CN101864098A - In situ reduction preparation method of polymer/graphene composites - Google Patents
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Abstract
聚合物/石墨烯复合材料的原位还原制备方法，其特点是采用超声波或者研磨方式将Hummers法制备的氧化石墨均匀分散在聚合物胶乳中，然后在胶乳中通入还原剂进行原位还原，使氧化石墨还原为石墨烯，从而得到稳定的聚合物/石墨烯复合乳液，再经过破乳、凝聚、干燥，得到聚合物/石墨烯复合母料。将干燥后的聚合物/石墨烯复合母料与各种助剂按一定比例加入到聚合物基体中，进一步通过双辊混合、硫化、熔融挤出或注塑，获得具有良好性能的聚合物/石墨烯复合材料。该方法制备半导体或导体聚合物/石墨烯复合材料具有较好的物理机械性能。The in-situ reduction preparation method of the polymer/graphene composite material is characterized in that the graphite oxide prepared by the Hummers method is uniformly dispersed in the polymer latex by ultrasonic or grinding, and then a reducing agent is introduced into the latex for in-situ reduction. The graphite oxide is reduced to graphene to obtain a stable polymer/graphene composite emulsion, and then undergoes demulsification, coagulation and drying to obtain a polymer/graphene composite masterbatch. The dried polymer/graphene composite masterbatch and various additives are added to the polymer matrix in a certain proportion, and the polymer/graphene with good properties is obtained through twin-roll mixing, vulcanization, melt extrusion or injection molding vinyl composites. The semiconductor or conductive polymer/graphene composite material prepared by the method has good physical and mechanical properties.
Description
Technical field
The present invention relates to a kind of in-situ reduction preparation method of polymer/graphene composite material, belong to the preparation field of polymkeric substance.
Background technology
Graphene is a kind of by sp
2The carbonaceous novel material of the tightly packed bi-dimensional cellular shape crystalline network that forms of the carbon atom of hydridization, thickness is one or more atomic shells.Can be divided into one or more layers Graphene according to the number of plies.The history in existing more than 60 year of the theoretical investigation of Graphene, and can real self-existent two-dimentional Graphene lamella utilize the method for the high oriented graphite of tape stripping to obtain by the Novoselov of Univ Manchester UK etc. up to 2004.Up to the present, Graphene is by the preparation of following several method: 1) chemical vapor deposition method (Eizenberg M., Blakely J. M. Surf. Sci.1970,82,228-236.); 2) epitaxial growth method (Berger C. Song Z., Li X., Wu X.et al. Science 2006,312,1191-1196.); 3) the mechanically peel method (Novoselov K. S., GeimA.K., Morozov S.V., et al.Science 2004,306,666-669.); 4) reduction-oxidation graphite method (Stankovich S. Piner R.D., Nguyen S.T., Ruoff R.S. Carbon 2006,44,3342-3347.Stankovich S., PinerR.D., ChenX., et al.J. Mater.Chem.2006,16,155-158.).The 4th kind of method makes the mass production Graphene be applied to matrix material becomes possibility.In five sixties of 20th century a large amount of reports about the graphite oxide aqeous suspension are just arranged.(Boehm H.P., Eckel M, Scholz W.Anorg.Allg.Chem.1967,353,236-242.) because of the graphite oxide possess hydrophilic property, so can be stripped from the suspension that forms graphene oxide fully by ultrasonication.(Park S., RuoffR.S. Nat.Nanotechnol.2009,4,217-224.) in aqeous suspension, the chemical reduction of graphene oxide can be used for the Graphene lamella of mass production chemical modification.The existing individual layer of Graphene prepared by this method multiwalled arranged again.Because Graphene has good mechanical property, electric property and thermal property are so there is a lot of relevant Graphenes/polymer composites report recently.At present, the Graphene filler successfully is distributed to polystyrene, and polyacrylonitrile is in the matrixes such as Resins, epoxy and polymethylmethacrylate.(Stankovich S., Dikin D.A., Dommett D., Kohlhaas K.Et al.Nature 2006,442,282-286.Ramanathan T., Abdala A.A., Stankovich S., Dikin D.A.et al.Nat.Nanotechnol.2008,3,327-331.Rafiee M.A., Rafiee J., Wang Z., et al.ACSNano, 2009,3,3884-3890.) Graphene/polymer composites can be realized the mutual supplement with each other's advantages or the reinforcement of material.Graphene can greatly improve the mechanical property of polymer materials, and this is owing to the high specific surface area of Graphene, strong nano material-basal body interface effect and sp
2The mechanical property that hydridization carbon is good.Simultaneously, Graphene/polymer composites has good electrical conductivity, can make flexible conductive film material, radiowave there is certain screening ability, can be applicable to the defence and military field and prepare antistatic coating, radar absorbing, and the stealth material of submarine aircraft.In addition, Graphene is at preparation nano-electron field-effect transistor, and also there is good application prospects energy reserves and thermally conductive material aspect.At present, polymer/graphene composite material is generally by solution, melting mixing and in-situ polymerization preparation, but because Graphene is easy to assemble, up to the present, experimental result and theoretical prediction are still far apart.The key issue that needs to solve is the scattering problem of Graphene in polymeric matrix.
