US20200131378A1 - Composite conductive polymers, preparation method and application thereof - Google Patents
Composite conductive polymers, preparation method and application thereof Download PDFInfo
- Publication number
- US20200131378A1 US20200131378A1 US16/245,098 US201916245098A US2020131378A1 US 20200131378 A1 US20200131378 A1 US 20200131378A1 US 201916245098 A US201916245098 A US 201916245098A US 2020131378 A1 US2020131378 A1 US 2020131378A1
- Authority
- US
- United States
- Prior art keywords
- acid
- monomer
- group
- mixed solution
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Definitions
- Embodiments of the present disclosure relate to a composite conductive polymer containing metal, a preparation method and applications thereof.
- Conductive polymers can be classified into composite conductive polymers and structural conductive polymers, according to the structure, composition and preparation method.
- the composite conductive polymers is a multi-phase polymer composite material with conductive properties prepared by using a polymer structural material as a matrix, which is incorporated with conductive fillers such as carbon powder and metal powder, and employing techniques such as dispersion, layering and surface recombination.
- the composite conductive polymers with advantages of simple process, low price and good practicality, easy to be commercially produced, is more developed than structural conductive polymers.
- the composite conductive polymers membranes mainly include electrochemical polymerization and chemical polymerization.
- the composite conductive polymers can be formed on the conductive substrates by electrochemical polymerization, and the thickness of the resulting film can be controlled by adjusting the current and voltage.
- the electrochemical polymerization processes are complicated, costly, restricted by demand for conductive substrates and difficult to be applicable in large scale production, while preparation of composite conductive polymers by chemical polymerization has the advantages of simple preparation process, low cost and mass production.
- the following problems often emerge in the process of preparing the composite conductive polymers by chemical polymerization: 1. it is difficult to avoid the use of toxic solvents such as chloroform, toluene, tetrahydrofuran during synthesis process; 2.
- an oxidant with a single component is used in the synthesis process, resulting in long polymerization time, generally more than 20 h; 3. the doping processes of some composite conductors in which the dopants exist in the form of ions are complicated and cumbersome to manipulate; 4. most of the composite conductive polymers which are prepared by chemical polymerization methods are solid powder and difficult to form film, thus greatly limiting the application field of the product.
- Embodiments of the present disclosure provide a composite conductive polymer comprising an elementary metal and a polymer, and materials for synthesizing the composite conductive polymer comprise a mixed solution A and a monomer-containing solution for polymerization.
- the elementary metal is, for example, at least one selected from the group consisting of Cu, Pd, Ag, Pt and Au, and for example, the elementary metal is selected from Cu, Ag.
- the monomer for synthesizing the polymer is at least one selected from the group consisting of pyrrole, aniline, thiophene and derivatives thereof, for example, the monomer is thiophene or derivatives thereof; and the derivatives of thiophene is, for example, a thiophene substituted by a C 1 -C 10 alkyl group and/or C 1 -C 10 alkoxy group.
- the mixed solution A comprises the following two components:
- a strong oxidant selected from at least one of permanganate, persulfate, dichromate and perchlorate; wherein, the permanganate, persulphate, dichromate or perchlorate is, for example, a potassium salt or a sodium salt.
- an oxidizing agent containing a metal ion capable of being reduced to elementary substance is at least one selected from the group consisting of Cu salt, Pd salt, Ag salt, Pt salt and Au salt, and for example, the oxidizing agent is Cu 2+ salt or Ag + salt, such as CuCl 2 or AgNO 3 .
- the mixed solution A may further comprise an acid as component (iii).
- the acid is, for example, at least one selected from the group consisting of boric acid, phosphoric acid, carboxyl group-containing organic acid, sulfonic acid group-containing (—SO 3 H) organic acid, sulfinic acid group-containing organic acid, and organic acid containing sulphur carboxylic acid group (RCOSH), such as boric acid.
- a concentration of the component (i) in the mixed solution A is from 0.2 wt % to 1 wt %, for example, from 0.4 wt % to 0.6 wt %, and for another example, 0.5 wt %; a concentration of the component (ii) in the mixed solution A is, for example, from 0.05 mol/L to 2.00 mol/L, for example, from 0.10 mol/L to 1.5 mol/L, and for another example, from 0.15 mol/L to 1.0 mol/L; and a concentration of the component (iii) in the mixed solution A is, for example, from 5 g/L to 15 g/L, for example, from 8 g/L to 12 g/L, and for another example, 10 g/L.
- a concentration of the monomer is, for example, from 10 mL/L to 30 mL/L, for example, 20 mL/L; for example, a pH of the monomer-containing solution can be further adjusted to 1.8 to 2.2 by using a pH-adjusting acid.
- the pH is adjusted to 2.
- the pH-adjusting acid may be selected from the group consisting of phosphoric acid and boric acid.
- the pH-adjusting acid is phosphoric acid.
- a concentration of the pH-adjusting acid is, for example, from 1 mL/L to 5 mL/L.
