CN109467772A - A kind of graphene composite neoprene thermo electric material and preparation method thereof - Google Patents
A kind of graphene composite neoprene thermo electric material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene composite neoprene thermo electric materials, including following raw materials according: neoprene, polyethylene terephthalate 5, formic acid, haloflex, dimethyl sulfoxide, silica trimethyl silicane alkoxy esters of silicon acis, copolymer-maleic anhydride, terpinol, hydroxy silicon oil, graphene oxide, conductive black, silane coupling agent, dibenzoyl peroxide, anti-aging agent, zinc stearate.The present invention also provides the preparation methods of above-mentioned graphene composite neoprene thermo electric material；Graphene composite neoprene thermo electric material of the invention not only thermal conductivity effect and mechanical strength also have the characteristics that mechanical property is good, good stability of the dimension, good weatherability, can satisfy the requirement of industry, with good application prospect.
Description
Technical field
The present invention relates to composite electric hating material technical field, specifically a kind of graphene composite neoprene thermo electric material and
Preparation method.
Background technique
Rubber, such as natural rubber, butadiene rubber, isoprene rubber, nitrile rubber, neoprene have high resiliency, can be wide
It is general to be used for the crowds such as daily necessity (rubber overshoes), auto industry (tire), medical industry (medicinal bottle stopper), electrical industry (wire and cable)
Conglomerate and field are good electrical insulators.
Graphene is that single layer of carbon atom accumulates the honeycomb two dimensional crystal to be formed in the form of Sp2, and graphene has big
Specific surface area and excellent electricity, calorifics and mechanical property.Three-dimensional grapheme is to be crosslinked based on two-dimensional graphene piece by space
The tridimensional network of formation, in addition to the proper property with two-dimensional graphene, three-dimensional graphite is thermally conductive in space, conductive and macro
Measuring high quality preparation aspect has unique advantage.For example, grapheme material has unique two-dimension phonon transmission characteristic, high
Theoretical thermal conductivity, be the highest material of current thermal coefficient, while graphene has highest electronics conduction of velocity, about
The 1/300 of the light velocity, and the hardness of graphene is big, up to 500 times of steel.
Thermo electric material is the material that thermal energy can be converted electrical energy by self-resistance, and common thermo electric material is by gold
Category, semiconductor or conductive particle high molecular material are compounded.Graphene-based rubber composite material is usually as conductive, shielding
Material is applied in electronic technology field, and the research in thermo electric material is less.In use, only considering its electric conductivity substantially, not
Have and considers the mechanical performances such as plasticity, tensile strength, elongation rate of tensile failure.To adapt to complicated working environment, thermo electric material will have
Standby requirement is higher and higher, and such as easy to form, sizing, conductive stable, plasticity are high, and flexibility is high, at low cost etc..
Although also having the precedent for being added to graphene and preparing thermo electric material in rubber at present, the electric heating being prepared into
The physicochemical property of material tends not to fully meet demand, and graphene is expensive, is not applied for heavy industrialization
The demand of production.Therefore, it is less to research and develop a kind of graphene dosage, but there is same excellent conductive heat-conducting effect and mechanical strength
Thermo electric material product, realize graphene compounded rubber popularization and application be particularly important.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, adapts to realistic development, provides a kind of compound neoprene of graphene
Rubber thermo electric material and its preparation method and application.
In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
A kind of graphene composite neoprene thermo electric material, the raw material including following parts by weight: neoprene 80~100
Part, 50~80 parts of polyethylene terephthalate, 50~80 parts of formic acid, 40~60 parts of haloflex, dimethyl sulfoxide 30
~50 parts, 20~30 parts of silica, 10~25 parts of trimethyl silicane alkoxy esters of silicon acis, 15~20 parts of copolymer-maleic anhydride,
10~15 parts of terpinol, 3~5 parts of hydroxy silicon oil, 3~5 parts of graphene oxide, 3~5 parts of conductive black, silane coupling agent 1~3
Part, 1~3 part of dibenzoyl peroxide, 1~3 part of anti-aging agent and 0~1 part of zinc stearate.
