CN103748032A - Method for manufacturing conductive water-dispersible nano particles - Google Patents
Method for manufacturing conductive water-dispersible nano particles Download PDFInfo
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- CN103748032A CN103748032A CN201280028262.8A CN201280028262A CN103748032A CN 103748032 A CN103748032 A CN 103748032A CN 201280028262 A CN201280028262 A CN 201280028262A CN 103748032 A CN103748032 A CN 103748032A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to a method for manufacturing conductive water-dispersible nano particles, and more specifically, to a method for manufacturing conductive water-dispersible nano particles characterized by comprising the following steps: (a) making an emulsion by mixing an aqueous solution of thiophene, furan or pyrrole monomers; a compound selected from the group consisting of HCl, HF, HBr and HI; a stabilizer; and a first oxidant; (b) mixing a second oxidant with the emulsion of step (a), then creating conductive particles while stirring the mixture in the emulsion state; and (c) drying the conductive particles in the emulsion state of step (b). When compared to conductive water-dispersible nano particles prepared by conventional methods, the conductive water-dispersible nano particles manufactured according to the present invention demonstrate high electrical conductivity and excellent process ability.
Description
Technical field
The present invention relates to the manufacture method of electric conductivity water-dispersable nanoparticles, it,, according to existing method, has high polymerization degree, and the conducting polymer of manufacturing has good processability and electrical conductivity.
Background technology
Conducting polymer is as a kind of material of ease for use of electricity, magnetic, optical property and general high molecular physical property and the processing can simultaneously with metal, and it is lightweight and soft, and can free adjustment electrical conductivity and electronic state.Thus, can replace existing metal and be applicable to the scope in the fields such as electronic material very wide.The purposes of general conducting polymer is as follows: 1) antistatic additive, waits the static preventing in surface generations such as plastics, macromolecules by coating; 2) capacitor (condenser), replaces electrolyte and uses; 3) tellite (printed circuit board) applies, because it is gold-plated to replace existing metal, so can minimize by environmental pollution; 4) organic electroluminescent (EL, electroluminescence) device, as the hole injection layer (hole injecting layer) of tin indium oxide (ITO, indium tin oxide) substrate.
In addition, conducting polymer has good electric conductivity, but compares with existing general macromolecule, has following shortcoming: for example the mechanical performance of processability is not enough a little.In other words, there is following shortcoming: poor heat stability, solvent resistance (particularly alkali resistance) is low, and the long-term limitation of using.
Particularly, conducting polymer only just has electric conductivity in the situation that P type adulterates, and in the situation that N-type is adulterated, does not have electric conductivity.
In other words, the important role of alloy.Conventionally, the polythiophene (Polythiophene) generating by oxidation high molecular weight reactive is because the oxidant using when manufacturing process is carried out alloy effect, so have electrical conductivity.But, by oxidation high molecular weight reactive polythiophene powder of manufacturing under organic solvent condition, have insolublely, in addition, under the aqueous solution, the polythiophene of the doping of manufacturing exists to be scattered in the state of the aqueous solution by the surfactant that uses etc.In other words, the polythiophene by the manufacturing of oxidation macromolecule method all has insoluble in any solvent.
In addition, polypyrrole and poly-furans are not soluble in organic solvent, thereby be difficult for processing, and the activity to the molecule of polymer backbone (Backbone) limits, thereby can affect electric conductivity, and not only in the doping step of polypyrrole and poly-furans, and very unstable in unadulterated step.
Thus, require now exploitation to be easy to be dissolved in the conducting polymer in various solvents, and record accordingly the manufacture method of polythiophene nano particle in korean patent application No. 10-2005-0093714 and No. 10-2008-0064545, but still in the urgent need to thering is the manufacture method of the conductive nanometer particle of good electrical conductivity and processability.
Summary of the invention
The present invention proposes in order to address the above problem, its object is to provide a kind of manufacture method of electric conductivity water-dispersable nanoparticles and the electric conductivity water-dispersable nanoparticles of manufacturing accordingly, the above-mentioned electric conductivity water-dispersable nanoparticles degree of polymerization is high, and the conducting polymer of manufacturing has good processability and higher electrical conductivity.