- Embodiments of the present disclosure further provide a film comprising the above composite conductive polymer.
- the square resistance of the film is from 500 ⁇ / ⁇ to 3 ⁇ 10 3 ⁇ / ⁇ ;
- a metal content of the film is from 1.00 wt % to 5.00 wt %, for example, from 1.50 wt % to 4.50 wt %, and for example, 2.00 ⁇ 0.50 wt %, 3.00 ⁇ 0.50 wt %, or 4.00 ⁇ 0.50 wt %.
- An embodiment of the present disclosure further provides a mixed solution A.
- the mixed solution A is as defined above.
- An embodiment of the present disclosure further provides use of the mixed solution A for preparing a metal-containing composite conductive polymer and a film thereof.
- the metal-containing composite conductive polymer is the composite conductive polymer as defined above
- the metal-containing composite conductive polymer film is the film of the composite conductive polymer as defined above.
- an embodiment of the present disclosure provides a method for preparing a composite conductive polymer, which comprises:
- the method comprises the steps of:
- the metal in the composite conductive polymer, exists in elementary form, for example, the metal is at least one selected from the group consisting of Cu, Pd, Ag, Pt and Au, for example, the elementary metal is selected from Cu, Ag.
- the insulating substrate is selected from an insulating material such as resin, rubber, glass, polyimide (PI) or polyethylene terephthalate (PET).
- the monomer is, for example, at least one selected from the group consisting of pyrrole, aniline, thiophene and derivatives thereof, for example, the monomer is thiophene or derivatives thereof, and the derivatives of thiophene are, for example, thiophene substituted by a C 1 -C 10 alkyl group and/or C 1 -C 10 alkoxy group.
- the mixed solution A comprises the following two components:
- a strong oxidant selected from at least one of permanganate, persulfate, dichromate and perchlorate;
- an oxidizing agent containing a metal ion capable of being reduced to elementary substance wherein, the permanganate, the persulphate, the dichromate or the perchlorate is, for example, a potassium salt or a sodium salt.
- the oxidizing agent containing a metal ion capable of being reduced to elementary substance is at least one selected from the group consisting of Cu salt, Pd salt, Ag salt, Pt salt and Au salt, and for example, the oxidizing agent is Cu 2+ salt or Ag + salt, such as CuCl 2 , or AgNO 3 .
- the mixed solution A may further comprise an acid as component (iii).
- a concentration of the component (i) in the mixed solution A is from 0.2 wt % to 1 wt %, for example, from 0.4 wt % to 0.6 wt %, and for another example, 0.5 wt %; a concentration of the component (ii) in the mixed solution A is, for example, from 0.05 mol/L to 2.00 mol/L, for example, from 0.10 mol/L to 1.5 mol/L, and for another example, from 0.15 mol/L to 1.0 mol/L.
- the concerntration of the component (ii) can be 0.30 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L or 0.70 mol/L; and a concentration of the component (iii) in the mixed solution A is, for example, from 5 g/L to 15 g/L, for example, from 8 g/L to 12 g/L, and for another example, 10 g/L.
- a temperature under which the insulating substrate is placed in the mixed solution A is from 60° C. to 130° C.
- the temperature is from 80° C. to 110° C., from 85° C. to 95° C., and 90° C.
- a time for placing is, for example, 5 min-20 min, for example 6 min-15 min, and for example 10 min.
- the insulating substrate is placed in the mixed solution A to form an oxide layer.
- a concentration of the thiophene monomer is from 10 mL/L to 30 mL/L, for example, 20 mL/L
- a temperature for polymerization of the monomer is from 15° C. to 45° C., for example at room temperature
- a time for polymerization of the monomer is from 2 h to 8 h, for example from 3 h to 6 h, for example 4 h.
- a small amount of pH-adjusting acid is added to adjust a pH of the solution for polymerization.
- the pH-adjusting acid is, for example, selected from phosphoric acid and boric acid.
- the acid is phosphoric acid with a concentration from 1 mL/L to 5 mL/L.
- the method further comprises a pretreatment step (step before the step (a)): degreasing, washing the insulating substrate followed by plasma processing.
- the degreasing liquid used is at least one selected from the group consisting of an alkaline agent, a surfactant, and a phosphate.
- the degreasing liquid is a mixture of sodium hydroxide, sodium dodecylbenzenesulfonate, sodium carbonate, and trisodium phosphate.
- a ratio of the above components in the mixture is, for example, 15-25 g/L: 0.5-2 g/L: 1-5 g/L: 3-7 g/L; for example 20 g/L: 1 g/L: 3 g/L: 5 g/L; for example, the degreasing process is carried out at 40° C.-80° C. (for example, 40° C.-60° C.) for 3 min-30 min (for example, 3 min-10 min) followed by washing and drying.
- the plasma process is carried out under atmospheric pressure of 70 pa-120 pa and with a frequency of 80 w-100 w. For example, the pressure is 90 pa, and the frequency is 90 w.
