CN106010148B - Highly conductive coating of silvering graphite olefinic carbon pipe compound resin and preparation method thereof - Google Patents
Highly conductive coating of silvering graphite olefinic carbon pipe compound resin and preparation method thereof Download PDFInfo
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- CN106010148B CN106010148B CN201610567265.9A CN201610567265A CN106010148B CN 106010148 B CN106010148 B CN 106010148B CN 201610567265 A CN201610567265 A CN 201610567265A CN 106010148 B CN106010148 B CN 106010148B
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a kind of highly conductive coating of silvering graphite olefinic carbon pipe compound resin and preparation method thereof, the highly conductive coating of silvering graphite olefinic carbon pipe compound resin is made up of each component of following quality proportioning, 5 ~ 15 parts of silvering graphite alkene；1 ~ 3 part of carbon pipe；20 ~ 60 parts of vinyl ester resin；1 ~ 2 part of coupling agent；Totally 1 ~ 3 part of lacquer type organic coating curing agent and lacquer type organic coating catalyst；Wherein lacquer type organic coating catalyst and lacquer type organic coating curing agent mass ratio are 2 ~ 4:1；20 ~ 60 parts of diluent.The present invention is that one kind possesses high conductivity, the heat-resisting weather-proof special functional coating of highly corrosion resistant.
Description
Technical field
The present invention relates to a kind of new function type composite coating, specially a kind of height of silvering graphite olefinic carbon pipe compound resin
Electrically-conducting paint and preparation method thereof, belong to technical field of coatings.
Background technology
With the high speed development of modern technologies, various new function paint industries also flourish therewith, particularly at certain
A little such as Aero-Space, Chemical Manufacture, building heat preservation, electromagnetic shielding, energy traffic specific application area, one kind need height to lead
Electricity, anti-corrosion, the new coating of anti-electromagnetic shielding are just increasingly causing the concern of people.
2004,Univ Manchester UKPhysicistAn DeliegaimuWithConstantine's Nuo Woxiao loves, into
Work(isolates graphene from graphite, it was demonstrated that therefore it can also obtain 2010 years Nobel's physics jointly with individualism, two people
Learn prize.Graphene has perfect two dimensional crystal structure, and its lattice is the hexagon surrounded by six carbon atom, thickness one
Individual atomic layer.Its electron mobility is more than 15000cm2/Vs, resistivity about 10 under normal temperature-6Ω cm, than copper or silver more
It is low, it is the minimum material of world resistivity.
The electric conductivity of electrically-conducting paint is determined by conductive filler, therefore the resistivity of filler turns into influence coatings conductive property
Key.At present, conductive filler mainly has metal and nonmetallic carbon material, and wherein metal is easier to that electrochemistry corruption occurs with soda acid
Erosion reaction, and density is big, addition is big, and cost is high, can not meet requirement.Therefore, by corrosion resistant carbon-based material
Turn into the focus of research as conductive filler.
At present, graphene simple composite resin, has applied for some patents of invention as a kind of anti-corrosion paint filler,
Such as number of patent application 201310300323.8 and 201210066163.0.But this only be merely add 1% or so amount can do
To obvious anti-corrosion lifting, but electric conductivity is not high.As electrically-conducting paint, grounding body aspect, only see and used using Nano graphite powder
In anti-corrosion application, such as number of patent application 201220675957.2.And it is used for grounding body also using graphene as conductive anti-corrosion coating
No.Invented in Application No. 201410112165.8, entitled " a kind of grounding body based on conductive nano corrosion-resistant coating "
In patent, its using CVD graphene layer as conductive film deposits on metallic matrix, the defects of very big be present in this way, into
This height, operability is poor, and graphene depositing base requires, and iron-based is with regard to improper.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide one kind to be provided simultaneously with high conductivity, high
Highly conductive coating of corrosion resistant silvering graphite olefinic carbon pipe compound resin and preparation method thereof.