To achieve these goals, the invention provides a kind of manufacture method of electric conductivity water-dispersable nanoparticles, it comprises the steps: a) in aqueous solvent thiophene (thiophene), pyrroles (pyrrole) or furans (furan) monomer, select compound, stabilizing agent and the first oxidant in the group that free HCI, HF, HBr and HI form to mix after, manufacture emulsion (emulsion);
B) in above-mentioned steps emulsion a), mix and stir the second oxidant, thus the electroconductive particle of manufacture emulsion state; And
C) to above-mentioned steps b) the electroconductive particle of emulsion state be dried.
In addition, the invention provides a kind of electric conductivity water-dispersable nanoparticles of manufacturing according to said method.
In addition, the invention provides a kind of electronic material, optical material, toner (toner) or ink that utilizes the manufacturing of above-mentioned electric conductivity water-dispersable nanoparticles.
The electric conductivity water-dispersable nanoparticles of the method according to this invention manufacturing is compared with the conductive nanometer particle of existing common manufacturing, shows good processability and high conductivity.
The specific embodiment
The present inventor is in order to overcome the problem of prior art, in repeatedly studying, be conceived to following and completed the present invention: as oxidant, utilize the second oxidant and other oxidants and stabilizing agent (Stabilizer) as denier molysite, above-mentioned other oxidants can again be oxidized it in the situation that above-mentioned the second oxidant will reduce, and especially, carry out at the same time under the existence of the composition of oxygen environment and the material of alloy (dopant) function, in the situation that will manufacture the emulsion of particle, can manufacture the polythiophene with good processability and electric conductivity, polypyrrole and poly-furans particle.
The manufacture method of electric conductivity water-dispersable nanoparticles of the present invention comprises the steps: a) in aqueous solvent thiophene, pyrroles or furans monomer, select compound, stabilizing agent and the first oxidant in the group that free HCI, HF, HBr and HI form to mix after, manufacture emulsion (emulsion); B) in above-mentioned steps emulsion a), mix and stir the second oxidant, thus the electroconductive particle of manufacture emulsion state; And c) to above-mentioned steps b) the electroconductive particle of emulsion state be dried.
The electric conductivity water-dispersable nanoparticles of manufacturing in the present invention can be expressed as following Chemical formula 1.
[Chemical formula 1]
In above-mentioned Chemical formula 1, X represents sulphur, nitrogen, oxygen, phosphorus, silicones or arsenic, R
1and R
2can be respectively alkylene (alkylene), alkylene group (Alkenylene), alkenyloxy (Alkenyloxy), alkene dioxy base (Alkenyl dioxy), alkynyloxy group (alkynyloxy), the alkynes dioxy base (alkynyl dioxy) of hydrogen, halogen (halogen), hydroxyl, C1-C10 alkyl, alkoxyl, carbonyl, 3 to 8 yuan alicyclic (membered alicyclic) or aromatic ring (Aromatic ring) structure independently, above-mentioned except hydrogen, carbon, oxygen atom, can contain the atoms such as nitrogen, sulphur, phosphorus, selenium, silicones.
In the present invention, thiophene as above-mentioned raw materials (Starting Material), pyrroles or furans monomer are to be fabricated to polythiophene by polymerisation, the raw material of polypyrrole and poly-furans, if in affiliated field common used thiophene, pyrroles and furans, use any one all harmless, and as an example, can be expressed as following Chemical formula 2, be preferably and utilize from alkyl epoxy (alkyl ethoxy), carboxyl (Carboxyl group)/sulfo group (Sulfone group) or above-mentioned in the thiophene that replaces of selected more than one substituting group, pyrroles or furans.
[Chemical formula 2]
In above-mentioned Chemical formula 2, X, R
1, R
2with above-mentioned defined identical.