- An embodiment of the present disclosure further provides a composite conductive polymer obtained by the above preparation methods, comprising an elementary metal.
- An embodiment of the present disclosure further provides use of the metal-containing composite conductive polymer in electroplating.
- an embodiment of the present disclosure provides a method for electroplating, which comprises: electroplating a substrate covered with the composite conductive polymer.
- the electroplating method comprises: placing a substrate covered with the composite conductive polymer in a plating solution, applying electric current, electroplating with air agitation at room temperature, and then washing and drying.
- the plating solution comprises copper sulfate pentahydrate, concentrated sulfuric acid and chloride ion, and a concentration of the copper sulfate pentahydrate in the plating solution is from 80 g/L to 120 g/L, for example, from 90 g/L to 110 g/L, and for example, 100 g/L; a concentration of concentrated sulfuric acid in the plating solution is from 80 mL/L to 120 mL/L, for example, from 90 mL/L to 110 mL/L, for example, 100 mL/L.
- a density of the applied current is from 2 A/dm 2 to 3 A/dm 2 , for example 2.5 A/dm 2 ; and time for electroplating with air inflation is, for example, 20 min-50 min, for example 25 min-35 min, for example 30 min.
- the composite conductive polymer synthesized by embodiments of the present disclosure, containing elementary metal, has good film-forming property and the film obtained can completely cover the surface of the insulating substrate, with a square resistance from 500 ⁇ / ⁇ to 3 ⁇ 10 3 ⁇ / ⁇ and excellent electrical conductivity, which therefore can be widely used in electroplating materials and semiconductor materials and other fields.
- the mixed solution A employed in embodiments of the present disclosure contributes to synchronization of polymerization and metal element formation, and enables short time to produce a composite conductive polymer.
- the preparation process of the composite conductive polymer according to embodiments of the present disclosure is simple and easy to operate, with low cost, during which, the solution employed in the polymerization reaction, without any toxic organic solvent, can be reused, thus is environment-friendly synthesis process for materials.
- FIG. 1 is a physical view of an original insulating substrate
- FIG. 2 is a physical view of the sample of FIG. 1 covered by a copper-containing conductive polythiophene, following the proceedings of example 1;
- FIG. 3 is an XRD pattern of the sample of FIG. 2 ;
- FIG. 4 is a physical view of the sample of FIG. 2 plated with copper.
- An insulating substrate epoxy resin substrate, as shown in FIG. 1
- a degreasing solution a mixture of 20 g/L sodium hydroxide, 1 g/L sodium dodecylbenzene sulfonate, 3 g/L sodium carbonate and 5 g/L of trisodium phosphate
- a degreasing solution a mixture of 20 g/L sodium hydroxide, 1 g/L sodium dodecylbenzene sulfonate, 3 g/L sodium carbonate and 5 g/L of trisodium phosphate
- the treated insulating substrate was immersed in a mixture of 0.5 wt % potassium permanganate, 0.1 mol/L CuCl 2 .2H 2 O and 10 g/L boric acid at 90° C. for 10 min to form an oxide layer on the insulating substrate, which was then washed and dried.
- the insulating substrate was immersed in a solution containing 20 mL/L of thiophene monomer for polymerization at room temperature (the solution for polymerization was purchased from Guangdong Guanghua Technology Co., Ltd., code 2303), added with 3 mL/L of phosphoric acid to adjust the pH value of the solution for polymerization, followed by reacting for 4 hours to obtain a copper-containing conductive polythiophene on the insulating substrate, and then washed and naturally dried.
- the solution for polymerization was purchased from Guangdong Guanghua Technology Co., Ltd., code 2303
- the copper-containing conductive polythiophene obtained by the polymerization of example 1 is shown in FIG. 2 .
- FIG. 2 By comparing FIG. 1 and FIG. 2 , it can be seen that the copper-containing polythiophene film prepared by the embodiment of the present disclosure has good coverage property.
- Information about the crystal face of the elementary copper contained in the product is detected by XRD, which shows a face-centered cubic structure (see FIG. 3 ).
- the obtained copper-containing polythiophene film was subjected to a four-probe detector to measure the square resistance to characterize its electrical conductivity, and the measured square resistance is 1.83 ⁇ 10 3 ⁇ / ⁇ .
- a content of copper in the copper-containing polythiophene film was measured by XPS to be 1.68 wt %.
- a substrate grown with a copper-containing conductive polythiophene was immersed in a plating solution comprising 100 g/L of copper sulfate pentahydrate, 100 mL/L of concentrated sulfuric acid, and 60 mg/L of chloride ion, applied a current of 2.5 A/dm 2 , plated with air agitation for 30 minutes at room temperature, and taken out for washing and drying.
- the copper conductive layer was evenly covered on the substrate, which was as shown in FIG. 4 , and it can be seen that the copper-containing conductive polythiophene film prepared by the present embodiment has excellent properties suitable for electroplating application.