The technical proposal of the invention is realized in this way：
The highly conductive coating of silvering graphite olefinic carbon pipe compound resin, is made up of, silver-plated stone each component of following quality proportioning
Black 5 ~ 15 parts of alkene；1 ~ 3 part of carbon pipe；20 ~ 60 parts of vinyl ester resin；1 ~ 2 part of coupling agent；Lacquer type organic coating curing agent and lacquer type organic coating catalysis
Totally 1 ~ 3 part of agent；Wherein lacquer type organic coating catalyst and lacquer type organic coating curing agent mass ratio are 2 ~ 4:1；20 ~ 60 parts of diluent.
The silvering graphite alkene is prepared as follows,
1）By 1g graphenes ultrasonic disperse in the strong alkali aqueous solution that 1L concentration is 0.2 ~ 1 mol/L, it is then heated to 80 ~
100 DEG C and kept for 0.5 ~ 2 hour, then with clear water washing and filtering, obtain the graphene after oil removing, roughening；
2）By step 1）Then the graphene dispersion being filtrated to get heats 10 ~ 30 into 1L sensitizing solution at 20 ~ 55 DEG C
Minute；The sensitizing solution is that stannic chloride, 4 ~ 7g/L sodium stannate and the 50 ~ 150mg/L hydrochloric acid that concentration is 20 ~ 30g/L are formed
Deionized water mixed solution；
3）The 2nd）0.5 ~ 1.5g activators palladium bichloride is added in step reaction system to heat 10 ~ 30 minutes at 45 DEG C；
4）By step 3）Reaction system filtering, by comprising the filtrate including graphene be distributed to 0.4L concentration for 0.1 ~
5 ~ 15 minutes in 0.3mol/L reducing solution；
5）By step 4）Reaction system filtering, filtrate input 500 ~ 1000mL silver ammino solutions in be slowly stirred 5 ~ 15 points
Clock；Ammoniacal liquor mass fraction is 15 ~ 30% in silver ammino solution, and silver nitrate concentration is 3.0~25.0g/L in silver ammino solution, and pH is
10.0~11.0；
6）The 5th）Walk in obtained reaction system and be added dropwise and step 4）Identical reducing solution and amount it is also identical, maintain temperature
25 ~ 30 DEG C of degree, until uniformly the silver layer of the bright silvery white of plating last layer, graphene are 1 with silver layer mass ratio on graphene:1~5；Cross
Filter and produce silvering graphite alkene.
The reducing solution is one or more of mixed solutions in glucose, sodium potassium tartrate tetrahydrate and tartaric acid.
The strong alkali aqueous solution is sodium hydroxide, a kind of aqueous solution or two kinds of mixed aqueous solution in potassium hydroxide.
The graphene is 2 ~ 20 micron order piece footpaths, less than 10 layers of graphene；The carbon pipe is more wall carbon pipes, caliber 5
~ 100nm, 0.1 ~ 50 μm of pipe range.
The coupling agent is silane coupling agent or titanate coupling agent；The lacquer type organic coating catalyst is blue water, lacquer type organic coating
Curing agent is plain boiled water；The diluent is styrene.
The silvering graphite alkene is 10 with carbon pipe mass ratio:2~3.
During preparation, vinyl ester resin and styrene are first hybridly prepared into the vinyl esters tree that mass concentration is 50 ~ 60%
Fat styrene solution；Again by silvering graphite alkene and carbon pipe ultrasonic disperse into vinyl ester resin styrene solution, then add idol
Join agent, then mixed 2 ~ 4 hours in ball milling or sand mill, is well mixed；Lacquer type organic coating catalyst and tree are sequentially added after taking-up
Fat paint curing agent, it is well mixed.
Compared with prior art, the present invention has the advantages that：
1st, because the contact interface resistance of graphene film is big, by the silver-plated electric conductivity that can improve macroscopic material, simultaneously
Coordinate the connection of stick-like highly conductive more wall carbon pipe enhancing conductive networks.Compared with existing product, silvering graphite alkene of the invention/
The highly conductive coating of carbon pipe compound ethylene base resin possesses high face electric conductivity, and surface resistance is less than 10 below Ω.