Summary of the invention
The objective of the invention is to provide a kind of in-situ reduction preparation method of polymer/graphene composite material at the deficiencies in the prior art, be characterized in adopting ultrasonic wave or lapping mode will be dispersed in by the graphite oxide of Hummers method preparation natural rubber latex and or synthetic latex in, make graphite oxide be homogeneously dispersed state, in latex, feed reductive agent then and carry out in-situ reducing, make graphite oxide be converted into Graphene, thereby obtain stable latex/Graphene composite emulsion, emulsion is through breakdown of emulsion, cohesion, can obtain the polymer/graphene composite master batch after the drying.Dried polymer/graphene composite master batch and various auxiliary agent are joined in the polymeric matrix by a certain percentage, further mix, vulcanize, melt extrude or injection moulding, obtain having the polymer/graphene composite material of superperformance by two rollers.
The objective of the invention is to realize that by following technical measures wherein said raw material mark is parts by weight except that specified otherwise.
The in-situ reduction preparation method of polymer/graphene composite material may further comprise the steps:
(1) preparation of polymer/graphene composite emulsion in-situ reducing
A) ultrasonic dispersion: with 0.01～10 part of graphite oxide, preferred 0.01～8 part and solvent add in the ultrasound wave irradiation reactor for 100～3000 parts, at ultrasonic power is 10～50000W, preferred 200～10000W, frequency is 10～100000Hz, preferred 200～20000Hz, 20～200 ℃ of temperature, preferred 40～100 ℃, 5 minutes～5 hours ultra-sonic dispersion time, preferred 30 minutes～2 hours, obtain graphite oxide solution, add 5～300 parts of polymer emulsions, preferred 10～200 parts, continue ultra-sonic dispersion 5 minutes～5 hours, and preferred 30 minutes～3 hours, added 0.01～100 part of reductive agent again, preferred 3～30 parts, continue ultra-sonic dispersion 5 minutes～10 hours, and preferred 2 hours～4 hours, obtained stable polymer/Graphene composite emulsion;
B) grind dispersing method: with 0.01～10 part of graphite oxide, in preferred 0.01～8 part and 100～3000 parts of adding shredders of solvent, ground 5 minutes～5 hours, preferred 30 minutes～2 hours, obtain graphite oxide solution, add 5～300 parts of polymer emulsions, preferred 10～200 parts, continue to grind 5 minutes～5 hours, preferred 30 minutes～3 hours, add 0.01～100 part of reductive agent again, preferred 3～30 parts, continue to grind 5 minutes～10 hours, preferred 2 hours～4 hours, obtain stable polymer/Graphene composite emulsion;
Wherein, the polymer emulsion solid content is 10%～85% natural rubber latex, styrene-butadiene latex, butadiene latex, isoprene rubber latex, nitrile rubber, isobutylene-isoprene latex, silicon rubber emulsion, polyacrylate dispersion, ABS emulsion, polyaminoester emulsion, EVA emulsion, at least a in PVA emulsion and the polymethylmethacrylate emulsion; Graphite oxide is one or more layers; Solvent is water, ethanol, ritalin, benzene, toluene, hexane, hexanaphthene, acetone, tetrahydrofuran (THF), N, at least a in dinethylformamide and the phenol; Reductive agent is at least a in hydrazine hydrate, sodium borohydride, n-Butyl Amine 99, quadrol, vitamins C and the natrium hydrocitricum;
(2) preparation of polymer/graphene composite master batch