- the composite conductive polymer was prepared referring to example 1, under the same conditions as example 1 except that the concentration of CuCl 2 .2H 2 O was changed to 0.5 mol/L. Finally, a copper-containing conductive polythiophene film on the surface of the substrate was obtained.
- the square resistance of the film is 590 ⁇ / ⁇ and the copper content of the film is 3.57 wt %.
- the composite conductive polymer was prepared referring to example 1, under the same conditions as example 1 except that 0.1 mol/L AgNO 3 was used instead of CuCl 2 .2H 2 O. Finally, a silver-containing conductive polythiophene film on the surface of the substrate was obtained.
- the square resistance of the film is 1.36 ⁇ 10 3 ⁇ /and the copper content of the film is 2.02 wt %.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Chemically Coating (AREA)
Abstract
Description
- The present application claims the priority of the Chinese Patent Application No. 201811244146.5 filed on Oct. 24, 2018, which is incorporated herein by reference as part of the disclosure of the present application.
- Embodiments of the present disclosure relate to a composite conductive polymer containing metal, a preparation method and applications thereof.
- Conductive polymers can be classified into composite conductive polymers and structural conductive polymers, according to the structure, composition and preparation method. The composite conductive polymers is a multi-phase polymer composite material with conductive properties prepared by using a polymer structural material as a matrix, which is incorporated with conductive fillers such as carbon powder and metal powder, and employing techniques such as dispersion, layering and surface recombination. The composite conductive polymers, with advantages of simple process, low price and good practicality, easy to be commercially produced, is more developed than structural conductive polymers.
- At present, common synthesis methods of the composite conductive polymers membranes mainly include electrochemical polymerization and chemical polymerization. The composite conductive polymers can be formed on the conductive substrates by electrochemical polymerization, and the thickness of the resulting film can be controlled by adjusting the current and voltage. The electrochemical polymerization processes are complicated, costly, restricted by demand for conductive substrates and difficult to be applicable in large scale production, while preparation of composite conductive polymers by chemical polymerization has the advantages of simple preparation process, low cost and mass production. However, the following problems often emerge in the process of preparing the composite conductive polymers by chemical polymerization: 1. it is difficult to avoid the use of toxic solvents such as chloroform, toluene, tetrahydrofuran during synthesis process; 2. an oxidant with a single component is used in the synthesis process, resulting in long polymerization time, generally more than 20 h; 3. the doping processes of some composite conductors in which the dopants exist in the form of ions are complicated and cumbersome to manipulate; 4. most of the composite conductive polymers which are prepared by chemical polymerization methods are solid powder and difficult to form film, thus greatly limiting the application field of the product.
- Embodiments of the present disclosure provide a composite conductive polymer comprising an elementary metal and a polymer, and materials for synthesizing the composite conductive polymer comprise a mixed solution A and a monomer-containing solution for polymerization.
- According to an embodiment of the present disclosure, in the composite conductive polymer, the elementary metal is, for example, at least one selected from the group consisting of Cu, Pd, Ag, Pt and Au, and for example, the elementary metal is selected from Cu, Ag.
- The monomer for synthesizing the polymer is at least one selected from the group consisting of pyrrole, aniline, thiophene and derivatives thereof, for example, the monomer is thiophene or derivatives thereof; and the derivatives of thiophene is, for example, a thiophene substituted by a C1-C10 alkyl group and/or C1-C10 alkoxy group.
- The mixed solution A comprises the following two components:
- (i) a strong oxidant selected from at least one of permanganate, persulfate, dichromate and perchlorate; wherein, the permanganate, persulphate, dichromate or perchlorate is, for example, a potassium salt or a sodium salt.
- (ii) an oxidizing agent containing a metal ion capable of being reduced to elementary substance; the oxidizing agent containing the metal ion capable of being reduced to elementary substance is at least one selected from the group consisting of Cu salt, Pd salt, Ag salt, Pt salt and Au salt, and for example, the oxidizing agent is Cu2+ salt or Ag+ salt, such as CuCl2 or AgNO3.
- The mixed solution A may further comprise an acid as component (iii). The acid is, for example, at least one selected from the group consisting of boric acid, phosphoric acid, carboxyl group-containing organic acid, sulfonic acid group-containing (—SO3H) organic acid, sulfinic acid group-containing organic acid, and organic acid containing sulphur carboxylic acid group (RCOSH), such as boric acid.
- A concentration of the component (i) in the mixed solution A is from 0.2 wt % to 1 wt %, for example, from 0.4 wt % to 0.6 wt %, and for another example, 0.5 wt %; a concentration of the component (ii) in the mixed solution A is, for example, from 0.05 mol/L to 2.00 mol/L, for example, from 0.10 mol/L to 1.5 mol/L, and for another example, from 0.15 mol/L to 1.0 mol/L; and a concentration of the component (iii) in the mixed solution A is, for example, from 5 g/L to 15 g/L, for example, from 8 g/L to 12 g/L, and for another example, 10 g/L.