2nd, vinyl ester resin is heat-resisting weather-proof, and the degree of cross linking is high, and hardness is suitable, and viscosity is small, is well suited for the charcoal of compound high imbibition
It is conductive filler, while the requirement of high corrosion environment can be met.Compared with existing invention, silvering graphite alkene/carbon pipe of the present invention is answered
The highly conductive coating for closing vinylite possesses very strong decay resistance.
3rd, the highly conductive preparation method for coating science of silvering graphite alkene/carbon pipe compound ethylene base resin of the invention is feasible,
Practice operability is high, is suitable for the anti-corrosion environment of electromagnetic shielding.
4th, the highly conductive coating of silvering graphite alkene of the present invention/carbon pipe compound ethylene base resin possesses long-term resistance to 100 DEG C ring
Border tests, and conductive corrosion resistance does not decline substantially.
In summary, silvering graphite of the invention alkene/highly conductive coating of carbon pipe compound ethylene base resin is that one kind possesses height
Electric conductivity, the heat-resisting weather-proof special functional coating of highly corrosion resistant.
Brief description of the drawings
Silvering graphite alkene scanning electron microscope (SEM) photograph prepared by Fig. 1-embodiment 1.
Silvering graphite alkene scanning electron microscope (SEM) photograph prepared by Fig. 2-embodiment 2.
After the highly conductive coating sample preparation (a) of the preparation of Fig. 3-embodiment 1 and encapsulation（b）Outward appearance of the salt spray resistance after 1000 hours
Figure.
The preparation flow figure of Fig. 4-silvering graphite of the present invention alkene/highly conductive coating of carbon pipe compound ethylene base resin.
Embodiment
The highly conductive coating of silvering graphite olefinic carbon pipe compound resin of the present invention, is made up of each component of following quality proportioning,
5 ~ 15 parts of silvering graphite alkene；1 ~ 3 part of carbon pipe；20 ~ 60 parts of vinyl ester resin；1 ~ 2 part of coupling agent；Lacquer type organic coating curing agent and resin
Paint totally 1 ~ 3 part of catalyst；Wherein lacquer type organic coating catalyst and lacquer type organic coating curing agent mass ratio are 2-4:1；20 ~ 60 parts of diluent.
The coupling agent is silane coupling agent or titanate coupling agent；The lacquer type organic coating catalyst is blue water, lacquer type organic coating
Curing agent is plain boiled water；The diluent is styrene.
Preferably, the silvering graphite alkene and carbon pipe mass ratio are 10:2~3.The carbon pipe is more wall carbon pipes, caliber 5 ~
100nm, 0.1 ~ 50 μm of pipe range.
The highly conductive preparation method for coating of silvering graphite olefinic carbon pipe compound resin of the present invention, first by vinyl ester resin and benzene
Ethene is hybridly prepared into the vinyl ester resin styrene solution that mass concentration is 50 ~ 60%；Again using as the silver-plated of conductive filler
Graphene and carbon pipe ultrasonic disperse are into vinyl ester resin styrene solution, then add coupling agent, then in ball milling or sand milling
2-4 hours are mixed in machine, are well mixed；Lacquer type organic coating catalyst and lacquer type organic coating curing agent are sequentially added after taking-up, is well mixed i.e.
Can.Its preparation flow is referring to Fig. 4.
Wherein silvering graphite alkene is prepared as follows,
1）By 1g graphenes ultrasonic disperse in the strong alkali aqueous solution that 1L concentration is 0.2 ~ 1 mol/L, it is then heated to 80 ~
100 DEG C and kept for 0.5 ~ 2 hour, then with clear water washing and filtering, obtain the graphene after oil removing, roughening；The highly basic is water-soluble
Liquid is sodium hydroxide, a kind of aqueous solution or two kinds of mixed aqueous solution in potassium hydroxide.
