CN101418107A - Nano graphite high conductivity composite material and preparation method - Google Patents
Nano graphite high conductivity composite material and preparation method Download PDFInfo
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- CN101418107A CN101418107A CNA2007101337296A CN200710133729A CN101418107A CN 101418107 A CN101418107 A CN 101418107A CN A2007101337296 A CNA2007101337296 A CN A2007101337296A CN 200710133729 A CN200710133729 A CN 200710133729A CN 101418107 A CN101418107 A CN 101418107A
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Abstract
The invention discloses a high-conductivity composite material made of nano graphite, which consists of the following components in weight percentage: 80 to 99 percent of polymer matrix, and 1 to 20 percent of the nano graphite. The nano graphite has high radius-thickness ratio; and less nano graphite can be used for forming an effective conducting network in a polymer, while low content of nano graphite conductive stuffing can make a conductive polymer material keep the prior good mechanical property. The high-conductivity composite material made of the nano graphite has a volume conductivity up to 2.5 x 10<-1> S/cm, and has excellent properties of low stuffing amount and high conductivity compared with the prior natural graphite and expansion graphite conductive composite materials.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of high conductivity composite material that contains nano-graphite with and preparation method thereof.
Background technology
Most polymer conductivities are very low, and the raising of polymer conductivity normally by adding a certain amount of electro-conductive material, connects into conductive path by conductive filler material, thereby makes polymer materials have certain electroconductibility.Conductive filler material mostly is natural graphite, expanded graphite, carbon black, acetylene black etc. in the prior art, conductive filler material loading level used in the system is big, the percolation threshold height, bigger to the intensity of matrix material and toughness infringement, and caused the decline of conducing composite material processing characteristics.At present, paracril/expanded graphite matrix material, its volume conductance only is 10 when expanded graphite packing content reaches 10wt%
-9The S/cm order of magnitude; Polypropylene/expanded graphite matrix material, its volume conductance only reaches 10 when expanded graphite packing content reaches 10wt%
-10The S/cm order of magnitude (referring to China Plastics, 2006, Vol.20,62-65); And polyethylene/expanded graphite matrix material, its volume conductance just can reach 10 when expanded graphite packing content reaches 36wt%
-4The S/cm order of magnitude, and expanded graphite packing content when reaching 2wt% its volume conductance only can reach 10
-12The S/cm order of magnitude (referring to Acta Materiae Compositae Sinica, 2005, Vol.22,15-21); Urethane/expanded graphite matrix material, its volume conductance just reaches 10 when expanded graphite packing content reaches 35wt%
-3The S/cm order of magnitude; Urethane/natural graphite matrix material, its volume conductance only reaches 10 when natural graphite packing content reaches 35wt%
-7The S/cm order of magnitude (referring to China Plastics, 2004, Vol.18,43-46).
Compare with above-mentioned graphite packing, the thickness of nano-graphite is nano level, and diameter is a micron order, has high radius-thickness ratio, therefore can reduce the consumption of conductive filler material greatly, reduces the percolation threshold of system, makes material have the light-weight characteristic.
Graphite is dispersed in the polymeric matrix, can prepares the polymer/graphite conducing composite material.If graphite disperses with the nano level graphite wafer in polymeric matrix, then the conduction of polymer/graphite conducing composite material exceedes that to ooze threshold values low, promptly under the low situation of graphite consumption, just can in the polymer/graphite conducing composite material, form the spatial conductive network, show excellent conductivity.
Summary of the invention
The objective of the invention is in order to overcome the low problem of polymer conductivity, the characteristic of combining nano graphite provides a kind of high conductivity light-weight polymer composites that contains nano-graphite.
Another object of the present invention provides a kind of preparation method of above-mentioned polymer composites.
Purpose of the present invention can reach by following measure:
A kind of nano graphite high conductivity composite material, it is made up of polymeric matrix and nano-graphite, and its weight percent content is: polymeric matrix 80～99%, nano-graphite 1～20%; Be preferably polymeric matrix 90～99%, nano-graphite 1～10%.Wherein polymeric matrix is polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, poly-n-methylolacrylamide, polyvinyl acetate (PVA), polyvinyl alcohol, Polyvinylpyrolidone (PVP) or polyoxyethylene glycol; Nano-graphite is the nano graphite flakes that is got by the graphite oxide reduction, its thickness 1～20 nanometer, and radius-thickness ratio is 100～2000.