- In the monomer-containing solution for polymerization, a concentration of the monomer is, for example, from 10 mL/L to 30 mL/L, for example, 20 mL/L; for example, a pH of the monomer-containing solution can be further adjusted to 1.8 to 2.2 by using a pH-adjusting acid. For example, the pH is adjusted to 2. The pH-adjusting acid may be selected from the group consisting of phosphoric acid and boric acid. For example, the pH-adjusting acid is phosphoric acid. A concentration of the pH-adjusting acid is, for example, from 1 mL/L to 5 mL/L.
- Embodiments of the present disclosure further provide a film comprising the above composite conductive polymer. The square resistance of the film is from 500Ω/□ to 3×103Ω/□; A metal content of the film is from 1.00 wt % to 5.00 wt %, for example, from 1.50 wt % to 4.50 wt %, and for example, 2.00±0.50 wt %, 3.00±0.50 wt %, or 4.00±0.50 wt %.
- An embodiment of the present disclosure further provides a mixed solution A. The mixed solution A is as defined above.
- An embodiment of the present disclosure further provides use of the mixed solution A for preparing a metal-containing composite conductive polymer and a film thereof. The metal-containing composite conductive polymer is the composite conductive polymer as defined above, and the metal-containing composite conductive polymer film is the film of the composite conductive polymer as defined above.
- In another aspect, an embodiment of the present disclosure provides a method for preparing a composite conductive polymer, which comprises:
- (a) providing the above mixed solution A and placing an insulating substrate in the mixed solution A;
- (b) placing the obtained insulating substrate in a monomer-containing solution and performing polymerization of the monomer.
- According to an embodiment of the present disclosure, the method comprises the steps of:
- (a) placing the insulating substrate in the mixed solution A to form an oxide layer on the insulating substrate, washing and drying the insulating substrate;
- (b) placing the obtained insulating substrate in the monomer-containing solution and performing polymerization of the monomer, to form metal-containing composite conductive polymer on the insulating substrate, washing and drying the insulating substrate.
- According to an embodiment of the present disclosure, in the composite conductive polymer, the metal exists in elementary form, for example, the metal is at least one selected from the group consisting of Cu, Pd, Ag, Pt and Au, for example, the elementary metal is selected from Cu, Ag.
- The insulating substrate is selected from an insulating material such as resin, rubber, glass, polyimide (PI) or polyethylene terephthalate (PET). The monomer is, for example, at least one selected from the group consisting of pyrrole, aniline, thiophene and derivatives thereof, for example, the monomer is thiophene or derivatives thereof, and the derivatives of thiophene are, for example, thiophene substituted by a C1-C10 alkyl group and/or C1-C10 alkoxy group.
- According to an embodiment of the present disclosure, the mixed solution A comprises the following two components:
- (i) a strong oxidant selected from at least one of permanganate, persulfate, dichromate and perchlorate; (ii) an oxidizing agent containing a metal ion capable of being reduced to elementary substance; wherein, the permanganate, the persulphate, the dichromate or the perchlorate is, for example, a potassium salt or a sodium salt. The oxidizing agent containing a metal ion capable of being reduced to elementary substance is at least one selected from the group consisting of Cu salt, Pd salt, Ag salt, Pt salt and Au salt, and for example, the oxidizing agent is Cu2+ salt or Ag+ salt, such as CuCl2, or AgNO3. The mixed solution A may further comprise an acid as component (iii).
- A concentration of the component (i) in the mixed solution A is from 0.2 wt % to 1 wt %, for example, from 0.4 wt % to 0.6 wt %, and for another example, 0.5 wt %; a concentration of the component (ii) in the mixed solution A is, for example, from 0.05 mol/L to 2.00 mol/L, for example, from 0.10 mol/L to 1.5 mol/L, and for another example, from 0.15 mol/L to 1.0 mol/L. For example, the concerntration of the component (ii) can be 0.30 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L or 0.70 mol/L; and a concentration of the component (iii) in the mixed solution A is, for example, from 5 g/L to 15 g/L, for example, from 8 g/L to 12 g/L, and for another example, 10 g/L.
- According to an embodiment of the present disclosure, in the step (a), a temperature under which the insulating substrate is placed in the mixed solution A is from 60° C. to 130° C. For example, the temperature is from 80° C. to 110° C., from 85° C. to 95° C., and 90° C.; and a time for placing is, for example, 5 min-20 min, for example 6 min-15 min, and for example 10 min. In the step (a), the insulating substrate is placed in the mixed solution A to form an oxide layer.
- According to an embodiment of the present disclosure, in the step (b), a concentration of the thiophene monomer is from 10 mL/L to 30 mL/L, for example, 20 mL/L, a temperature for polymerization of the monomer is from 15° C. to 45° C., for example at room temperature, and a time for polymerization of the monomer is from 2 h to 8 h, for example from 3 h to 6 h, for example 4 h. Further, a small amount of pH-adjusting acid is added to adjust a pH of the solution for polymerization. The pH-adjusting acid is, for example, selected from phosphoric acid and boric acid. For example, the acid is phosphoric acid with a concentration from 1 mL/L to 5 mL/L.