In the present invention, when the compound in the choosing group that freely above-mentioned HCI, HF, HBr and HI form becomes as acid (pH1-6) by reaction solution, act as alloy (dopant), particularly, be preferably HCI.Because use above-mentioned HCI etc., so can manufacture electrical conductivity and the processability of the electric conductivity water-dispersable nanoparticles of the manufacturing according to the present invention, compare with existing conducting polymer the conducting polymer significantly improving.Preferably, to use be 1 to 100 molar ratio (mole ratio) of monomer to the use amount of the compound such as above-mentioned HCI.In above-mentioned, at molar ratio lower than 1 in the situation that, the carrying out of deferred reaction, thereby yield rate is low, and the electrical conductivity of reduction reaction product, and in the situation that molar ratio surpasses 100, the acid number of product is high, thereby be difficult for neutralization, washing, therefore increase manufacturing expense, thereby commercially use some problems that exist.
In addition the solvent that used in the present invention, can mix and use and select free C
6-C
20aliphatic (Aliphatic) and aromatic hydrocarbon based (Aromatic hydrocarbons), halogen-containing hydro carbons (Halogen-containing hydrocarbons), ketone (Ketone), ether (Ether), C
2-C
20ethanol (Alcohol), sulfoxide (Sulfoxide), acid amides (Amide) and more than one or two in the group that forms of water.More specifically, C
6-C
20aliphatic and aromatic hydrocarbon based be hexane (hexane) as alkane (Alkane) class, heptane (heptane), octane (octane), nonane (nonane), decane (Decane), and as the benzene (Benzene) of alkylbenzene (alkylbenzene) class, toluene (Toluene), dimethylbenzene (xylene), isopropylbenzene (cumene), mesitylene (mesitylene), phenol (phenol), cresols (cresol) etc., halogen-containing hydro carbons is carbon tetrachloride (Carbon tetrachloride), chloroform (Chloroform), carrene (Dichloromethane), dichloroethanes (dichloroethane), Bromofume (Dibromoethane), trichloroethanes (Trichloroethane), tribromoethane (Tribromoethane), and as the dichloro-benzenes (Dichlorobenzene) of halobenzene (halobenzene) class, chlorobenzene (Chlorobenzene) etc., and ketone (ketone) class has acetone (acetone), acetone (propanone), butanone (butanone), pentanone (Pentanone), hexanone (Hexanone), heptanone (Heptanone), octanone (octanone), acetophenone (acetophe none) etc., and ether (Ether) class has diethyl ether (Diethyl ether), oxolane (THF), dipropyl ether (Dipropyl ether), butyl oxide (Dibutyl ether), methyl butyl ether (Methyl butyl ether), diphenyl ether (Diphenyl ether), dioxane (dioxane), diethylene glycol dimethyl ether (diglyme), diethylene glycol (DEG) (diethylene glycol), ethylene glycol (EG) etc., and C
2-C
20ethanol (Alcohol), sulfoxide series (Sulfoxide series) there is methyl-sulfoxide (dimethylsulfoxide, DMSO), and acid amides series (Amide series) has N, dinethylformamide (N, N-dimethylformamide, DMF), N-methylacetamide (NMAA), DMA (DMA), N-methyl propanamide (NMPA), 1-METHYLPYRROLIDONE (Nmethylpyrroli dinone, NMP).
Preferably, with respect to above-mentioned monomer 100 weight portions, above-mentioned solvent is used 1,000-3, and the content of 000 weight portion, and applicable polar solvent class, for example, have water and the C of 0-180 ℃ of temperature range
2-C
20ethanol, methyl-sulfoxide (DMSO), DMF (DMF), 1-METHYLPYRROLIDONE (NMP), ether (ether), ethylene glycol (Ethylene glycol) etc.
In addition, according to stabilizing agent of the present invention (Stabilizer) as the stability for giving particle after being mixed together with above-mentioned pyrroles and furans or its derivative, to achieve these goals, if in affiliated field common used stabilizing agent (Stabilizer), use any one all harmless, but as aforementioned stable agent, can be by poly-(styrene sulfonic acid) [poly (4-styrene sulfonic acid)], poly-(acrylic acid) [poly (acrylic acid)], poly-(methacrylic acid) [poly (methacrylic acid], poly-(maleic acid) [poly (maleic acid)], poly-(vinyl sulfonic acid) [poly (vinyl sulfonic acid)], DTAB [dodecyl trimethyl ammonium bromide], softex kw [cetyl trimethlammonium bromide], didodecyldimethylammbromide bromide [didodcyl dimethl ammonium bromide], span 80 [Span 80], [Tween 20 for polysorbas20, polyoxyethylene (20) sorbitanmonolaurate], perfluoro caprylic acid [Perfluorooctnoic acid], cetylpyridinium chloride [cetypyridinium chloride], benzalkonium chloride [benzalkonium chloride], benzethonium chloride [Benzethonium chloride] etc. can be used alone or use two or more.Optimal stabilizing agent (Stabilizer) is to be applicable to using polystyrolsulfon acid (Polystyrene sulfonic acid).