2）By step 1）Then the graphene dispersion being filtrated to get heats 10 ~ 30 into 1L sensitizing solution at 20 ~ 55 DEG C
Minute；The sensitizing solution is that stannic chloride, 4 ~ 7g/L sodium stannate and the 50 ~ 150mg/L hydrochloric acid that concentration is 20 ~ 30g/L are formed
Deionized water mixed solution；
3）The 2nd）0.5 ~ 1.5g activators palladium bichloride is added in step reaction system to heat 10 ~ 30 minutes at 45 DEG C；
4）By step 3）Reaction system filtering, by comprising the filtrate including graphene be distributed to 0.4L concentration for 0.1 ~
5 ~ 15 minutes in 0.3mol/L reducing solution；
5）By step 4）Reaction system filtering, filtrate input 500 ~ 1000mL silver ammino solutions in be slowly stirred 5 ~ 15 points
Clock；Silver ammino solution is silver nitrateAmmoniacal liquorSolution, ammoniacal liquor mass concentration 15-30%, is titrated in silver nitrate solution with it, drop
Silver nitrate concentration is 3.0~25.0g/L before fixed, and system pH value is 10.0 ~ 11.0 after titration.
6）The 5th）Walk in obtained reaction system and be added dropwise and step 4）Identical reducing solution and amount it is also identical, maintain temperature
25 ~ 30 DEG C of degree, until uniformly the silver layer of the bright silvery white of plating last layer, graphene are 1 with silver layer mass ratio on graphene:1~5；Cross
Filter and produce silvering graphite alkene.
The reducing solution is one or more of mixed solutions in glucose, sodium potassium tartrate tetrahydrate and tartaric acid.
The graphene is 2 ~ 20 micron order piece footpaths, less than 10 layers of graphene；
The present invention when graphene is silver-plated, be the graphene dispersion that will be sensitized into reductant solution, then ultrasonic one
Filtered after the section time, the graphene slurry filtered is distributed to a period of time in silver ammino solution so that graphenic surface is advance
Slowly plating last layer silver particles.Then reducing agent is added dropwise according still further to certain proportion and speed.Because of graphenic surface now
Through there is nano silver particles to do nucleus, the silver-plated uniformity and silver-colored preferential deposition rate substantially increase.Though this method reduction rate
It is so slow, but waste less, coating is firm.Then it can also be gone back by the graphene dispersion being sensitized into silver ammino solution by what is prepared
Former agent solution is added drop-wise in silver ammino solution with speed according to a certain percentage.This reduction rate is fast, but wastes more, many silver reduction
Onto chamber wall.
The specific preparation embodiment of a silvering graphite alkene given below：By 100g graphene ultrasonic disperses in 0.5mol/L
1L sodium hydrate aqueous solutions in, then heat 80 ~ 100 DEG C keep 1 hour, then with clear water washing and filtering.Then gone with 1L
Ionized water prepares 20 ~ 30g/L stannic chloride, 6g/L sodium stannates, and the mixed solution of 100mg/L hydrochloric acid cooks sensitizing solution.It will filter out
The graphene dispersion come heats 45 DEG C up to 20 minutes into sensitizing solution, and then plus 1g palladium bichlorides continue heating 20 minutes.Then will
Graphene dispersion after filtering is into glucose reducing solution 10 minutes, then in filtering input 500 ~ 1000ml silver ammino solutions
（Wherein the mass fraction of ammoniacal liquor is 25%, adjusts 3.0~25.0g/L silver nitrate solution pH to 10.0~11.0）Slowly
Stirring 10 minutes.The reducing solution of mixing is finally added dropwise, and maintains 25 ~ 30 DEG C, until uniformly plating last layer light on graphene
The white silver layer of silver lustre.
The present invention is described in further detail below by embodiment and test result.