Above-mentioned polymer/graphene composite emulsion is added 0.01～30 part of emulsion splitter, preferred 1～30 part, in 0～100 ℃ of temperature, preferred 10～100 ℃, breakdown of emulsion 1～60 minute, product be at vacuum tightness 0.1～0.01MPa, preferred 0.1～0.05MPa, dry to constant weight under 10～200 ℃ of the temperature, obtain the polymer/graphene composite master batch;
Wherein, emulsion splitter be in formic acid, sodium chloride solution, Klorvess Liquid, calcium chloride solution or the metabisulfite solution any;
(3) preparation of polymer/graphene composite material
With 0.01～100 part in polymkeric substance, preferred 60～80 parts, 0.01～100 part of polymer/graphene masterbatch, preferred 20～34 parts, with 0.01～100 part of filler, 0.01～20 part of sulphur, 0.01～20 part in zinc oxide, 0.01～10 part of antioxidant, 0.01～40 part in softening agent, 0.01～40 part of fire retardant, 0.01～10 part of catalyzer, 0.01～40 part of suds-stabilizing agent, 0.01～40 part of whipping agent, 0.01～10 part in anti-aging agent and vulcanization accelerator add single screw extrusion machine for 0.01～40 part, twin screw extruder, in Banbury mixer or the two roller mill, in 10～330 ℃ of temperature, preferred 130～230 ℃, melt blending 1～60 minute, mold pressing, extrude or injection moulding, obtain polymer/graphene composite material.
Polymkeric substance is at least a among natural rubber, styrene-butadiene rubber(SBR), divinyl rubber, polyisoprene rubber, paracril, isoprene-isobutylene rubber, chloroprene rubber, silicon rubber, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, polystyrene, polyacrylonitrile, polymeric amide, polyoxymethylene, Resins, epoxy, resol, urethane, polyvinyl chloride, poly(lactic acid), ABS, EVA and the PVA.
Filler is at least a in lime carbonate, carbon black, silicon-dioxide, kaolin and the mica powder.
Oxidation inhibitor is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) at least a in positive octadecanol ester of propionic acid and tricresyl phosphite (2, the 4-di-t-butyl) ester; Anti-aging agent is any in 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2,6 ditertiary butyl p cresol or 2-(2-hydroxyl-3,5 two fourth uncles base phenyl)-5-chlorinated benzotriazole.
Vulcanization accelerator is at least a in benzothiazolyl mercaptan, benzothiazyl disulfide, N-cyclohexyl 2-[4-morpholinodithio sulphenamide, tetramethylthiuram monosulfide, ziram, vulkacit D and the ethylene thiourea; Catalyzer is dibutyltin diacetate, triethylamine, N, N-dimethyl tetrahydrobenzene, two (2-dimethylaminoethyl) ether triethylenediamine and N, at least a in the N-lutidine.
Whipping agent is any in water, dichloro one fluoroethane or the pentamethylene; Suds-stabilizing agent is at least a in non-hydrolysis-type polysiloxane-polyether copolymer of silicon-carbon bond and the polyether-modified polysiloxane.
Fire retardant is chloro phosphoric acid ester or trimeric cyanamide.
Softening agent is at least a in stearic acid, phthalic ester and the aliphatics dicarboxylic acid esters.
The polymer/graphene composite material that the in-situ reduction preparation method of polymer/graphene composite material prepares.
Polymer/graphene composite material is used for electro-conductive material, stealth material, cushioning material, tire or thermally conductive material field.
Oxidation inhibitor, anti-aging agent, vulcanization accelerator, catalyzer, whipping agent, suds-stabilizing agent, fire retardant and softening agent, these auxiliary agents are technology known in the art, its precondition be these additives adding not with realize purpose of the present invention and obtain excellent results of the present invention having a negative impact.