Preferably, the raw material including following parts by weight: 90 parts of neoprene, 65 parts of polyethylene terephthalate, first
Sour 65 parts, 50 parts of haloflex, 40 parts of dimethyl sulfoxide, 25 parts of silica, 18 parts of trimethyl silicane alkoxy esters of silicon acis, horse
Come 17 parts of acid anhydride copolymer, 12 parts of terpinol, 4 parts of hydroxy silicon oil, 4 parts of graphene oxide, 4 parts of conductive black, silane coupling agent 2
Part, 2 parts of dibenzoyl peroxide, 2 parts of anti-aging agent and 1 part of zinc stearate.
Preferably, the melt index of the polystyrene is 1~100g/10min.
Preferably, the carbon content of the graphene oxide is not less than 90%, and specific surface area is 100~500m2/g。
Preferably, the anti-aging agent be selected from one of antioxidant MB Z, anti-aging agent RD, antioxidant NBC, antioxidant A W or
It is several.
The present invention discloses the preparation methods of above-mentioned graphene composite neoprene thermo electric material, including walk as follows
It is rapid:
(1) neoprene is added in formic acid, is dissolved under the conditions of 250~300 DEG C, obtain rubber emulsion；
(2) copolymer-maleic anhydride is added in dimethyl sulfoxide, stirring at normal temperature obtains polymer solution；
(3) graphene oxide is dissolved in the terpineol solution that silane coupling agent has been added, high-speed stirred and simultaneously under room temperature
After ultrasonic disperse 3~5 hours, trimethyl silicane alkoxy esters of silicon acis is added and is mixed, is stirred to react 18~24 under the conditions of 85 DEG C
Hour, hydrogen peroxide is then added and is stirred to react 1~3 hour, then adjusts pH to 4~6,75 DEG C are stirred to react 8~12 hours, obtain
Graphene dispersing solution；
(4) the graphene dispersing solution grinding is added in conductive black and obtains 350~500 mesh slurries in 3~5 hours, it is spraying
It is dried to obtain powder；
(5) high-speed mixer is added in the polymer solution, powder and zinc stearate, high-speed stirred simultaneously mixes equal
Even, mixing temperature is 70~90 DEG C, and incorporation time is 1~2 hour, is subsequently placed in vacuum drying oven and dries under the conditions of 100~120 DEG C
It is 12~16 hours dry, obtain mixture；
(6) mixture is sent into kneading machine, sequentially adds the rubber emulsion, polyethylene terephthalate
Ester, haloflex, silica, hydroxy silicon oil and anti-aging agent are kneaded 25~45 minutes under the conditions of 110~220 DEG C, are mixed
Refine object；Then dibenzoyl peroxide is added, vulcanizes 3~5 hours under the conditions of 180~260 DEG C, obtains sulfide；
(7) sulfide is placed in vacuum drying oven at 200~250 DEG C and is dried 8~12 hours, then put into twin-screw
Extruder, 200~280 DEG C, preheat 5~15 minutes, 300~400 DEG C under the conditions of 5~10MPa under the conditions of melt, 180~280
DEG C, hot pressing squeezes out under the conditions of 10~25MPa, the sizing of water circulating cooling obtains graphene composite neoprene thermo electric material.
Further, the mass volume ratio of graphene dispersing solution and hydrogen peroxide described in step (3) is 1: 100g/ml.
Further, step (3) adjusts pH using 0.5mol/L phosphoric acid solution.
Further, spray drying EAT described in step (4) is 250 DEG C, 180 DEG C of leaving air temp.
Further, the speed of high-speed stirred described in step (5) is 10000~30000r/min.
Compared with prior art, the advantages and positive effects of the present invention are as follows:
Rubber emulsion, polymer solution and graphene dispersing solution are successively mixed, be kneaded and vulcanized by the present invention, the process
Filler loading can not only be reduced, additionally it is possible to make to connect between filler even closer, be equivalent to and improve thermo electric material unit
The content of volume conduction filler reaches the resistivity of design to improve electric conductivity；
Graphene dispersing solution is dispersed in the co-mixing system of rubber emulsion and polymer solution, is formed conductive and led
Heat passage makes thermo electric material have excellent electric conductivity and good heating conduction；
Graphene sheet layer structure is effectively combined on a microscopic level with the space structure of copolymer-maleic anhydride and is significantly improved
The processing fluidity of product, has widened the scope of application of thermo electric material.