A kind of preparation method of nano graphite high conductivity composite material, earlier graphite oxide is scattered in the liquid medium, dispersion liquid is through supersound process, mix with polymerization single polymerization monomer solution again carry out in-situ polymerization or with the direct intercalation of polymers soln, make plural gel or composite solution; At last plural gel or composite solution are handled through the reductive agent reduction, washing is dry, obtains nano graphite high conductivity composite material.Wherein graphite oxide and polymer/polymer monomer weight ratio are preferably 1:99～1:4.
Earlier graphite oxide is scattered in the liquid medium, dispersity is 0.03～1g/100ml, and preferred 0.06～0.4g/100ml, dispersion solvent are selected from one or more in water, ethanol, acetone, Virahol, dimethyl formamide or the methyl-sulphoxide; The graphite oxide dispersion liquid supersound process time is 10min～5h, preferred 0.5～3h; The graphite oxide dispersion liquid is dissolved in polymer monomer in the solvent with comprising elder generation mixing of polymerization single polymerization monomer, mixes with the graphite oxide dispersion liquid again, also comprises polymer monomer directly is dissolved in the dispersion liquid of graphite oxide; Mix the concentration of polymers soln before or polymer monomer solution smaller or equal to its maxima solubility with the graphite oxide dispersion liquid, the solvent of dissolve polymer or polymerization single polymerization monomer is selected from one or more in water, ethanol, acetone, Virahol, dimethyl formamide or the methyl-sulphoxide, and it can be the same or different with the solvent that disperses graphite oxide; The in-situ polymerization that carries out after the mixing is conventional in-situ polymerization, used initiator is a normal starter, as ammonium persulphate etc., or redox initiation system, as persulphate-bisulfite salt initiators etc., it is monomeric 0.5 ‰～1% that its consumption is generally, and preferred methods is for to react reactant 4～12 hours under 50～80 ℃ of nitrogen protections among the present invention; The graphite oxide dispersion liquid mixes the graphite oxide dispersion liquid for elder generation with the direct intercalation process of polymers soln with polymers soln, mixed solution is carried out ultrasonication again, and ultrasonic treatment time is 1～180min, best 1～60min; When reduction is handled, with reductive agent reduction 10～30h under 80～120 ℃, wherein reductive agent is hydrazine hydrate, dimethylhydrazine or the mixture of the two, and wherein the reductive agent consumption is (0.03～0.6mol) reductive agent/1g graphite oxide, preferred (0.1～0.3mol) reductive agent/1g graphite oxide.
Supersound process of the present invention can be used conventional ultrasonic device, and preferred ultrasonic frequency is 25～120kHz.
In above-mentioned preparation method, graphite oxide is to be that raw material gets by Hummer method oxide treatment that (the Hummer method is referring to J.Am.Chem.Soc.1958 with the natural graphite; 80:1339), comprise the graphite oxide slurry of oxidation gained and the product after the vacuum-drying, thickness 1～20 nanometer, radius-thickness ratio is 100～2000.
Wherein polymkeric substance is polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, polyvinyl acetate (PVA), poly-n-methylolacrylamide, polyvinyl alcohol, Polyvinylpyrolidone (PVP) or polyoxyethylene glycol, wherein:
Polyacrylamide:
Polyacrylic acid:
Polymethyl acrylate:
Polymethylmethacrylate:
Butyl polyacrylate:
Polyvinyl acetate (PVA)
Poly-n-methylolacrylamide:
Polyvinyl alcohol:
Polyvinylpyrolidone (PVP):
Polyoxyethylene glycol:
Polymethyl acrylic acid:
Wherein polymerization single polymerization monomer is selected from one or more in acrylamide, N hydroxymethyl acrylamide, methyl acrylate, methyl methacrylate, butyl acrylate or the Vinyl Acetate Monomer.
A kind of preferred manufacturing procedure of high conductivity polymer composites of the present invention is as follows:
A. polymkeric substance carries out directly reducing behind the solution blending:
(1) graphite oxide is dispersed in the liquid medium, is prepared into to disperse liquid A stand-by, and dispersion concentration is 1g/100ml～1g/3000ml, best 1g/250ml～1g/1500ml.Get a certain amount of polymer dissolution and be prepared into solution B in the solvent of proper ratio.
(2) with dispersion liquid A supersound process, the supersound process time is 10 minutes～5 hours, best 0.5～3 hour.Be mixed with into mixed solution A B with solution B then;
(3) with mixed solution A B ultrasonic sonication 1～60 minute, best 3～20 minutes.Add an amount of reductive agent reduction, then polymer composites is separated out, flush away reductive agent, oven dry.
B. reduce behind the polymer monomer in-situ polymerization:
(1) graphite oxide is dispersed in the liquid medium, is prepared into to disperse liquid A stand-by, and dispersion concentration is 0.03g/100ml～1g/100ml, best 0.07g/100ml～0.4g/100ml.Monomer is dissolved in the solution C that a certain proportion of solvent is prepared into proper ratio.
(2) with dispersion liquid A supersound process, the supersound process time is 10 minutes-5 hours, best 0.5-3 hour.Be mixed with into mixed solution A C with solution C then, add initiator etc. then and carry out in-situ polymerization, obtain containing the composition polymer D of graphite oxide.
(3) will contain the composition polymer gel of graphite oxide or solution D and add an amount of reductive agent reduction, then polymer composites be separated out flush away reductive agent, oven dry.
The drying conditions of product of the present invention is in the vacuum drying oven 25 ℃～50 ℃, best 30 ℃, dry 16～48 hours, best 24 hours.
After adopting such scheme, nano-graphite of the present invention has high radius-thickness ratio, uses less nano-graphite just can form effective conductive network in polymkeric substance.And low nano-graphite conductive filler material content can make conducting polymer materials keep original excellent mechanical performances.Nano-graphite/polyoxyethylene glycol matrix material wherein, when the nano-graphite filler content was 2wt%, its volume conductance can reach 7.9*10
-2S/cm, when the nano-graphite filler content is 6wt%, its volume conductance even can reach 2.5*10
-1S/cm contrast the excellent properties that traditional natural graphite, expanded graphite conducing composite material have low sizing amount high conductivity, and other nano-graphite conducing composite materials of the present invention has similar characteristic too.
Embodiment
1, related concrete pharmaceutical chemicals among the present invention:
N hydroxymethyl acrylamide (analytical pure): Tianjin chemical reagent institute; Acrylamide (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Polyoxyethylene glycol-4000 (chemical pure): Shanghai Ling Feng chemical reagent company limited; Polyvinylpyrolidone (PVP) K-30 (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Ammonium persulphate (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Hydrazine hydrate (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group, concentration 85%; Acetone (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Natural graphite: Chemical Reagent Co., Ltd., Sinopharm Group, 12000 orders; The vitriol oil (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Potassium permanganate (analytical pure): Dihua worker company limited is won in Tianjin; SODIUMNITRATE (analytical pure): Shanghai green grass or young crops is analysed Chemical Industry Science Co., Ltd; Hydrogen peroxide 30% (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group.
2, graphite oxide preparation method:
Get a certain amount of natural graphite, SODIUMNITRATE, add the vitriol oil that places ice bath constantly to stir, an amount of potassium permanganate slowly adds wherein, prevent that mixeding liquid temperature from surpassing 20 ℃, remove ice bath, mixed solution is placed 35 ℃ of water-bath constant temperature 30min-7h, best 4h, with the deionized water dilution, mixeding liquid temperature sharply rises, holding temperature is at 90 ℃ of-98 ℃ of 15min, dilute once more with deionized water, add hydrogen peroxide and become glassy yellow to the mixed solution color, filtered while hot, rare HCl washing 3 times, deionized water is washed till no SO
4 2-Ion, it is stand-by to get the gluey graphite oxide of suction filtration gained brown.Wherein oxidized graphite flake thickness is 1～10 nanometer, and radius-thickness ratio is 100～2000.
Embodiment 1:
Graphite oxide 0.1g is scattered in 50mlH
2O, supersound process 3h, n-methylolacrylamide 5g is dissolved in 50mlH
2O; solution mixes the back in-situ polymerization, and (initiator: ammonium persulphate 0.005g): 70 ℃ of nitrogen protections are reacted down and were made polymer gel in 10 hours; get and make gel 20g; with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours; separate out with acetone; filter the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 5.8*10
-4S/cm.
Embodiment 2:
Graphite oxide 0.1g is scattered in 50mlH
2O, supersound process 3h, acrylamide 5g is dissolved in 50mlH
2O; solution mixes the back in-situ polymerization, and (initiator: ammonium persulphate 0.005g): 65 ℃ of nitrogen protections are reacted down and were made polymer gel in 10 hours; get and make gel 5g; with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours; separate out with acetone; filter the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 1.2*10
-4S/cm.
Embodiment 3:
Graphite oxide 0.1g is scattered in 50mlH
2O, supersound process 3h, polyoxyethylene glycol 5g is dissolved in 25mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 7.9*10
-2S/cm.
Embodiment 4:
Graphite oxide 0.2g is scattered in 100mlH
2O, supersound process 3h, polyoxyethylene glycol 5g is dissolved in 25mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 1.9*10
-1S/cm.
Embodiment 5:
Graphite oxide 0.3g is scattered in 150mlH
2O, supersound process 3h, polyoxyethylene glycol 5g is dissolved in 25mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 2.5*10
-1S/cm.
Embodiment 6:
Graphite oxide 0.2g is scattered in 100mlH
2O, supersound process 3h, Polyvinylpyrolidone (PVP) 2g is dissolved in 20mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 1.5*10
-5S/cm.
Embodiment 7:
Graphite oxide 0.1g is scattered in 50mlH
2O, supersound process 3h, polyvinyl alcohol 5g is dissolved in 20mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 7.4*10
-3S/cm.
Embodiment 8:
Graphite oxide 0.1g is scattered in 50mlH
2O, supersound process 3h, polyacrylic acid 5g is dissolved in 20mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 8.9*10
-3S/cm.
Embodiment 9:
Graphite oxide 0.1g is scattered in 50mlH
2O, supersound process 3h, polymethyl acrylic acid 5g is dissolved in 20mlH
2O, solution mix the back with the 50ml hydrazine hydrate 100 ℃ of reductase 12s 4 hours, separate out with acetone, filter, the flush away reductive agent, 30 ℃ of dryings are 24 hours in the vacuum drying oven.
Above-mentioned polymer composites volume conductance can reach 2.3*10
-2S/cm.
Claims (15)
1, a kind of nano graphite high conductivity composite material is characterized in that it is made up of polymeric matrix and nano-graphite, and its weight percent content is: polymeric matrix 80～99%, nano-graphite 1～20%.
2,, it is characterized in that the weight percent content of polymeric matrix and nano-graphite is in this matrix material: polymeric matrix 90～99%, nano-graphite 1～10% by the described nano graphite high conductivity composite material of claim 1.
3,, it is characterized in that described polymeric matrix is polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, polyvinyl acetate (PVA), poly-n-methylolacrylamide, polyvinyl alcohol, Polyvinylpyrolidone (PVP) or polyoxyethylene glycol by claim 1 or 2 described nano graphite high conductivity composite materials.
4,, it is characterized in that described nano-graphite is the nano graphite flakes that is got by the graphite oxide reduction by claim 1 or 2 described nano graphite high conductivity composite materials.
5, the preparation method of the described nano graphite high conductivity composite material of a kind of claim 1, it is characterized in that earlier graphite oxide being scattered in the liquid medium, dispersion liquid is through supersound process, mix with polymerization single polymerization monomer again carry out in-situ polymerization or with the direct intercalation of polymers soln, make plural gel or composite solution; At last plural gel or composite solution are handled through the reductive agent reduction, washing is dry, obtains nano graphite high conductivity composite material.
6, by the described preparation method of claim 5, it is characterized in that graphite oxide and polymer/polymer monomer weight ratio are 1:99～1:4.
7, by the described preparation method of claim 5, it is characterized in that the dispersity of graphite oxide in liquid medium is 0.03～1g/100ml; Described liquid medium is selected from one or more in water, ethanol, acetone, Virahol, dimethyl formamide or the methyl-sulphoxide.