Embodiment 1
First silvering graphite alkene processed as follows：
By 10g graphenes ultrasonic disperse in the 0.5L aqueous solution of 0.5mol/L sodium hydroxide, 80 DEG C of guarantors are then heated
Hold 1 hour, then with clear water washing and filtering.Then with 0.5L deionized waters prepare 30g/L stannic chloride, 6g/L sodium stannates,
50mg/L hydrochloric acid（30%）Mixed solution cook sensitizing solution.By graphene dispersion into sensitizing solution, 45 DEG C up to 20 minutes are heated, so
Afterwards plus 0.5g palladium bichlorides continue heating 20 minutes.Then filter after graphene dispersion arrive to 200ml 20g/L glucose with
10 minutes in 200ml 30g/L sodium potassium tartrate tetrahydrate mixing reducing solutions, then in filtering input 800ml silver ammino solutions（Wherein ammonia
The mass fraction 25% of water, adjust 30.5g/L silver nitrate solution pH to 10.5）It is slowly stirred 10 minutes.Mixing is finally added dropwise
Reducing solution, and 28 DEG C are maintained, until the uniformly silver layer of the bright silvery white of plating last layer on graphene, filters and produce silver-plated stone
Black alkene.Fig. 1 is silvering graphite alkene scanning electron microscope (SEM) photograph prepared by embodiment 1.
Then composite electrically-conducting paint is prepared, is made as follows：
By silvering graphite alkene and 5g carbon pipes elder generation's ultrasonic disperse into the 60% of 110g vinyl ester resin styrene solution,
1.5g titanate coupling agents are added again, are then mixed 2.5 hours, are uniformly dispersed in ball milling or sand mill.Added after taking-up different
Cobalt octoate 4g stirs, and then adds 1g methyl ethyl ketone peroxides and stirs, produces electrically-conducting paint.
Electrically-conducting paint is sprayed on steel disc matrix, spontaneous curing can obtain high conductive coating after 4 hours.By made from
Sample uses cross cut test method, carries out adhesive force test by GB/T9286-1998, while sample is according to GB/T10125-2012
Salt spray test is carried out, as a result as shown in table 1.
The highly conductive coating property test result of the silvering graphite alkene of table 1/carbon pipe compound ethylene base resin
| Project | Salt spray resistance 1000h | Impact strength/cm | Adhesive force/level | Surface drying time/h | Do solid work the time/h | Surface resistance/Ω |
| As a result | It is intact | 50 | 1 | 4 | 24 | 9.0 |
Fig. 3 is the steel disc sample preparation (a) of the highly conductive coating of silvering graphite alkene/carbon pipe compound ethylene base resin prepared by this example
After encapsulation（b）Outside drawing of the salt spray resistance after 1000 hours.By figure it can be found that highly conductive anticorrosive paint prepared by the present invention exists
After 1000 hours standard salt spray tests, bubble-free, discoloration and obscission, antiseptic property are excellent.
Embodiment 2
First silvering graphite alkene processed as follows：
By 12g graphenes ultrasonic disperse in the 0.5L aqueous solution of 0.5mol/L potassium hydroxide, 80 DEG C of guarantors are then heated
Hold 1 hour, then with clear water washing and filtering.Then with 0.5L deionized waters prepare 30g/L stannic chloride, 6g/L sodium stannates,
50mg/L hydrochloric acid（30%）Mixed solution cook sensitizing solution.By graphene dispersion into sensitizing solution, 45 DEG C up to 20 minutes are heated, so
Afterwards plus 0.5g palladium bichlorides continue heating 20 minutes.Then the graphene dispersion after filtering is into 800ml silver ammino solutions（Wherein ammoniacal liquor
Mass fraction 25%, adjust 15.5g/L silver nitrate solution pH to 11）It is slowly stirred 10 minutes.40g/L is finally added dropwise dropwise
Sodium potassium tartrate tetrahydrate mixing reducing solution, and 38 DEG C are maintained, until the uniformly silver layer of the bright silvery white of plating last layer, mistake on graphene
Filter and produce silvering graphite alkene.Fig. 2 is silvering graphite alkene scanning electron microscope (SEM) photograph prepared by embodiment 2.