The present invention, which prepares graphene composite neoprene thermo electric material using blended melting method, has production continuously, very
The advantages of being suitble to large-scale production.
Graphene composite neoprene thermo electric material of the invention not only thermal conductivity effect and mechanical strength, but also
Also have the characteristics that mechanical property is good, good stability of the dimension, good weatherability, can satisfy the requirement of industry, has and preferably answer
Use prospect.
Specific embodiment
It elaborates below to specific embodiments of the present invention.
Embodiment 1
A kind of graphene composite neoprene thermo electric material, the raw material including following parts by weight: 80 parts of neoprene, poly- pair
50 parts of ethylene terephthalate, 50 parts of formic acid, 40 parts of haloflex, 30 parts of dimethyl sulfoxide, 20 parts of silica, front three
10 parts of base silane oxygroup esters of silicon acis, 15 parts of copolymer-maleic anhydride, 10 parts of terpinol, 3 parts of hydroxy silicon oil, 3 parts of graphene oxide,
3 parts of conductive black, 1 part of silane coupling agent, 1 part of dibenzoyl peroxide and 1 part of antioxidant MB Z.
The melt index of the polystyrene is 1g/10min.
The carbon content of the graphene oxide is 90%, specific surface area 100m2/g。
The preparation method of above-mentioned graphene composite neoprene thermo electric material, includes the following steps:
(1) neoprene is added in formic acid, is dissolved under the conditions of 250 DEG C, obtain rubber emulsion；
(2) copolymer-maleic anhydride is added in dimethyl sulfoxide, stirring at normal temperature obtains polymer solution；
(3) graphene oxide is dissolved in the terpineol solution that silane coupling agent has been added, high-speed stirred and simultaneously under room temperature
After ultrasonic disperse 3 hours, trimethyl silicane alkoxy esters of silicon acis is added and is mixed, be stirred to react 18 hours under the conditions of 85 DEG C, so
Hydrogen peroxide is added afterwards to be stirred to react 1 hour, adjusts pH to 4,75 DEG C are stirred to react 8 hours, obtain graphene dispersing solution；
(4) the graphene dispersing solution grinding is added in conductive black and obtains 350 mesh slurries in 3 hours, spray drying obtains
Powder；
(5) high-speed mixer is added in the polymer solution and powder, high-speed stirred is simultaneously uniformly mixed, mixing temperature
It is 70 DEG C, incorporation time is 1 hour, is subsequently placed in vacuum drying oven under the conditions of 100~120 DEG C and dries 12 hours, is mixed
Object；
(6) mixture is sent into kneading machine, sequentially adds the rubber emulsion, polyethylene terephthalate
Ester, haloflex, silica, hydroxy silicon oil and antioxidant MB Z are kneaded 25 minutes under the conditions of 110 DEG C, obtain mixture；
Then dibenzoyl peroxide is added, vulcanizes 3 hours under the conditions of 180 DEG C, obtains sulfide；
(7) sulfide is placed in vacuum drying oven at 200 DEG C and is dried 8 hours, then put into double screw extruder,
200 DEG C, preheat 5 minutes, 300 DEG C under the conditions of 5MPa under the conditions of melt, 180 DEG C, hot pressing squeezes out under the conditions of 10MPa, water circulation is cold
But it is formed, obtains graphene composite neoprene thermo electric material.
The mass volume ratio of graphene dispersing solution described in step (3) and hydrogen peroxide is 1: 100g/ml.
Step (3) adjusts pH using 0.5mol/L phosphoric acid solution.
Spray drying EAT described in step (4) is 250 DEG C, 180 DEG C of leaving air temp.
The speed of high-speed stirred described in step (5) is 10000r/min.
Embodiment 2
A kind of graphene composite neoprene thermo electric material, the raw material including following parts by weight: 90 parts of neoprene, poly- pair
65 parts of ethylene terephthalate, 65 parts of formic acid, 50 parts of haloflex, 40 parts of dimethyl sulfoxide, 25 parts of silica, front three
18 parts of base silane oxygroup esters of silicon acis, 17 parts of copolymer-maleic anhydride, 12 parts of terpinol, 4 parts of hydroxy silicon oil, 4 parts of graphene oxide,
4 parts of conductive black, 2 parts of silane coupling agent, 2 parts of dibenzoyl peroxide, 2 parts of antioxidant NBC, 1 part of zinc stearate.