Preferably, with respect to above-mentioned monomer 100 weight portions, the use amount of aforementioned stable agent (Stabilizer) is 0.01 to 2,000 weight portion.At above-mentioned content lower than 0.01 weight portion in the situation that, cannot reach the concentration that forms micella, thereby can not act as stabilizing agent (Stabilizer), therefore cannot cause the neutralization of chain-type nano particle, and produce the phenomenon of particle condensation, if surpass 2,000 weight portions, the quantitative change of stabilizing agent (Stabilizer) obtain very excessive, thereby be difficult for to form above-mentioned chain-type nano particle.
In addition, the in the situation that of being used for reducing after above-mentioned the second oxidant is oxidized thiophene, pyrroles or furans monomer according to the first oxidant of the present invention, again the second oxidant of reduction is oxidized, thereby make the second oxidant there is oxidizing force, if can realize above-mentioned purpose, use any one all harmless, preferably, preferably compare the relative oxidant with higher oxidizing force with the second oxidant, preferably, preferably use peroxidating class [H
2o
2, (NH
4)
2s
2o
8, O
2] or oxyacid class [HMnO
4, HNO
3], halogen [F
2, CI
2, Br
2] or above-mentioned mixture.
Preferably, 0.01 to 10 molar ratio (mole ratio) that the addition of above-mentioned the first oxidant is monomer.In the situation that the content of above-mentioned the first oxidant is lower than 0.01 molar ratio, be difficult for producing the reaction that the second oxidant is reduced, thereby reduce the degree of polymerization of chain-type nano particle, and in the situation that surpassing 10 molar ratio, can produce on the contrary the phenomenon that reduces degree of neutralization, thereby can reduce physical characteristic.
In addition, in the present invention, above-mentioned the second oxidant, as for monomer is oxidized, if can realize the oxidant of above-mentioned purpose, is used any one all harmless, but be preferably metal oxide, for example, and FeCI preferably
3, Fe (SO
4)
26H
20 iron such as grade (III) chelate, or iron (II) chelate or said mixture etc., its use amount is used 0.001 to 5 molar ratio (mole ratio) with respect to above-mentioned monomer.In the present invention, in the situation that the use amount of the second oxidant with respect to monomer lower than 0.001 molar ratio, polymerization rate is very slow, in its use amount, be that 5 molar ratios are above in the situation that, increase polymerization rate and electrical conductivity, but reduce the physical property of the conducting polymer of manufacturing.
In the present invention, the second oxidant can directly be mixed in the mixture for the raw material of polymerisation, for example, the mixture of the mixture such as monomer, HCI, stabilizing agent (Stabilizer), the first oxidant and solvent, but preferably, be dissolved under the state of deionized water (Deionized water, DI Water) and/or organic solvent, be mixed into the mixture of above-mentioned raw materials.
In addition, preferably, in the present invention, the reaction temperature of macromolecular polymerization reaction is 0-180 ℃, or the boiling temperature of the solvent using, and carries out stirring for 6 to 24 hours at 0 to 180 ℃ of temperature, thereby by emulsion oxidation polymerization step, can manufacture electric conductivity water-dispersable nanoparticles.