Performance test
The mechanical property of the polymer/graphene composite material that in-situ reduction preparation method prepares, plastic materials adopts the testing method of GB/T 1447-2005, the tensile strength that records is 30～120MPa, tensile modulus is 300～5000MPa, adopt the testing method of GB/T 1449-2005, recording flexural strength is 40～170MPa; Rubber type of material adopts the GB/T528-1998 testing method, and the tensile strength that records is 30～50MPa, and adopting GB/T 529-1999 test tear strength is 20～80MPa, sees for details shown in table 1 and the table 2.
The present invention has following advantage
1, the in-situ reduction preparation method of the present invention's employing is uniformly dispersed Graphene in polymeric matrix, obtains high-quality product, compare with the polymeric matrix physical and mechanical properties that does not add Graphene, and tensile strength, tensile modulus has improved 5～80%.And can prepare semi-conductor or conductor polymer/graphene composite material.
2, preparation technology is simple, and temperature of reaction is lower, is easy to control, and energy consumption is low.
3, do not produce waste gas and waste liquid in the production process of the present invention, environmentally friendly.
Embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
Graphite oxide 2.5kg and the adding of 1600kg water are had in the reactor of ultrasonic generating unit, ultrasonic power is 200W, frequency is 200Hz, and temperature is 40 ℃, ultra-sonic dispersion 1 hour, obtain graphite oxide solution, add natural rubber latex 32.3kg, continued ultra-sonic dispersion 1 hour, add hydrazine hydrate 12kg, with continuing ultra-sonic dispersion 2 hours, obtain natural rubber latex/Graphene composite emulsion.With formic acid emulsion splitter 5kg, in 80 ℃ of temperature, breakdown of emulsion 5 minutes, product be at vacuum tightness 0.09MPa, dries to constant weight under 40 ℃ of the temperature, obtains natural rubber/Graphene composite master batch.
The Graphene that the 20kg natural rubber coats, 80kg natural rubber, 5kg zinc oxide, the 3kg stearic acid, 3kg sulphur, 4kg N-sec.-propyl-N '-diphenyl-para-phenylene diamine, 1.5kgN-cyclohexyl 2-[4-morpholinodithio sulphenamide and 0.3kg benzothiazyl disulfide mix by two rollers, the time is 20 minutes.Prepare natural rubber/graphene composite material by molded vulcanization, curing temperature is 130 ℃, and curing time is 50 minutes.
Embodiment 2
Graphite oxide 100kg and 3000kg ethanol are added in the shredder, milling time is 1.5 hours, obtain graphite oxide solution, add polymethylmethacrylate emulsion 300kg, ground 1.5 hours, add sodium borohydride solution 8kg again, continue to grind 2 hours, obtain polymethylmethacrylate/Graphene composite emulsion.Use sodium chloride solution 30kg, in 100 ℃ of temperature, breakdown of emulsion 60 minutes, product be at vacuum tightness 0.1MPa, dries to constant weight under 230 ℃ of the temperature, obtains polymethylmethacrylate/Graphene composite master batch.
The Graphene that the 34kg polymethylmethacrylate coats, the 70kg polymethylmethacrylate, two (tribromophenoxy) ethane of 13kg and 7kg lead sesquioxide are by extruding preparation polymethylmethacrylate/graphene composite material, and extrusion temperature is 200 ℃.
Embodiment 3
Graphite oxide 0.01kg and 100kgDMF are added in the ultrasound wave irradiation reactor, start ultrasonic cell disruptor, ultrasonic power is 10000W, and frequency is 20000Hz, temperature is 60 ℃, 30 minutes ultra-sonic dispersion time obtained graphite oxide solution, added EVA latex 5kg, continued ultrasonic 30 minutes, add quadrol 4kg again, continued ultrasonic 3 hours, prepare stable EVA/ Graphene composite emulsion.Utilize metabisulfite solution 1kg, in 10 ℃ of temperature, breakdown of emulsion 1 minute, product be at vacuum tightness 0.05MPa, dries to constant weight under 50 ℃ of the temperature, obtains EVA/ Graphene composite master batch.
The Graphene that 21kgEVA coats, 80kg EVA, 20kg lime carbonate and 3kg stearic acid extrude by twin screw extruder earlier and mix, and extrusion temperature is 180 ℃.Granulation, after the drying again injection moulding prepare the EVA/ graphene composite material.Injection temperature is 180 ℃.