Then composite electrically-conducting paint is prepared, is made as follows：
By silvering graphite alkene and 5g carbon pipes elder generation's ultrasonic disperse into the 60% of 110g vinyl ester resin styrene solution,
1.5g titanate coupling agents are added again, are then mixed 2.5 hours, are uniformly dispersed in ball milling or sand mill.Added after taking-up different
Cobalt octoate 3g stirs, and then adds 1g methyl ethyl ketone peroxides and stirs, produces electrically-conducting paint.Then
Electrically-conducting paint is sprayed on steel disc matrix, spontaneous curing can obtain high conductive coating after 4 hours.By made from
Sample uses cross cut test method, carries out adhesive force test by GB/T9286-1998, while sample is according to GB/T10125-2012
Salt spray test is carried out, as a result as shown in table 2.
The highly conductive coating property test result of the silvering graphite alkene of table 2/carbon pipe compound ethylene base resin
| Project | Salt spray resistance 1000h | Impact strength/cm | Adhesive force/level | Surface drying time/h | Do solid work the time/h | Surface resistance/Ω |
| As a result | It is intact | 45 | 1 | 5 | 24 | 8.8 |
As a result show that coating property indices prepared by embodiment 2 are superior.
Embodiment 3
First silvering graphite alkene processed as follows：
By 12g graphenes ultrasonic disperse in the 0.5L aqueous solution of 0.5mol/L potassium hydroxide, 80 DEG C of guarantors are then heated
Hold 1 hour, then with clear water washing and filtering.Then with 0.5L deionized waters prepare 30g/L stannic chloride, 6g/L sodium stannates,
50mg/L hydrochloric acid（30%）Mixed solution cook sensitizing solution.By graphene dispersion into sensitizing solution, 45 DEG C up to 20 minutes are heated, so
Afterwards plus 0.5g palladium bichlorides continue heating 20 minutes.Then filter after graphene dispersion arrive to 200ml 20g/L glucose with
10 minutes in 300ml 30g/L sodium potassium tartrate tetrahydrate mixing reducing solutions, then in filtering input 1000ml silver ammino solutions（Wherein
The mass fraction 25% of ammoniacal liquor, adjust 20.5g/L silver nitrate solution pH to 10.5）It is slowly stirred 10 minutes.Finally it is added dropwise mixed
The reducing solution of conjunction, and maintain 28 DEG C, until the uniformly silver layer of the bright silvery white of plating last layer on graphene, filter produce it is silver-plated
Graphene.
Then composite electrically-conducting paint is prepared, is made as follows：
By silvering graphite alkene and 5g carbon pipes elder generation's ultrasonic disperse into the 60% of 110g vinyl ester resin styrene solution,
1.5g titanate coupling agents are added again, are then mixed 2.5 hours, are uniformly dispersed in ball milling or sand mill.Added after taking-up different
Cobalt octoate 3g stirs, and then adds 1g methyl ethyl ketone peroxides and stirs, produces electrically-conducting paint.
Electrically-conducting paint is sprayed on steel disc matrix, spontaneous curing can obtain high conductive coating after 4 hours.By made from
Sample uses cross cut test method, carries out adhesive force test by GB/T9286-1998, while sample is according to GB/T10125-2012
Salt spray test is carried out, as a result as shown in table 3.
The highly conductive coating property test result of the silvering graphite alkene of table 3/carbon pipe compound ethylene base resin
| Project | Salt spray resistance 1000h | Impact strength/cm | Adhesive force/level | Surface drying time/h | Do solid work the time/h | Surface resistance/Ω |
| As a result | It is intact | 50 | 1 | 5 | 24 | 7.8 |
As a result show that coating property indices prepared by embodiment 3 are superior.
The above embodiment of the present invention is only example to illustrate the invention, and is not the embodiment party to the present invention
The restriction of formula.For those of ordinary skill in the field, it is different that other can also be made on the basis of the above description
The change and variation of form, all embodiments can not be exhaustive here.It is every to belong to technical scheme institute
Row of the obvious changes or variations amplified out still in protection scope of the present invention.