More preferably, the present invention includes following steps, thereby can manufacture electric conductivity water-dispersable nanoparticles: I) emulsion manufacturing step, it is with respect to replacing or unsubstituted thiophene, pyrroles or furans monomer 100 weight portions, drop into 0.01 to 2, the first oxidant of 0.01 to 10 molar ratio (mole ratio) of the stabilizing agent of 000 weight portion and above-mentioned monomer, there is 1 of above-mentioned monomer, 000 to 2, the HCI of the temperature range of 0 to 180 ℃ of 000 weight portion is in 1 to 6 acid solution thereby be mixed in pH; II) seed emulsion (seed emulsion) manufacturing step, it is in above-mentioned steps I) emulsion in, with respect to above-mentioned monomer, according to 0.001 to 5.0 molar ratio (mole ratio), mix after the second oxidant, at 0 to 180 ℃, carry out stirring for 10 to 30 minutes; III) emulsion oxidation polymerization step, it is by above-mentioned steps II) seed emulsion at 0 to 180 ℃ of temperature, carry out stirring for 6 to 24 hours.
In addition, in the present invention, above-mentioned steps c) dry is that the electroconductive particle of emulsion state is carried out to dry step, can at normal temperature-70 ℃, be dried.
In addition, the invention provides the electric conductivity water-dispersable nanoparticles according to said method manufacturing, above-mentioned electric conductivity water-dispersable nanoparticles has the size of 10nm to 1 μ m, compares with existing conducting polymer, has good processability and high conductivity.
In addition, the invention provides a kind of electronic material, optical material, toner and/or ink that utilizes above-mentioned electric conductivity water-dispersable nanoparticles to manufacture, according to the present invention, the polypyrrole of manufacturing, poly-furans or polythiophene nano particle have good processability and electric conductivity, therefore electronic material, optical material, toner and/or ink etc. be can be used in, and material, conductive layer material, pattern manufactured materials, printing ink material etc. regulated applicable to power conversion and energy storage material, anti-static material, electric charge.In addition, according to electronic material of the present invention, toner and/or ink etc. mean the polypyrrole that includes the manufacturing according to the present invention, the electronic material of poly-furans or polythiophene, toner and/or ink, if include the common product in the affiliated field of above-mentioned formation, any product all belongs to according to electronic material of the present invention, toner and/or ink, as preferred electronic material, there is photocell, capacitor (using as electrolytical substitute) and tellite (printed circuit board) coating agent are (as the gold-plated replacement of existing metal, environmental pollution minimizes) and/or charged preventor (by coating, wait and prevent at plastics, the upper static producing in the surface such as macromolecule).
Below, in order to help the understanding of the present invention, proposed preferred embodiment, but following examples are example the present invention, scope of the present invention is not limited to following examples.
[embodiment 1]
To the hydrochloric acid solution 7.9g of deionized water 89g and 37% weight, mix rear stirring as polystyrolsulfon acid (the Polystyrene sulfonic acid) aqueous solution 6.9g of 18% weight of stabilizing agent (Stabilizer), thereby completely steady dissolution agent (Stabilizer), above-mentioned deionized water be by distilled water utilize cation and anion exchange resin according to order carry out by after be fabricated to 25 ℃.Afterwards, mix 3.4-ethene dioxythiophene (3.4-ethylenedioxythiophene) 0.5g as monomer, and at 5 ℃ of temperature, carry out reaction in about 30 minutes, thereby manufacture emulsion.
Afterwards, in the reactor of sealing (closed), aqueous hydrogen peroxide solution 0.3g as 30% weight of the first oxidant in said mixture is mixed in to deionized water 5g with the second oxidant ferric sulfate (ferric sulfate) [Fe2 (SO4) 3] 7mg as initator, thereby manufacture, include after the mixed solution of the second oxidant, above-mentioned seed emulsion mixture is stirred 12 hours at 25 ℃ of temperature, thus poly-(3.4-ethene dioxythiophene) particle of manufacture emulsion state.
Afterwards, the polypyrrole particle of the emulsion state of above-mentioned manufacturing is dried under the scope of normal temperature to 70 ℃, thereby manufactures poly-(3.4-ethene dioxythiophene) particle.
Its result, the conversion ratio of poly-(3.4-ethene dioxythiophene) emulsion is 99%, the polypyrrole particle size of manufacturing is average 50nm, this is passed through to rod type coating method (Bar coating method, #7bar) make conductive membrane, thereby the result that effects on surface resistance is measured is for having obtained 10
5.0ohm/sq..