Embodiment 4
Graphite oxide 8kg and 900kg water are added in the shredder, and milling time is 2 hours, obtains graphite oxide solution, add nitrile rubber 20kg, continue to grind 2 hours, add n-Butyl Amine 99 7kg again, continued ultrasonic 4 hours, and prepared stable nitrile rubber/Graphene composite emulsion.Klorvess Liquid 20kg, in 50 ℃ of temperature, breakdown of emulsion 10 minutes, product be at vacuum tightness 0.1MPa, dries to constant weight under 100 ℃ of the temperature, obtains paracril/Graphene composite master batch.
The Graphene that the 22kg paracril coats, the 80kg paracril, the 40kg carbon black, 7kg zinc oxide, the 6kg stearic acid, 7kg sulphur, 0.2kg benzothiazolyl mercaptan and 6kg phthalic ester mix by Banbury mixer, and temperature is 100 ℃, and the time is 30 minutes.Sulfuration preparation paracril/graphene composite material, curing temperature is 180 ℃, curing time is 50 minutes.
Embodiment 5
Graphite oxide 1.25kg and 300kg water are added in the ultrasound wave irradiation reactor, start the ultrasonic cleaning instrument, power is 200W, and frequency is 600Hz, temperature is 40 ℃, 1 hour ultra-sonic dispersion time obtained graphite oxide solution, added natural rubber latex 40kg, continued ultra-sonic dispersion 1 hour, add hydrazine 3kg again, continued ultra-sonic dispersion 2 hours, prepare stable natural rubber latex/Graphene composite emulsion.Use formic acid 10kg, in 50 ℃ of temperature, breakdown of emulsion 20 minutes, product be at vacuum tightness 0.1MPa, dries to constant weight under 80 ℃ of the temperature, obtains natural rubber/Graphene composite master batch.
The Graphene that the 24kg natural rubber coats, 60kg natural rubber, 20kg styrene-butadiene rubber(SBR), the 45kg carbon black, 8kg zinc oxide, 4kg sulphur, 5kg stearic acid and 5kg four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester mixes by two rollers, and the time is 25 minutes.Sulfuration preparation natural rubber/styrene-butadiene rubber(SBR)/graphene composite material, curing temperature is 160 ℃, curing temperature is 45 minutes.
Embodiment 6
Graphite oxide 1.25kg and 500kg water are added in the ultrasound wave irradiation reactor, start the ultrasonic cleaning instrument, ultrasonic power is 200W, and frequency is 600Hz, temperature is 100 ℃, 2 hours ultra-sonic dispersion time obtained graphite oxide solution, added natural rubber latex 40kg, continued ultra-sonic dispersion 3 hours, add hydrazine 3kg again, continued ultra-sonic dispersion 4 hours, obtain stable ABS latex/Graphene composite emulsion.Ammonium chloride solution 8kg, in 70 ℃ of temperature, breakdown of emulsion 40 minutes, product be at vacuum tightness 0.08MPa, dries to constant weight under 30 ℃ of the temperature, obtains ABS/ Graphene composite master batch.
The Graphene that the 24kg natural rubber coats, 60kg natural rubber, 20kgABS, 10kg carbon black, 8kg zinc oxide, 4kg sulphur, 4kg stearic acid and 5kg β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid mixes by Banbury mixer, and the time is 25 minutes, and temperature is 100 ℃.Sulfuration preparation natural rubber/ABS/ graphene composite material, curing temperature is 160 ℃, curing temperature is 45 minutes.
Comparison example 1
Natural rubber latex 32.3kg and 1600kg water are added in the reactor, and with formic acid emulsion splitter 5kg, in 80 ℃ of temperature, breakdown of emulsion 5 minutes, product be at vacuum tightness 0.09MPa, dries to constant weight under 40 ℃ of the temperature, obtains breakdown of emulsion rubber.