Claims (6)
1. the highly conductive coating of silvering graphite olefinic carbon pipe compound resin, it is characterised in that：By each component structure of following quality proportioning
Into 5 ~ 15 parts of silvering graphite alkene；1 ~ 3 part of carbon pipe；20 ~ 60 parts of vinyl ester resin；1 ~ 2 part of coupling agent；Lacquer type organic coating curing agent and
Totally 1 ~ 3 part of lacquer type organic coating catalyst；Wherein lacquer type organic coating catalyst and lacquer type organic coating curing agent mass ratio are 2 ~ 4:1；Diluent 20 ~ 60
Part；
The silvering graphite alkene is prepared as follows,
1）By 1g graphenes ultrasonic disperse in the strong alkali aqueous solution that 1L concentration is 0.2 ~ 1 mol/L, 80 ~ 100 are then heated to
DEG C and kept for 0.5 ~ 2 hour, then with clear water washing and filtering, obtain the graphene after oil removing, roughening；
2）By step 1）Then the graphene dispersion being filtrated to get heats 10 ~ 30 points into 1L sensitizing solution at 20 ~ 55 DEG C
Clock；The sensitizing solution is that stannic chloride, 4 ~ 7g/L sodium stannate and the 50 ~ 150mg/L hydrochloric acid that concentration is 20 ~ 30g/L are formed
Deionized water mixed solution；
3）The 2nd）0.5 ~ 1.5g activators palladium bichloride is added in step reaction system to heat 10 ~ 30 minutes at 45 DEG C；
4）By step 3）Reaction system filtering, by comprising the filtrate including graphene be distributed to 0.4L concentration for 0.1 ~
5 ~ 15 minutes in 0.3mol/L reducing solution；
5）By step 4）Reaction system filtering, filtrate input 500 ~ 1000mL silver ammino solutions in be slowly stirred 5 ~ 15 minutes；
Ammoniacal liquor mass fraction is 15 ~ 30% in silver ammino solution, and silver nitrate concentration be 3.0~25.0g/L in silver ammino solution, pH for 10.0~
11.0；
6）The 5th）Walk in obtained reaction system and be added dropwise and step 4）Identical reducing solution and amount it is also identical, maintain temperature 25
~ 30 DEG C, until uniformly the silver layer of the bright silvery white of plating last layer, graphene are 1 with silver layer mass ratio on graphene:1~5；Filtering is
Obtain silvering graphite alkene；
The reducing solution is one or more of mixed solutions in glucose, sodium potassium tartrate tetrahydrate and tartaric acid.
2. the highly conductive coating of silvering graphite olefinic carbon pipe compound resin according to claim 1, it is characterised in that：It is described strong
Aqueous alkali is sodium hydroxide, a kind of aqueous solution or two kinds of mixed aqueous solution in potassium hydroxide.
3. the highly conductive coating of silvering graphite olefinic carbon pipe compound resin according to claim 1, it is characterised in that：The stone
Black alkene is 2 ~ 20 micron order piece footpaths, less than 10 layers of graphene；The carbon pipe is more wall carbon pipes, 5 ~ 100nm of caliber, pipe range 0.1
~50μm。
4. the highly conductive coating of silvering graphite olefinic carbon pipe compound resin according to claim 1, it is characterised in that：The idol
It is silane coupling agent or titanate coupling agent to join agent；The lacquer type organic coating catalyst is blue water, and lacquer type organic coating curing agent is plain boiled water；Institute
It is styrene to state diluent.
5. the highly conductive coating of silvering graphite olefinic carbon pipe compound resin according to claim 1, it is characterised in that：The plating
Silver-colored graphene is 10 with carbon pipe mass ratio:2~3.
6. the highly conductive preparation method for coating of silvering graphite olefinic carbon pipe compound resin described in claim 4, it is characterised in that：First will
Vinyl ester resin and styrene are hybridly prepared into the vinyl ester resin styrene solution that mass concentration is 50 ~ 60%；Again will plating
Silver-colored graphene and carbon pipe ultrasonic disperse is into vinyl ester resin styrene solution, then adds coupling agent, then in ball milling or sand
Mix 2 ~ 4 hours, be well mixed in grinding machine；Lacquer type organic coating catalyst and lacquer type organic coating curing agent are sequentially added after taking-up, is well mixed
.
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