- According to an embodiment of the present disclosure, the method further comprises a pretreatment step (step before the step (a)): degreasing, washing the insulating substrate followed by plasma processing. In the degreasing step, the degreasing liquid used is at least one selected from the group consisting of an alkaline agent, a surfactant, and a phosphate. For example, the degreasing liquid is a mixture of sodium hydroxide, sodium dodecylbenzenesulfonate, sodium carbonate, and trisodium phosphate. A ratio of the above components in the mixture is, for example, 15-25 g/L: 0.5-2 g/L: 1-5 g/L: 3-7 g/L; for example 20 g/L: 1 g/L: 3 g/L: 5 g/L; for example, the degreasing process is carried out at 40° C.-80° C. (for example, 40° C.-60° C.) for 3 min-30 min (for example, 3 min-10 min) followed by washing and drying. The plasma process is carried out under atmospheric pressure of 70 pa-120 pa and with a frequency of 80 w-100 w. For example, the pressure is 90 pa, and the frequency is 90 w.
- An embodiment of the present disclosure further provides a composite conductive polymer obtained by the above preparation methods, comprising an elementary metal. An embodiment of the present disclosure further provides use of the metal-containing composite conductive polymer in electroplating.
- In another aspect, an embodiment of the present disclosure provides a method for electroplating, which comprises: electroplating a substrate covered with the composite conductive polymer.
- According to an embodiment of the present disclosure, the electroplating method comprises: placing a substrate covered with the composite conductive polymer in a plating solution, applying electric current, electroplating with air agitation at room temperature, and then washing and drying.
- The plating solution comprises copper sulfate pentahydrate, concentrated sulfuric acid and chloride ion, and a concentration of the copper sulfate pentahydrate in the plating solution is from 80 g/L to 120 g/L, for example, from 90 g/L to 110 g/L, and for example, 100 g/L; a concentration of concentrated sulfuric acid in the plating solution is from 80 mL/L to 120 mL/L, for example, from 90 mL/L to 110 mL/L, for example, 100 mL/L.
- A density of the applied current is from 2 A/dm2 to 3 A/dm2, for example 2.5 A/dm2; and time for electroplating with air inflation is, for example, 20 min-50 min, for example 25 min-35 min, for example 30 min.
- The beneficial effects of the disclosure are as follows:
- 1. The composite conductive polymer synthesized by embodiments of the present disclosure, containing elementary metal, has good film-forming property and the film obtained can completely cover the surface of the insulating substrate, with a square resistance from 500Ω/□ to 3×103Ω/□ and excellent electrical conductivity, which therefore can be widely used in electroplating materials and semiconductor materials and other fields.
- 2. The mixed solution A employed in embodiments of the present disclosure contributes to synchronization of polymerization and metal element formation, and enables short time to produce a composite conductive polymer.
- 3. The preparation process of embodiments of the present disclosure enables a composite conductive polymer film to grow on all kinds of insulating materials.
- 4. The preparation process of the composite conductive polymer according to embodiments of the present disclosure is simple and easy to operate, with low cost, during which, the solution employed in the polymerization reaction, without any toxic organic solvent, can be reused, thus is environment-friendly synthesis process for materials.
-
FIG. 1 is a physical view of an original insulating substrate; -
FIG. 2 is a physical view of the sample ofFIG. 1 covered by a copper-containing conductive polythiophene, following the proceedings of example 1; -
FIG. 3 is an XRD pattern of the sample ofFIG. 2 ; -
FIG. 4 is a physical view of the sample ofFIG. 2 plated with copper. - The preparation method of the present invention will be further described in detail below with reference to specific examples. It is understood that the following examples are merely illustrative of the invention and are not to be construed as limiting the scope of the invention. The technology implemented based on the above description of the present invention is intended to be within the scope of the present invention. The experimental methods used in the following examples are all conventional methods unless otherwise specified; The reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
- An insulating substrate (epoxy resin substrate, as shown in
FIG. 1 ), after reacting with a degreasing solution (a mixture of 20 g/L sodium hydroxide, 1 g/L sodium dodecylbenzene sulfonate, 3 g/L sodium carbonate and 5 g/L of trisodium phosphate) at 50° C. for 5 minutes, was washed and dried. Then, the degreased insulating substrate was subjected to air plasma treatment at room temperature for 5 minutes, under a pressure of 90 Pa, and a frequency of 90 W. Subsequently, the treated insulating substrate was immersed in a mixture of 0.5 wt % potassium permanganate, 0.1 mol/L CuCl2.2H2O and 10 g/L boric acid at 90° C. for 10 min to form an oxide layer on the insulating substrate, which was then washed and dried. After that, the insulating substrate was immersed in a solution containing 20 mL/L of thiophene monomer for polymerization at room temperature (the solution for polymerization was purchased from Guangdong Guanghua Technology Co., Ltd., code 2303), added with 3 mL/L of phosphoric acid to adjust the pH value of the solution for polymerization, followed by reacting for 4 hours to obtain a copper-containing conductive polythiophene on the insulating substrate, and then washed and naturally dried. - The copper-containing conductive polythiophene obtained by the polymerization of example 1 is shown in
FIG. 2 . By comparingFIG. 1 andFIG. 2 , it can be seen that the copper-containing polythiophene film prepared by the embodiment of the present disclosure has good coverage property. Information about the crystal face of the elementary copper contained in the product is detected by XRD, which shows a face-centered cubic structure (seeFIG. 3 ). - The obtained copper-containing polythiophene film was subjected to a four-probe detector to measure the square resistance to characterize its electrical conductivity, and the measured square resistance is 1.83×103Ω/□. In addition to this, a content of copper in the copper-containing polythiophene film was measured by XPS to be 1.68 wt %.