The melt index of the polystyrene is 50g/10min.
The carbon content of the graphene oxide is 100%, specific surface area 300m2/g。
The preparation method of above-mentioned graphene composite neoprene thermo electric material, includes the following steps:
(1) neoprene is added in formic acid, is dissolved under the conditions of 270 DEG C, obtain rubber emulsion；
(2) copolymer-maleic anhydride is added in dimethyl sulfoxide, stirring at normal temperature obtains polymer solution；
(3) graphene oxide is dissolved in the terpineol solution that silane coupling agent has been added, high-speed stirred and simultaneously under room temperature
After ultrasonic disperse 4 hours, trimethyl silicane alkoxy esters of silicon acis is added and is mixed, be stirred to react 22 hours under the conditions of 85 DEG C, so
Hydrogen peroxide is added afterwards to be stirred to react 2 hours, adjusts pH to 5,75 DEG C are stirred to react 10 hours, obtain graphene dispersing solution；
(4) the graphene dispersing solution grinding is added in conductive black and obtains 400 mesh slurries in 4 hours, spray drying obtains
Powder；
(5) high-speed mixer is added in the polymer solution, powder and zinc stearate, high-speed stirred simultaneously mixes equal
Even, mixing temperature is 80 DEG C, and incorporation time is 1.5 hours, is subsequently placed in vacuum drying oven at 110 DEG C and dries 14 hours, obtains
Mixture；
(6) mixture is sent into kneading machine, sequentially adds the rubber emulsion, polyethylene terephthalate
Ester, haloflex, silica, hydroxy silicon oil and antioxidant NBC are kneaded 35 minutes under the conditions of 160 DEG C, obtain mixture；
Then dibenzoyl peroxide is added, vulcanizes 4 hours under the conditions of 220 DEG C, obtains sulfide；
(7) sulfide is placed in vacuum drying oven at 230 DEG C and is dried 10 hours, then put into double screw extruder,
240 DEG C, preheat 10 minutes, 350 DEG C under the conditions of 8MPa under the conditions of melt, 250 DEG C, hot pressing squeezes out under the conditions of 15MPa, water circulation is cold
But it is formed, obtains graphene composite neoprene thermo electric material.
The mass volume ratio of graphene dispersing solution described in step (3) and hydrogen peroxide is 1: 100g/ml.
Step (3) adjusts pH using 0.5mol/L phosphoric acid solution.
Spray drying EAT described in step (4) is 250 DEG C, 180 DEG C of leaving air temp.
The speed of high-speed stirred described in step (5) is 20000r/min.
Embodiment 3
A kind of graphene composite neoprene thermo electric material, the raw material including following parts by weight: 100 parts of neoprene gathers
80 parts of ethylene glycol terephthalate, 80 parts of formic acid, 60 parts of haloflex, 50 parts of dimethyl sulfoxide, 30 parts of silica, three
25 parts of methyl-monosilane oxygroup esters of silicon acis, 20 parts of copolymer-maleic anhydride, 15 parts of terpinol, 5 parts of hydroxy silicon oil, graphene oxide 5
Part, 5 parts of conductive black, 3 parts of silane coupling agent, 3 parts of dibenzoyl peroxide, 3 parts of anti-aging agent RD, 1 part of zinc stearate.
The melt index of the polystyrene is 100g/10min.
