene/organic siliconresin electrically-conducting paint is brushed into the stainless steel substrates, aluminium flake, copper sheet in 120mm × 50mm respectively
On, placed 30 minutes under normal temperature, place into after being dried 2 hours at baking oven, 100 DEG C and take out.It is determined according to GB/T 1720~1979
Adhesive force is 1 grade, 1 grade, 1 grade respectively.
Graphene/organic siliconresin electrically-conducting paint is brushed into the epoxy sheet in three pieces of 50mm × 15mm × 2mm respectively
（Make tender by oneself）On, placed 30 minutes under normal temperature, place into after being dried 3 hours at baking oven, 70 DEG C and take out.With its electricity of multitester measuring
Resistance is 303 Ω, 298 Ω, 287 Ω respectively.
Embodiment 16
By butyl acetate, toluene, water by weight 40：50：780 add in hydrolytic reaction pot, are well mixed；Again by phenyl
Trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane, dimethylbenzene, by weight 95：60：15：
12：After 300 is well mixed, the solution that was slowly added to turn one's coat in 5 hours is answered in kettle, stirring reaction 60 minutes；By the water obtained by reaction
The static split-phase of thing is solved, water layer is removed, then is washed to neutrality, cooling adds TMAH, the polycondensation reaction 80 at 40 DEG C
Neutralized after minute, then distill out under the conditions of pressure is -0.08MPa the mixed solvents such as toluene, further polycondensation to solid content is
50%（Mass fraction）Transparent silicon resin solution, dimethylbenzene is added after cooling and is diluted to solid content for 20%（Mass fraction）Silicon
Resin solution.
Graphene, organic siliconresin are pressed 2.5：500 weight ratio adds grinding 3 hours in ball mill, then spout bag
Dress, is made graphene/organic siliconresin electrically-conducting paint.
Graphene/organic siliconresin electrically-conducting paint is brushed into the stainless steel substrates, aluminium flake, copper sheet in 120mm × 50mm respectively
On, placed 30 minutes under normal temperature, place into after being dried 2 hours at baking oven, 100 DEG C and take out.It is determined according to GB/T 1720~1979
Adhesive force is 1 grade, 1 grade, 1 grade respectively.
Graphene/organic siliconresin electrically-conducting paint is brushed into the epoxy sheet in three pieces of 50mm × 15mm × 2mm respectively
（Make tender by oneself）On, placed 30 minutes under normal temperature, place into after being dried 3 hours at baking oven, 70 DEG C and take out.With its electricity of multitester measuring
Resistance is 743 Ω, 782 Ω, 786 Ω respectively.
Claims (1)
1. a kind of graphene organic siliconresin conducing composite material, it is characterised in that：Described graphene organic siliconresin is conductive
Composite is added to ground and mixed in ball mill by graphene and methyl phenyl silicone resin and is uniformly made for 3~5 hours, described
The weight ratio of graphene and methyl phenyl silicone resin is 1:20~500；
Described methyl phenyl silicone resin is made by following methods：
A, 20~40 parts of butyl acetate, 40~60 parts of toluene, 500~780 parts of water, phenyl trichlorosilane are weighed according to parts by weight
75~95 parts, 50~70 parts of diphenyl dichlorosilane, 10~18 parts of dimethyldichlorosilane, 10~15 parts of methyl trichlorosilane,
300~380 parts of dimethylbenzene；
B, the butyl acetate for now weighing step A, toluene and water are added in reactor, are well mixed, are obtained mixture A；Again
Phenyl trichlorosilane, diphenyl dichlorosilane, dimethyldichlorosilane, methyl trichlorosilane and dimethylbenzene are well mixed, obtained
To mixture B；
C, the mixture B in step B was added in 3~6 hours in the reactor equipped with mixture A, stirring reaction 30~
60 minutes, obtain hydrolysate；Hydrolysate is washed to neutrality, 0.008~0.05% tetramethyl of hydrolysate quality is added after cooling
Base ammonium hydroxide, acid adding is neutralized to neutrality after polycondensation reaction 40~80 minutes at 30~50 DEG C, then pressure be -0.05~-
Distilled under the conditions of 0.08MPa to the transparent methyl phenyl silicone resin solution that solid content is 50%, dimethylbenzene is added after cooling and is diluted to
Solid content is 20% methyl phenyl silicone resin solution.
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| CN115139579A (en) * | 2022-06-15 | 2022-10-04 | 苏州泰吉诺新材料科技有限公司 | High-thermal-conductivity graphene/silica gel foam multilayer composite material and preparation method and application thereof |
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