- A substrate grown with a copper-containing conductive polythiophene was immersed in a plating solution comprising 100 g/L of copper sulfate pentahydrate, 100 mL/L of concentrated sulfuric acid, and 60 mg/L of chloride ion, applied a current of 2.5 A/dm2, plated with air agitation for 30 minutes at room temperature, and taken out for washing and drying. The copper conductive layer was evenly covered on the substrate, which was as shown in
FIG. 4 , and it can be seen that the copper-containing conductive polythiophene film prepared by the present embodiment has excellent properties suitable for electroplating application. - The composite conductive polymer was prepared referring to example 1, under the same conditions as example 1 except that the concentration of CuCl2.2H2O was changed to 0.5 mol/L. Finally, a copper-containing conductive polythiophene film on the surface of the substrate was obtained.
- The square resistance of the film is 590Ω/□ and the copper content of the film is 3.57 wt %.
- The composite conductive polymer was prepared referring to example 1, under the same conditions as example 1 except that 0.1 mol/L AgNO3 was used instead of CuCl2.2H2O. Finally, a silver-containing conductive polythiophene film on the surface of the substrate was obtained.
- The square resistance of the film is 1.36×103Ω/and the copper content of the film is 2.02 wt %.
- The embodiments of the present disclosure have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the invention are intended to be included within the scope of the present invention.
Claims (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/182,814 US11655379B2 (en) | 2018-10-24 | 2021-02-23 | Composite conductive polymers, preparation method and application thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811244146.5A CN111171356B (en) | 2018-10-24 | 2018-10-24 | Method for preparing composite conductive polymer |
CN201811244146.5 | 2018-10-24 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/182,814 Continuation US11655379B2 (en) | 2018-10-24 | 2021-02-23 | Composite conductive polymers, preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US20200131378A1 true US20200131378A1 (en) | 2020-04-30 |
Family
ID=70325073
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/245,098 Abandoned US20200131378A1 (en) | 2018-10-24 | 2019-01-10 | Composite conductive polymers, preparation method and application thereof |
US17/182,814 Active 2039-06-25 US11655379B2 (en) | 2018-10-24 | 2021-02-23 | Composite conductive polymers, preparation method and application thereof |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/182,814 Active 2039-06-25 US11655379B2 (en) | 2018-10-24 | 2021-02-23 | Composite conductive polymers, preparation method and application thereof |
Country Status (2)
Country | Link |
---|---|
US (2) | US20200131378A1 (en) |
CN (1) | CN111171356B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114609197B (en) * | 2022-03-25 | 2023-11-21 | 电子科技大学 | Gas-sensitive material, preparation method and NH (NH) thereof 3 Application in gas sensor |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0263730A (en) * | 1988-08-31 | 1990-03-05 | Teijin Ltd | Porous conductive composite material and preparation thereof |
JPH04141910A (en) * | 1990-09-29 | 1992-05-15 | Achilles Corp | Conductive vacuum-molded product |
FR2691988B1 (en) | 1992-06-05 | 1995-07-13 | Commissariat Energie Atomique | METHOD OF IMPREGNATING A CONTINUOUS SUBSTRATE WITH AN ELECTRONIC CONDUCTIVE POLYMER. |
DE10124631C1 (en) | 2001-05-18 | 2002-11-21 | Atotech Deutschland Gmbh | Direct electrolytic metallization of insulating substrate surface, used in circuit board production, e.g. for metallizing fine holes, uses pretreatment with water-soluble polymer and acid solutions of permanganate and thiophen compound |
EP1551847B1 (en) | 2002-10-07 | 2006-07-05 | Agfa-Gevaert | 3,4-alkylenedioxythiophene compounds and polymers thereof |
WO2005010100A1 (en) | 2003-07-25 | 2005-02-03 | Kaneka Corporation | Resin composition containing ultrafine particles |
DE102004037542A1 (en) * | 2004-08-03 | 2006-02-23 | Chemetall Gmbh | Method, useful to protect metallic surface with corrosion inhibitor composition coating comprises applying coating on metallic surface, where the components comprising: deposit substance; and further components and/or matrix substance |
EP1897974B1 (en) * | 2006-09-07 | 2012-08-01 | Enthone Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
CN1958852A (en) * | 2006-10-11 | 2007-05-09 | 扬州大学 | Electrochemical method for synthesizing Nano particles of polyaniline with transition metal being doped |