In addition, in poly-(3.4-ethene dioxythiophene) the emulsion 10g manufacturing, dissolve 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) (DMSO), the ethylene glycol (ethylene glycol) of 0.1-10g, thereby the result of manufacturing conductive membrane by rod type coating method is for having obtained 100 to 10
5.0ohm/sq. sheet resistance value.
[embodiment 2]
By the method identical with embodiment 1, implement, be used as polystyrolsulfon acid (Polystyrene sulfonic acid) the solution 69g of 18% weight of stabilizing agent (Stabilizer), and be mixed in deionized water 5g the ferric sulfate 7mg as the second oxidant as initator, thereby manufacture, include after the mixed solution of the second oxidant, this is mixed in after above-mentioned emulsion, at the temperature of 25 ℃, react approximately 30 minutes, thereby manufacture seed emulsion.
Afterwards, in sealing (closed) reactor, seed emulsion mixture is stirred 12 hours at 25 ℃ of temperature, thus poly-(3.4-ethene dioxythiophene) particle of manufacture emulsion state.
Its result, the conversion ratio of poly-(3.4-ethene dioxythiophene) emulsion is 96%, the polypyrrole particle size of manufacturing is average 10-50nm, this is passed through to rod type coating method (Bar coating method, #7bar) make conductive membrane, thereby the result that effects on surface resistance is measured is for having obtained 10
5.0ohm/sq..
In addition, in poly-(3.4-ethene dioxythiophene) the emulsion 10g manufacturing, dissolve NMP, DMSO, the Ethylene glycol of 0.1-10g, thereby the result of manufacturing conductive membrane by rod type coating method is for having obtained 100 to 10
6.0ohm/sq. sheet resistance value.
As mentioned above, the those skilled in the art under the present invention are interpreted as, and the present invention does not change its technological thought or essential feature, can be embodied as other concrete forms yet.Therefore being interpreted as going up in all respects at above-mentioned described embodiment is all example, is not limited to this.Scope of the present invention is interpreted as, the form of the implication of the patent request scope that will narrate in the back and scope all changes of deriving from its equivalent concepts or distortion should comprise within the scope of the invention, rather than above-mentioned carried out detailed description.
In industry, utilize possibility
The electric conductivity water-dispersable nanoparticles of the method according to this invention manufacturing is compared with the conductive nanometer particle of existing common manufacturing, has good processability and high conductivity.
Claims (12)
1. a manufacture method for electric conductivity water-dispersable nanoparticles, is characterized in that, comprises the steps:
A) in aqueous solvent to thiophene, pyrroles or furans monomer, select compound, stabilizing agent and the first oxidant in the group that free HCI, HF, HBr and HI form to mix after, manufacture emulsion;
B) in above-mentioned steps emulsion a), mix and stir the second oxidant, thus the electroconductive particle of manufacture emulsion state; And
C) to above-mentioned steps b) the electroconductive particle of emulsion state be dried.
2. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
In above-mentioned steps, use HCI in a).
3. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
Above-mentioned steps a) in, the compound in the group of selecting free HCI, HF, HBr and HI to form is dropped into according to the 1-100 molar ratio of above-mentioned monomer (mole ratio).
4. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
Above-mentioned steps a) in, with respect to used monomer 100 weight portions, drop into the stabilizing agent of 0.01-2000 weight portion.
5. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
Above-mentioned steps a) in, the first oxidant is dropped into according to 0.01 to 10 molar ratio (mole ratio) of above-mentioned monomer.
6. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
At above-mentioned steps b) in, the second oxidant is dropped into according to 0.001 to 5.0 molar ratio (mole ratio) of above-mentioned monomer.
7. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
Aforementioned stable agent is polystyrolsulfon acid.
8. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
Above-mentioned the first oxidant is to select free H
2o
2, (NH
4)
2s
2o
8, HMnO
4, HNO
3, HCIO
4, F
2, CI
2and Br
2more than one in the group forming.
9. the manufacture method of electric conductivity water-dispersable nanoparticles according to claim 1, is characterized in that:
Above-mentioned the second oxidant is to select free FeCI
3, Fe (SO
4)
26H
2more than one in the group that O and iron (II) chelate forms.