20kg breakdown of emulsion rubber, 0kg natural rubber, 5kg zinc oxide, the 3kg stearic acid, 3kg sulphur, 4kg N-sec.-propyl-N '-diphenyl-para-phenylene diamine, 1.5kg N-cyclohexyl 2-[4-morpholinodithio sulphenamide and 0.3kg benzothiazyl disulfide mix by two rollers, the time is 20 minutes.Prepare the natural rubber material by molded vulcanization, curing temperature is 150 ℃, and curing time is 50 minutes.
Comparison example 2
With polymethylmethacrylate emulsion 300kg and 3000kg ethanol, use sodium chloride solution 30kg, in 100 ℃ of temperature, breakdown of emulsion 60 minutes, product be at vacuum tightness 0.1MPa, dries to constant weight under 230 ℃ of the temperature, obtains the polymethylmethacrylate masterbatch.
34kg polymethylmethacrylate masterbatch, the 70kg polymethylmethacrylate, two (tribromophenoxy) ethane of 13kg and 7kg lead sesquioxide are by extruding preparation polymethylmethacrylate/graphene composite material, and extrusion temperature is 200 ℃.
Table 1 does not add the natural rubber of Graphene and natural rubber/graphene composite material of the present invention's preparation compares *
| Torque capacity N.m | Tensile strength MPa | Tensile modulus MPa | 300% stress at definite elongation MPa | Elongation at break % | Tear strength N/mm | Specific conductivity S/m | |
| Comparison example 1 | ??2.2 | ??17 | ??7.6 | ??2.4 | ??579 | ??32 | ??- |
| Embodiment 1 | ??2.4 | ??25 | ??8.8 | ??6.6 | ??563 | ??49 | ??0.009 |
* according to the tensile property of GB/T 528-1998 test comparison example 1 and embodiment 1, according to the tear resistance of GB/T 529-1999 test comparison example 1 and embodiment 1, according to the conductivity of GB2439-2001 test comparison example 1 and embodiment 1.
Table 2 does not add the polymethylmethacrylate of Graphene and polymethylmethacrylate/graphene composite material of the present invention's preparation compares *
| Tensile strength MPa | Tensile modulus GPa | Elongation at break % | Flexural strength MPa | Specific conductivity S/m | |
| Comparison example 2 | ?60 | ?2.4 | ??2.2 | ??98 | ??- |
| Embodiment 2 | ?76 | ?2.9 | ??3.0 | ??118 | ??0.0013 |
* according to the tensile property of GB/T 1447-2005 test comparison example 2 and embodiment 2, according to the flexural strength of GB/T 1449-2005 test comparison example 2 and embodiment 2.
Annotate: the non-hydrolysis-type polysiloxane-polyether copolymer of silicon-carbon bond is that rain field, Shanghai chemical industry company limited produces.
Polyether-modified polysiloxane is that Guangzhou Si Luoke chemistry company limited produces.
Claims (10)
1. the in-situ reduction preparation method of polymer/graphene composite material is characterized in that this method may further comprise the steps:
(1) preparation of polymer/graphene composite emulsion in-situ reducing
A) ultrasonic dispersion: graphite oxide 0.01～10 weight part and solvent 100～3000 weight parts are added in the ultrasound wave irradiation reactor, at ultrasonic power is 10～50000W, frequency is 10～100000Hz, 20～200 ℃ of temperature, 5 minutes～5 hours ultra-sonic dispersion time, obtain graphite oxide solution, add polymer emulsion 5～300 weight parts, continued ultra-sonic dispersion 5 minutes～5 hours, add 0.01～100 part of reductive agent again, continue ultra-sonic dispersion 5 minutes～10 hours, and obtained stable polymer/Graphene composite emulsion;
B) grind dispersing method: graphite oxide 0.01～10 weight part and solvent 100～3000 weight parts are added in the shredder, ground 5 minutes～5 hours, obtain graphite oxide solution, add polymer emulsion 5～300 weight parts, continue to grind 5 minutes～5 hours, add reductive agent 0.01～100 weight part again, continue to grind 5 minutes～10 hours, obtain stable polymer/Graphene composite emulsion;
Wherein, the polymer emulsion solid content is 10%～85% natural rubber latex, styrene-butadiene latex, butadiene latex, isoprene rubber latex, nitrile rubber, isobutylene-isoprene latex, silicon rubber emulsion, polyacrylate dispersion, ABS emulsion, polyaminoester emulsion, EVA emulsion, at least a in PVA emulsion and the polymethylmethacrylate emulsion; Graphite oxide is one or more layers; Solvent is water, ethanol, ritalin, benzene, toluene, hexane, hexanaphthene, acetone, tetrahydrofuran (THF), N, at least a in dinethylformamide and the phenol; Reductive agent is at least a in hydrazine hydrate, sodium borohydride, n-Butyl Amine 99, quadrol, vitamins C and the natrium hydrocitricum;
(2) preparation of polymer/graphene composite master batch
Above-mentioned polymer/graphene composite emulsion is added emulsion splitter 0.01～30 weight part, and in 0～100 ℃ of temperature, breakdown of emulsion 1～60 minute, product be at vacuum tightness 0.1～0.01MPa, dries to constant weight under 10～200 ℃ of the temperature, obtains the polymer/graphene composite master batch;
Wherein, emulsion splitter be in formic acid, sodium chloride solution, Klorvess Liquid, calcium chloride solution or the metabisulfite solution any;
(3) preparation of polymer/graphene composite material
With polymkeric substance 0.01～100 weight part, polymer/graphene masterbatch 0.01～100 weight part and filler 0.01～100 weight part, sulphur 0.01～20 weight part, zinc oxide 0.01～20 weight part, antioxidant 0.01～10 weight part, softening agent 0.01～40 weight part, fire retardant 0.01～40 weight part, catalyzer 0.01～10 weight part, suds-stabilizing agent 0.01～40 weight part, whipping agent 0.01～40 weight part, anti-aging agent 0.01～10 weight part and vulcanization accelerator 0.01～40 weight part add single screw extrusion machine, twin screw extruder, in Banbury mixer or the two roller mill, in 10～330 ℃ of melt blendings of temperature 1～60 minute, mold pressing, extrude or injection moulding, obtain polymer/graphene composite material.
2. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1 is characterized in that polymkeric substance is at least a among natural rubber, styrene-butadiene rubber(SBR), divinyl rubber, polyisoprene rubber, paracril, isoprene-isobutylene rubber, chloroprene rubber, silicon rubber, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, polystyrene, polyacrylonitrile, polymeric amide, polyoxymethylene, Resins, epoxy, resol, urethane, polyvinyl chloride, poly(lactic acid), ABS, EVA and the PVA.
3. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1 is characterized in that filler is at least a in lime carbonate, carbon black, silicon-dioxide, kaolin and the mica powder.
4. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1, it is characterized in that oxidation inhibitor is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) at least a in positive octadecanol ester of propionic acid and tricresyl phosphite (2, the 4-di-t-butyl) ester; Anti-aging agent is any in 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2,6 ditertiary butyl p cresol or 2-(2-hydroxyl-3,5 two fourth uncles base phenyl)-5-chlorinated benzotriazole.
5. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1 is characterized in that vulcanization accelerator is at least a in benzothiazolyl mercaptan, benzothiazyl disulfide, N-cyclohexyl 2-[4-morpholinodithio sulphenamide, tetramethylthiuram monosulfide, ziram, vulkacit D and the ethylene thiourea; Catalyzer is dibutyltin diacetate, triethylamine, N, N-dimethyl tetrahydrobenzene, two (2-dimethylaminoethyl) ether triethylenediamine and N, N-lutidine at least a.
6. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1 is characterized in that whipping agent is any in water, dichloro one fluoroethane or the pentamethylene; Suds-stabilizing agent is at least a in non-hydrolysis-type polysiloxane-polyether copolymer of silicon-carbon bond and the polyether-modified polysiloxane.
7. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1 is characterized in that fire retardant is chloro phosphoric acid ester or trimeric cyanamide.
8. the in-situ reduction preparation method of polymer/graphene composite material according to claim 1 is characterized in that softening agent is at least a in stearic acid, phthalic ester and the aliphatics dicarboxylic acid esters.
9. the polymer/graphene composite material for preparing according to the in-situ reduction preparation method of the described polymer/graphene composite material of claim 1.
10. be used for electro-conductive material according to the described polymer/graphene composite material of claim 9, stealth material, cushioning material, tire or thermally conductive material field.
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