EP2447296B1 (en) | 2010-10-29 | 2018-01-10 | MacDermid Enthone Inc. | Compostion and method for the deposition of conductive polymers on dielectric substrates |
US20140021400A1 (en) | 2010-12-15 | 2014-01-23 | Sun Chemical Corporation | Printable etchant compositions for etching silver nanoware-based transparent, conductive film |
WO2012170643A1 (en) | 2011-06-07 | 2012-12-13 | Ndsu Research Foundation | Template-free aqueous synthesis of conductive polymer nanoparticles |
US10043598B2 (en) | 2011-08-01 | 2018-08-07 | National Institute For Materials Science | Process for precipitation of conducting polymer/metal composites, and conducting polymer/metal composites |
WO2014101193A1 (en) | 2012-12-31 | 2014-07-03 | Jiangnan University | Dithienylpyrrole-based biosensors and methods for their preparation and use |
CN104031244B (en) * | 2014-01-08 | 2016-11-23 | 上海大学 | The method quickly preparing polythiophene in mixed solvent system |
CN104861189B (en) | 2015-05-25 | 2018-04-13 | 华南理工大学 | A kind of method of poly- 3,4 ethylenedioxy thiophenes of fabricated in situ/nanometer metallic silver transparent conducting coating |
CN109485833A (en) | 2018-11-08 | 2019-03-19 | 上海萃励电子科技有限公司 | A kind of synthetic method of Cu-PEDOT composite conductive powder |
-
2018
- 2018-10-24 CN CN201811244146.5A patent/CN111171356B/en active Active
-
2019
- 2019-01-10 US US16/245,098 patent/US20200131378A1/en not_active Abandoned
-
2021
- 2021-02-23 US US17/182,814 patent/US11655379B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US11655379B2 (en) | 2023-05-23 |
CN111171356B (en) | 2021-06-22 |
CN111171356A (en) | 2020-05-19 |
US20210179866A1 (en) | 2021-06-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10221357B2 (en) | Etching of plastic using acidic solutions containing trivalent manganese | |
Fenelon et al. | The electropolymerization of pyrrole at a CuNi electrode: corrosion protection properties | |
DE3544957A1 (en) | METHOD FOR PRODUCING AN ELECTRICALLY CONDUCTING COMPOSITE POLYMER MOLDED BODY | |
Bazzaoui et al. | A simple method for acrylonitrile butadiene styrene metallization | |
CN110029382B (en) | Surface treatment process for direct electroplating and related direct electroplating process | |
US11655379B2 (en) | Composite conductive polymers, preparation method and application thereof | |
CN108305704A (en) | A kind of graphene-based High-conductivity carbon slurry and preparation method thereof | |
CA1237092A (en) | Metallisation process for electrically insulating comformable films made from thermally stable plastics, and articles thus made | |
JP2008097949A (en) | Conductive paste | |
Richardson et al. | Electronic properties of intrinsically conducting polymer-cellulose based composites | |
TWI438301B (en) | Metal plated article of molded form and method for producing it | |
Lai et al. | Rapid metallization by copper electroplating on insulating substrate using silver nanowires conductive composite as seed layer | |
KR101396919B1 (en) | Method of improving adhesion between polymer film and metal layer | |
EP2920341B1 (en) | Electrolytic generation of manganese (iii) ions in strong sulfuric acid | |
KR102373554B1 (en) | Method for metallizing dielectric substrate surface, and dielectric substrate provided with metal film | |
US10246788B2 (en) | Electrolytic generation of manganese (III) ions in strong sulfuric acid using an improved anode | |
CN113692111B (en) | High-corrosion-resistance flexible copper-clad plate and preparation method thereof | |
CN101736331A (en) | Adhesive layer forming liquid and adhesive layer forming process | |
JP5310993B2 (en) | Plating undercoating on styrene resin substrate and plated product of styrene resin substrate produced using the same | |
EP0505880B1 (en) | Electron induced transformation of an isoimide to an N-imide and uses thereof | |
CN112185606B (en) | High-molecular flexible conductive film and preparation method thereof | |
CN111349254A (en) | Method for preparing polythiophene film in large area | |
JP4614445B2 (en) | Conductive thin film, flexible member using the same, transparent electrode member, and electromagnetic shielding coating film | |
Eftekhari | Enhanced stability of hexacyanoferrate-based modified electrodes prepared under centrifugal fields | |
KR101152287B1 (en) | Orgarnic-Inorganic Light-Emitting Complex |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UNIVERSITY OF ELECTRONIC SCIENCE AND TECHNOLOGY OF CHINA, CHINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHOU, GUOYUN;HONG, YAN;LI, JIUJUAN;AND OTHERS;SIGNING DATES FROM 20181206 TO 20181209;REEL/FRAME:047960/0711 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |