CN101418107B - Nano graphite high conductivity composite material and preparation method - Google Patents

Nano graphite high conductivity composite material and preparation method Download PDF

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Publication number
CN101418107B
CN101418107B CN2007101337296A CN200710133729A CN101418107B CN 101418107 B CN101418107 B CN 101418107B CN 2007101337296 A CN2007101337296 A CN 2007101337296A CN 200710133729 A CN200710133729 A CN 200710133729A CN 101418107 B CN101418107 B CN 101418107B
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graphite
nano
composite material
reductive agent
graphite oxide
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CN101418107A (en
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赵超越
庞斌
杜宁
陈桥
吴刚
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Toray Fibers and Textiles Research Laboratories China Co Ltd
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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

Nano graphite high conductivity composite material and preparation method thereof
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 through adding a certain amount of electro-conductive material, connects into conductive path by conductive filler material, thereby makes polymer materials have certain electroconductibility.Mostly conductive filler material 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; Percolation threshold is high, and is bigger to the intensity and the toughness infringement of matrix material, and caused the decline of conducing composite material processing characteristics.At present, paracril/expanded graphite matrix material, its volume conductance is merely 10 when expanded graphite packing content reaches 10wt% -9The S/cm order of magnitude; Vestolen PP 7052/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 Vilaterm/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.
The object of the invention can reach through 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 SEPIGEL 305, ROHM, polymethyl acrylic acid, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, gathers NMA, PVA, Z 150PH, PVP K120 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 be 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, N 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; The concentration of mixing polymers soln before or polymer monomer solution with the graphite oxide dispersion liquid is smaller or equal to its maxima solubility; The solvent of dissolve polymer or polymerization single polymerization monomer is selected from one or more in water, ethanol, acetone, Virahol, N 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; Like ammonium persulphate etc., or redox initiation system, like persulphate-bisulfite salt initiators etc.; It is monomeric 0.5 ‰～1% that its consumption is generally, and preferred methods is that reactant was reacted 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, again mixed solution is carried out ultrasonication, 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 80, 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 SEPIGEL 305, ROHM, polymethyl acrylic acid, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, PVA, gathers NMA, Z 150PH, PVP K120 or polyoxyethylene glycol, wherein:
Polyacrylamide:
Figure S2007101337296D00031
polyacrylic acid:
Figure S2007101337296D00032
Polymethylacrylate:
Figure S2007101337296D00033
poly (methyl methacrylate):
Figure S2007101337296D00034
PBA:
Figure S2007101337296D00035
PVAc
Figure S2007101337296D00036
Poly-hydroxymethyl acrylamide:
Figure S2007101337296D00037
PVA:
Figure S2007101337296D00038
Polyvinylpyrrolidone:
Figure S2007101337296D00041
Polyethylene Glycol:
Figure S2007101337296D00042
Polymethyl acrylic acid:
Figure S2007101337296D00043
Wherein polymerization single polymerization monomer is selected from one or more in acrylic amide, N hydroxymethyl acrylamide, methyl acrylate, TEB 3K, Bing Xisuandingzhi or the Vinyl Acetate Monomer.
A kind of preferred manufacturing procedure of high conductivity polymer composites of the present invention is following:
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 for use, 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 for use, 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.
Composition polymer gel or the solution D that (3) will contain graphite oxide add an amount of reductive agent reduction, then polymer composites are 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 in polymkeric substance, form effective conductive network.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; Acrylic amide (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Polyoxyethylene glycol-4000 (CP): Shanghai Ling Feng chemical reagent ltd; PVP K120 K-30 (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Ammonium persulphate (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group; Hydrazine Hydrate 80 (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 ltd 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 diluted with deionized water at 90 ℃ of-98 ℃ of 15min once more, adds hydrogen peroxide to mixed solution color and becomes glassy yellow; Filtered while hot, rare HCl washing 3 times, deionized water is washed till no 5O 4 2-Ion, it is for use 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, NMA 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, 100 ℃ of reductase 12s 4 hours, separate out with acetone with the 50ml Hydrazine Hydrate 80; 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 50ml H 2O, supersound process 3h, acrylic amide 5g is dissolved in 50ml H 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, 100 ℃ of reductase 12s 4 hours, separate out with acetone with the 50ml Hydrazine Hydrate 80; 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 50ml H 2O, supersound process 3h, polyoxyethylene glycol 5g is dissolved in 25ml H 2O, solution mix the back with the 50ml Hydrazine Hydrate 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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 100ml H 2O, supersound process 3h, polyoxyethylene glycol 5g is dissolved in 25ml H 2O, solution mix the back with the 50ml Hydrazine Hydrate 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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 150ml H 2O, supersound process 3h, polyoxyethylene glycol 5g is dissolved in 25ml H 2O, solution mix the back with the 50ml Hydrazine Hydrate 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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, PVP K120 2g is dissolved in 20mlH 2O, solution mix the back with the 50ml Hydrazine Hydrate 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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, Z 150PH 5g is dissolved in 20mlH 2O, solution mix the back with the 50ml Hydrazine Hydrate 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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, ROHM 5g is dissolved in 20mlH 2O, solution mix the back with the 50ml Hydrazine Hydrate 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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 80 100 ℃ of reductase 12s 4 hours, separate out with acetone, filtration, 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 (2)

1. the preparation method of a nano graphite high conductivity composite material is characterized in that earlier graphite oxide being scattered in the liquid medium, and dispersion liquid with the direct intercalation of polymers soln, makes composite solution again through supersound process; At last composite solution is handled through the reductive agent reduction; Washing is dry; Obtain the nano graphite high conductivity composite material be made up of polymeric matrix and nano-graphite, this nano graphite high conductivity composite material weight percent content is: polymeric matrix 90～99%, nano-graphite 1～10%;
Wherein, 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;
The dispersity of graphite oxide in liquid medium is 0.03～1g/100ml; Described liquid medium is a water; Polymkeric substance is a polyoxyethylene glycol; Reductive agent is a Hydrazine Hydrate 80, and wherein the reductive agent consumption is 0.03～0.6mol reductive agent/1g graphite oxide;
When reduction is handled, with reductive agent reduction 10～30h under 80～120 ℃;
Graphite oxide and polymer weight ratio are 1: 99～1: 4.
2. by the described preparation method of claim 1, it is characterized in that the graphite oxide dispersion liquid supersound process time is 10min～5h.
CN2007101337296A 2007-10-22 2007-10-22 Nano graphite high conductivity composite material and preparation method Expired - Fee Related CN101418107B (en)

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