8, by the described preparation method of claim 5, it is characterized in that the graphite oxide dispersion liquid supersound process time is 10min～5h.
9, by the described preparation method of claim 5, it is characterized in that polymerization single polymerization monomer is selected from one or more in acrylamide, N hydroxymethyl acrylamide, methyl acrylate, methyl methacrylate, butyl acrylate or the Vinyl Acetate Monomer.
10,, it is characterized in that the direct intercalation process of graphite oxide dispersion liquid and polymers soln is earlier the graphite oxide dispersion liquid to be mixed with polymers soln, carries out ultrasonication with mixed solution again by the described preparation method of claim 5.
11,, it is characterized in that described polymkeric substance is polyacrylamide, polyacrylic acid, polymethyl acrylic acid, poly-n-methylolacrylamide, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, polyvinyl acetate (PVA), polyvinyl alcohol, Polyvinylpyrolidone (PVP) or polyoxyethylene glycol by claim 5 or 10 described preparation methods.
12, by the described preparation method of claim 10, it is characterized in that graphite oxide and mixed with polymers liquid ultrasonic treatment time are 1～60min.
13, by claim 5 or 10 described preparation methods, it is characterized in that ultrasonic frequency is 25～120kHz.
14, by the described preparation method of claim 5, when it is characterized in that reduction is handled, with reductive agent reduction 10～30h under 80～120 ℃.
15, by claim 5 or 14 described preparation methods, it is characterized in that reductive agent is hydrazine hydrate, dimethylhydrazine or the mixture of the two, wherein the reductive agent consumption is 0.03～0.6mol reductive agent/1g graphite oxide.
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| CN102154053A (en) * | 2011-03-28 | 2011-08-17 | 陈强 | Nanographite additive for water-based cutting fluid and preparation method thereof |
| CN102585335A (en) * | 2012-03-14 | 2012-07-18 | 吉林大学 | Method for preparing polyethylene/graphene conductive composite material |
| CN103172857A (en) * | 2013-04-11 | 2013-06-26 | 常州和方环保科技有限公司 | Preparation method and use of high-conductivity composite material |
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| CN102154053A (en) * | 2011-03-28 | 2011-08-17 | 陈强 | Nanographite additive for water-based cutting fluid and preparation method thereof |
| CN102585335A (en) * | 2012-03-14 | 2012-07-18 | 吉林大学 | Method for preparing polyethylene/graphene conductive composite material |
| CN102585335B (en) * | 2012-03-14 | 2013-05-22 | 吉林大学 | Method for preparing polyethylene/graphene conductive composite material |
| CN103172857A (en) * | 2013-04-11 | 2013-06-26 | 常州和方环保科技有限公司 | Preparation method and use of high-conductivity composite material |
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| CN105706179B (en) * | 2014-01-09 | 2017-12-19 | 波音公司 | Electric conductor and its method of formation |
| CN104774413B (en) * | 2015-04-22 | 2017-01-18 | 哈尔滨工业大学 | Polymer-based composite material sensing civil engineering structure super-deformation, and preparation method and application thereof |
| CN104774413A (en) * | 2015-04-22 | 2015-07-15 | 哈尔滨工业大学 | Polymer-based composite material sensing civil engineering structure super-deformation, and preparation method and application thereof |
| CN105131333A (en) * | 2015-09-21 | 2015-12-09 | 武汉纺织大学 | Preparation method of carbon black fluid |
| CN105131333B (en) * | 2015-09-21 | 2018-01-19 | 武汉纺织大学 | A kind of preparation method of carbon black fluid |
| CN106158074A (en) * | 2016-09-08 | 2016-11-23 | 芜湖桑乐金电子科技有限公司 | A kind of lubrication conductive graphite paste and preparation method thereof |
| CN106517173A (en) * | 2016-10-28 | 2017-03-22 | 蚌埠玻璃工业设计研究院 | Preparation method of graphene dispersion liquid |
| CN107353558A (en) * | 2017-05-27 | 2017-11-17 | 南通成山高分子材料有限公司 | A kind of conducting polymer composite |
| CN109306143A (en) * | 2017-07-28 | 2019-02-05 | 张家港市六福新材料科技有限公司 | A kind of conductive nano composite material and preparation method thereof based on graphite |
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