The carbon content 120% of the graphene oxide, specific surface area 500m2/g。
The preparation method of above-mentioned graphene composite neoprene thermo electric material, includes the following steps:
(1) neoprene is added in formic acid, is dissolved under the conditions of 300 DEG C, obtain rubber emulsion；
(2) copolymer-maleic anhydride is added in dimethyl sulfoxide, stirring at normal temperature obtains polymer solution；
(3) graphene oxide is dissolved in the terpineol solution that silane coupling agent has been added, high-speed stirred and simultaneously under room temperature
After ultrasonic disperse 5 hours, trimethyl silicane alkoxy esters of silicon acis is added and is mixed, be stirred to react 24 hours under the conditions of 85 DEG C, so
Hydrogen peroxide is added afterwards to be stirred to react 3 hours, adjusts pH to 6,75 DEG C are stirred to react 12 hours, obtain graphene dispersing solution；
(4) the graphene dispersing solution grinding is added in conductive black and obtains 500 mesh slurries in 5 hours, spray drying obtains
Powder；
(5) high-speed mixer is added in the polymer solution, powder and zinc stearate, high-speed stirred simultaneously mixes equal
Even, mixing temperature is 90 DEG C, and incorporation time is 2 hours, is subsequently placed in vacuum drying oven under the conditions of 120 DEG C and dries 16 hours, obtains
To mixture；
(6) mixture is sent into kneading machine, sequentially adds the rubber emulsion, polyethylene terephthalate
Ester, haloflex, silica, hydroxy silicon oil and anti-aging agent RD are kneaded 45 minutes under the conditions of 220 DEG C, obtain mixture；So
After dibenzoyl peroxide is added, vulcanize 5 hours under the conditions of 260 DEG C, obtain sulfide；
(7) sulfide is placed in vacuum drying oven at 250 DEG C and is dried 12 hours, then put into double screw extruder,
280 DEG C, preheat 15 minutes, 400 DEG C under the conditions of 10MPa under the conditions of melt, 280 DEG C, hot pressing squeezes out under the conditions of 25MPa, water circulation
Cooling and shaping obtains graphene composite neoprene thermo electric material.
The mass volume ratio of graphene dispersing solution described in step (3) and hydrogen peroxide is 1: 100g/ml.
Step (3) adjusts pH using 0.5mol/L phosphoric acid solution.
Spray drying EAT described in step (4) is 250 DEG C, 180 DEG C of leaving air temp.
The speed of high-speed stirred described in step (5) is 30000r/min.
Comparative example 1
(1) 100 parts of nitrile rubber, 25 parts of organic siliconresin, 20 parts of acrylic resin, 10 parts of sepiolite powder, peroxide are weighed
Change 8 parts of diisopropylbenzene (DIPB), 7 parts of gelatin, 5 parts of barium stearate, 5 parts of diisononyl phthalate, Brij phosphate 4
Part, 3 parts of graphene, 2 parts of conductive black, 1 part of silane coupling agent, 3 parts of fatty alcohol polyoxyethylene ether, 3 parts of antioxidant MB Z；
(2) suitable quantity of water is added in graphene, sepiolite powder, conductive black, grinding obtains 450 mesh slurries in 3 hours, spraying dry
Dry to obtain powder, spray dryer inlet air temperature is 250 DEG C, 180 DEG C of leaving air temp；
(3) powder is added nitric acid, reacted 5 minutes, is sent into kneading machine after drying, then successively plus nitrile rubber,
Organic siliconresin, acrylic resin, cumyl peroxide, gelatin carry out mixing 25min, and melting temperature is 95 DEG C, add
Barium stearate, diisononyl phthalate, Brij phosphate, silane coupling agent are kneaded 5min；
(4) fatty alcohol polyoxyethylene ether, antioxidant MB Z is added in the raw material after mixing, and adds 20 parts of deionized waters, surpassed
Sonication 2.5h obtains stock suspension, and the frequency of ultrasonic treatment is 25KHz, and the power of ultrasonic treatment is 1200W；
(5) stock suspension after ultrasonic treatment is dried, then puts into double screw extruder, in 370 DEG C of temperature
The lower melting of degree, squeezes out, wherein filtering is to carry out vacuum filtration 25min with the nylon leaching film of 450 mesh, vacuum pressure is after filtering
15kPa, the revolving speed of double screw extruder are 180rpm, and pressure is 15kPa in extrusion process；
(6) raw material after squeezing out is cooled down, and is then stretched, the parameter of drawing process are as follows: and temperature of heat plate is 75 DEG C,
Hot plate temperature is 130 DEG C, and stretching ratio is 3.3 times, and finally thermal finalization under the conditions of 280 DEG C, obtains the graphene of thermal conductivity
Composite rubber material.