10. the electric conductivity water-dispersable nanoparticles that manufacture method according to claim 1 is manufactured.
The manufacture method of 11. electric conductivity water-dispersable nanoparticles according to claim 10, is characterized in that:
The size of above-mentioned electric conductivity water-dispersable nanoparticles is 10-1000nm.
12. electronic material, optical material, toner or the inks that utilize electric conductivity water-dispersable nanoparticles that claim 10 is recorded to manufacture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2011-0054542 | 2011-06-07 | ||
| KR1020110054542A KR20120135690A (en) | 2011-06-07 | 2011-06-07 | Preparation method of nano particles having conductivity and water dispersibility |
| PCT/KR2012/004436 WO2012169767A2 (en) | 2011-06-07 | 2012-06-05 | Method for manufacturing conductive water-dispersible nano particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103748032A true CN103748032A (en) | 2014-04-23 |
Family
ID=47296578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280028262.8A Pending CN103748032A (en) | 2011-06-07 | 2012-06-05 | Method for manufacturing conductive water-dispersible nano particles |
Country Status (4)
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|---|---|
| KR (1) | KR20120135690A (en) |
| CN (1) | CN103748032A (en) |
| TW (1) | TW201302844A (en) |
| WO (1) | WO2012169767A2 (en) |
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| KR100684913B1 (en) * | 2005-10-06 | 2007-02-20 | 연세대학교 산학협력단 | Preparation method of polythiophene nanoparticles and derivatives thereof by oxidation polymerization of thiophene emulsion in aqueous phase |
| CN1934159A (en) * | 2004-03-17 | 2007-03-21 | E.I.内穆尔杜邦公司 | Water dispersible polypyrroles made with polymeric acid colloids for electronics applications |
| CN1976969A (en) * | 2004-03-17 | 2007-06-06 | E.I.内穆尔杜邦公司 | Water dispersible polydioxythiophenes with polymeric acid colloids and a water-miscible organic liquid |
| CN101033294A (en) * | 2007-04-04 | 2007-09-12 | 同济大学 | Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method |
| KR20100004404A (en) * | 2008-07-03 | 2010-01-13 | 주식회사 제이앤드제이 캐미칼 | Nanoparticles comprising polythiophene or its derivatives enclosed by conductive polymers and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101000496B1 (en) * | 2008-09-19 | 2010-12-14 | (주)폴리메리츠 | Method of manufacturing nanoparticles of poly3,4-ethylenedioxythiophene |
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2011
- 2011-06-07 KR KR1020110054542A patent/KR20120135690A/en not_active Application Discontinuation
-
2012
- 2012-06-05 CN CN201280028262.8A patent/CN103748032A/en active Pending
- 2012-06-05 WO PCT/KR2012/004436 patent/WO2012169767A2/en active Application Filing
- 2012-06-06 TW TW101120274A patent/TW201302844A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934159A (en) * | 2004-03-17 | 2007-03-21 | E.I.内穆尔杜邦公司 | Water dispersible polypyrroles made with polymeric acid colloids for electronics applications |
| CN1976969A (en) * | 2004-03-17 | 2007-06-06 | E.I.内穆尔杜邦公司 | Water dispersible polydioxythiophenes with polymeric acid colloids and a water-miscible organic liquid |
| KR100684913B1 (en) * | 2005-10-06 | 2007-02-20 | 연세대학교 산학협력단 | Preparation method of polythiophene nanoparticles and derivatives thereof by oxidation polymerization of thiophene emulsion in aqueous phase |
| CN101033294A (en) * | 2007-04-04 | 2007-09-12 | 同济大学 | Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method |
| KR20100004404A (en) * | 2008-07-03 | 2010-01-13 | 주식회사 제이앤드제이 캐미칼 | Nanoparticles comprising polythiophene or its derivatives enclosed by conductive polymers and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120135690A (en) | 2012-12-17 |
| WO2012169767A3 (en) | 2013-04-04 |
| TW201302844A (en) | 2013-01-16 |
| WO2012169767A2 (en) | 2012-12-13 |
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