Comparative example 2
A kind of graphite-based composite high-molecular thermo electric material, the component including following mass parts: 100 parts of EP rubbers, 50 parts
Composite graphite base conductive material and 44.6 parts of compounding agent；The composite graphite base conductive material includes that mass fraction is
20% crystalline flake graphite, 20% graphite fibre, 40% spray carbon black, 20% calcined petroleum coke；The compounding agent includes 0.5 part of DCP,
3 parts of white carbon blacks, 0.1 part of hydroxy silicon oil, 1 part of antioxidant MB, 40 parts of fire retardants.
Further, crystalline flake graphite, phosphorus content is 99% or more, and partial size is less than 35 μm；Graphite fibre, through stone at 2500 DEG C
Blackization processing, phosphorus content is 99.19% or more；Spray carbon black, phosphorus content is 99.19% or more, and partial size is less than 20 μm；Calcine stone
Oil coke, phosphorus content are greater than 99.15%, and partial size is less than 35 μm.
Further, the fire retardant is mixed using 60% chlorosulfonated polyethylene and 40% haloflex.
A kind of preparation method of graphite-based composite high-molecular thermo electric material, includes the following steps:
(1) preparation of composite graphite base conductive material: crystalline flake graphite is weighed according to above-mentioned mass ratio, graphite fibre, is sprayed
Carbon black, calcined petroleum coke are uniformly mixed；
(2) be kneaded: according to above-mentioned mass ratio weigh EP rubbers, white carbon black, hydroxy silicon oil, antioxidant MB, fire retardant,
Composite graphite base conductive material made from step (1) is divided into three equal parts by DCP, by EP rubbers, white carbon black, composite graphite base
Conductive material, hydroxy silicon oil, composite graphite base conductive material, antioxidant MB, composite graphite base conductive material, fire retardant successively add
Enter in two-roll mill, Bao Tong 8~10 times, obtains rubber compound；
(3) back mixing: being put into baking oven for rubber compound obtained by step (2) and be heat-treated, and open mill is then added and returns white silk, is added
It DCP, Bao Tong 2 times, parks at room temperature 24 hours, so that various compounding agents is sufficiently worked with raw rubber, mill is then added again
Machine returns white silk, sufficiently soft to sizing material, can blanking slice after surface is smooth；
(4) it filters: by step (3) resulting sizing material, being packed into rubber strainer filtering, using 80 mesh screens, obtain embryo glue；
(5) vulcanize: loading onto power supply line, the filtered embryo glue compression moulding of step (4) then puts molding product
Enter and carry out one step cure in vulcanizing tank, to keep physical property and the chemical property of product more stable, quality more preferably, is carried out product
Post vulcanization, one step cure temperature are 160 DEG C, time 5min, and post vulcanization temperature is 200 DEG C, time 120min.
Measure the properties of thermo electric material prepared by Examples 1 to 3 and comparative example 1 and 2.
The properties measurement result of 1 thermo electric material of table
Table 1 the result shows that, graphene composite neoprene thermo electric material of the invention not only thermal conductivity effect and machinery
Excellent strength, but also have the characteristics that mechanical property is good, good stability of the dimension, good weatherability, it can satisfy the requirement of industry,
With good application prospect.
Above-described embodiment is only more excellent embodiment of the invention, is implemented according to the technical essence of the invention to above
Any simple modification, modification and the alternate variation that example is made, belong in the range of technical solution of the present invention.
Claims (10)
1. a kind of graphene composite neoprene thermo electric material, which is characterized in that the raw material including following parts by weight: neoprene
80~100 parts, 50~80 parts of polyethylene terephthalate, 50~80 parts of formic acid, 40~60 parts of haloflex, dimethyl
30~50 parts of sulfoxide, 20~30 parts of silica, 10~25 parts of trimethyl silicane alkoxy esters of silicon acis, copolymer-maleic anhydride 15~
20 parts, 10~15 parts of terpinol, 3~5 parts of hydroxy silicon oil, 3~5 parts of graphene oxide, 3~5 parts of conductive black, silane coupling agent
1~3 part, 1~3 part of dibenzoyl peroxide, 1~3 part of anti-aging agent and 0~1 part of zinc stearate.
2. a kind of graphene composite neoprene thermo electric material according to claim 1, which is characterized in that including following heavy
Measure the raw material of part: 90 parts of neoprene, 65 parts of polyethylene terephthalate, 65 parts of formic acid, 50 parts of haloflex, diformazan
40 parts of base sulfoxide, 25 parts of silica, 18 parts of trimethyl silicane alkoxy esters of silicon acis, 17 parts of copolymer-maleic anhydride, terpinol 12
Part, is prevented always 4 parts of hydroxy silicon oil, 4 parts of graphene oxide, 4 parts of conductive black, 2 parts of silane coupling agent, 2 parts of dibenzoyl peroxide
2 parts and 1 part of zinc stearate of agent.
3. a kind of graphene composite neoprene thermo electric material according to claim 1, which is characterized in that the polyphenyl second
The melt index of alkene is 1~100g/10min.
4. a kind of graphene composite neoprene thermo electric material according to claim 1, which is characterized in that the oxidation stone
The carbon content of black alkene is not less than 90%, and specific surface area is 100~500m2/g。
5. a kind of graphene composite neoprene thermo electric material according to claim 1, which is characterized in that the anti-aging agent
Selected from one or more of antioxidant MB Z, anti-aging agent RD, antioxidant NBC, antioxidant A W.
6. a kind of preparation method of graphene composite neoprene thermo electric material as claimed in any one of claims 1 to 5, wherein,
It is characterized in that, includes the following steps:
(1) neoprene is added in formic acid, is dissolved under the conditions of 250~300 DEG C, obtain rubber emulsion；
(2) copolymer-maleic anhydride is added in dimethyl sulfoxide, stirring at normal temperature obtains polymer solution；
(3) graphene oxide is dissolved in the terpineol solution that silane coupling agent has been added, high-speed stirred and while ultrasound under room temperature
After dispersion 3~5 hours, trimethyl silicane alkoxy esters of silicon acis is added and is mixed, is stirred to react 18~24 hours under the conditions of 85 DEG C,
Then hydrogen peroxide is added to be stirred to react 1~3 hour, then adjusts pH to 4~6,75 DEG C are stirred to react 8~12 hours, obtain graphite
Alkene dispersion liquid；
(4) the graphene dispersing solution grinding is added in conductive black and obtains 350~500 mesh slurries in 3~5 hours, be spray-dried
Obtain powder；
(5) high-speed mixer is added in the polymer solution, powder and zinc stearate, high-speed stirred is simultaneously uniformly mixed, and is mixed
Closing temperature is 70~90 DEG C, and incorporation time is 1~2 hour, is subsequently placed in vacuum drying oven and dries 12 under the conditions of 100~120 DEG C
~16 hours, obtain mixture；
(6) by the mixture be sent into kneading machine, sequentially add the rubber emulsion, polyethylene terephthalate,
Haloflex, silica, hydroxy silicon oil and anti-aging agent are kneaded 25~45 minutes under the conditions of 110~220 DEG C, are kneaded
Object；Then dibenzoyl peroxide is added, vulcanizes 3~5 hours under the conditions of 180~260 DEG C, obtains sulfide；
(7) sulfide is placed in vacuum drying oven at 200~250 DEG C and is dried 8~12 hours, then put into twin-screw extrusion
Machine, 200~280 DEG C, preheat 5~15 minutes, 300~400 DEG C under the conditions of 5~10MPa under the conditions of melt, 180~280 DEG C, 10
Hot pressing squeezes out under the conditions of~25MPa, and the sizing of water circulating cooling obtains graphene composite neoprene thermo electric material.
7. a kind of preparation method of graphene composite neoprene thermo electric material according to claim 6, which is characterized in that
The mass volume ratio of graphene dispersing solution described in step (3) and hydrogen peroxide is 1: 100g/ml.
8. a kind of preparation method of graphene composite neoprene thermo electric material according to claim 6, which is characterized in that
Step (3) adjusts pH using 0.5mol/L phosphoric acid solution.
9. a kind of preparation method of graphene composite neoprene thermo electric material according to claim 6, which is characterized in that
Spray drying EAT described in step (4) is 250 DEG C, 180 DEG C of leaving air temp.
10. a kind of preparation method of graphene composite neoprene thermo electric material according to claim 6, feature exist
In the speed of high-speed stirred described in step (5) is 10000~30000r/min.
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