CN102876037B - Method for preparing metal/polyaniline/plastic composite film through electrochemical in-situ polymerization - Google Patents
Method for preparing metal/polyaniline/plastic composite film through electrochemical in-situ polymerization Download PDFInfo
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Abstract
The invention discloses a method for preparing a metal/polyaniline/plastic composite film through electrochemical in-situ polymerization. The method comprises the following steps of: 1) preparing a polyaniline/plastic conductive composite film, namely performing electrooxidation polymerization of polyaniline in an aniline-acid solution by taking a plastic microporous film as a base film to obtain the polyaniline/plastic conductive composite plastic film, wherein the electric conductivity of the polyaniline/plastic conductive composite plastic film is 1 to 59.5S.cm<-1>; and 2) preparing a polyaniline/plastic/metal conductive composite film, namely electrodepositing silver on the surface of the polyaniline/plastic conductive composite film to obtain the polyaniline/plastic/metal conductive plastic composite film, wherein the electric conductivity of the polyaniline/plastic/metal conductive plastic composite film is 10<2> to 10<4>S.cm<-1>. The conductive plastic composite film prepared by the method has high electric conductivity and thermal stability and excellent mechanical properties, is high in performance price ratio and light in mass, realizes the organic combination of conductive polymers and metal particles, overcomes the unworkability of the polyaniline, and expands the application range of the conductive polymers. The method is simple and easy; and the obtained composite film can be used as a photoelectronic device, and is used for various fields such as detection and sensing, and electromagnetic shielding.
Description
Technical field
The invention discloses the method that metal/polyaniline/composite plastic film is prepared in the polymerization of a kind of electrochemical in-situ; Belong to conductive composite film technical field of material.
Background technology
Polyaniline (PANI) has high, the unique mechanism of doping effect of specific conductivity, and environmental stability is good, monomer low cost and other advantages, is one of conductive polymers with actual application prospect, is subject to extensive concern both domestic and external and conducts a research.Because single PANI has finite conductivity, and insolublely not melt, be difficult to the shortcomings such as machine-shaping, serious hamper it and apply in every field.Therefore by making it can make full use of superposing of electroconductibility with the matrix material disperseed or the method such as lamination is formed and improve its electroconductibility with metal powder, steel fiber etc., both can be utilized in the performance complement advantage to improve its processing forming with superpolymer compound, have very important significance.
PANI/ polymer composites is easily shaping, but its specific conductivity increase rate compared with simple PANI is little, be difficult to reach higher service requirements, and metal is excellent conductor, PANI and metal composite greatly can be improved electroconductibility, a small amount of metallics is introduced as Au Ag Pt Pd, copper etc. in PANI, the matrix material formed is compared with single PANI, cost is low, its conductivity, electrochemical response performance and electrocatalysis characteristic etc. are obtained for further lifting, can meet business demand even for aerospace cause.
Under electric field action, containing in the solution of aniline monomer, obtain conductive type polyaniline composite film in the direct electrolytic oxidation polymerization doping of cellular plastic film surface, its processing forming can be improved.The method is simple to operate, and be polymerized, a step of adulterating completes, the processibility of the polyaniline both improved, also improves specific conductivity to a certain extent.
Patent CN101225178 reports the conductive composite film of in-situ polymerization polyaniline in polysulfone membrane, and adopt chemistry polymerizing in situ method to produce, complex steps, and the specific conductivity of composite membrane is not high, the scope of specific conductivity only has 7.21 × 10
-4scm
-1~ 0.286Scm
-1
Patent CN101033301 reports the preparation method of polyaniline/polybutadiene rubber conductivity composite membrane, with cis-1,4-polybutadiene rubber as body material, adopt solution blending teeming practice, be prepared into a doped polyaniline/polybutadiene rubber conductivity composite membrane, and select meta-cresol to carry out secondary doping as secondary doping agent to composite membrane; This film improves the processing forming of polyaniline, but the specific conductivity of this composite membrane is not high yet, only has 10
-1scm
-1
Above-mentioned patent Introduction be all organic hybrid films, there is complex process, the defects such as composite membrane electric conductivity is low.And seldom see the successful patent report of polymer and metal formation composite membrane so far.This is because metal and polymer are two kinds of diverse materials of chemical constitution, therefore both carry out compound tense, storeroom interface interaction makes it be difficult to dissolve each other, and the density of metal is generally much bigger than polymer, therefore can there is serious demixing phenomenon in compound tense, cause material homogeneity poor, and electric conductivity is not high.
Summary of the invention
The object of the invention is to provide a kind of electrochemical in-situ to be polymerized the method preparing metal/polyaniline/composite plastic film.The method preparation technology is simple, easy to operate, makes polyaniline and metal form three-dimensional network conductive path, obtained composite membrane good conductivity, good mechanical performance, Heat stability is good.
The method of metal/polyaniline/composite plastic film is prepared in a kind of electrochemical in-situ polymerization of the present invention, comprises the following steps:
The first step: the preparation of polyaniline/Plastic conductive composite membrane
With the stainless steel plate of cellular plastic film parcel for anode, stainless steel plate is negative electrode, and with aniline-acid solution for electrolytic solution, polyaniline/Plastic conductive composite membrane is prepared in electrooxidation polymerization; Described electrooxidation polymerization technique parameter is: temperature; 10 DEG C-80 DEG C; Current density is 5-20mAcm
-2;
Second step: the preparation of metal/polyaniline/Plastic conductive composite membrane
The first step gained is enclosed with the stainless steel plate of polyaniline/Plastic conductive composite membrane as negative electrode, graphite is as anode, and electrolytic solution is silver ion solution, at polyaniline/Plastic conductive composite membrane substrates silver, obtains metal/polyaniline/Plastic conductive composite membrane; Described galvanic deposit parameter is: silver ion solution ph is 0.5-4; Temperature; 20 DEG C-80 DEG C; Current density 5-20mAcm
-2.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, described cellular plastic film is selected from the one in polyvinyl alcohol, polysulfones, polyimide, polyvinylidene difluoride (PVDF), tetrafluoroethylene, and cellular plastic membrane pore size is 1-10 micron.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, and the solute of described aniline-acid solution is made up of aniline, mineral acid, organic acid mixture; In described aniline-acid solution, aniline, mineral acid, organic acid mol ratio are 1:1:9-5:10:10; Containing aniline in often liter of aniline-acid solution is 0.25 ~ 0.8 mole, containing mineral acid 1 ~ 2 mole, is 0.05 ~ 0.2 mole containing organic acid; Described mineral acid is selected from, one in sulfuric acid, hydrochloric acid, perchloric acid; Described organic acid is selected from the one in sulphosalicylic acid, tosic acid, camphorsulfonic acid.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, and described electrooxidation polymerization time is 1-60min.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, and the solute of described silver ion solution is the mixture of Silver Nitrate and tartrate or tartrate; Or be the mixture of Silver Nitrate and citric acid or Citrate trianion, solvent is distilled water; In described silver ion solution, the mol ratio of silver ions and citrate or tartrate ion is 1 ~ 2:1; Containing Silver Nitrate in often liter of silver ion solution is 0.1 ~ 0.3 mole, is 0.05 ~ 0.15 mole containing citrate or tartrate ion.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, and described tartrate is selected from the one in soluble tartrate, sodium tartrate or Seignette salt; Described Citrate trianion is selected from the one in Tripotassium Citrate, Trisodium Citrate.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, and electrooxidation polymerization adopts galvanostatic method, the one in constant voltage method, cyclic voltammetry.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, and the power supply of described electrooxidation polymerization is direct supply or the pulse power; Described direct supply is constant voltage or constant-current dc power supply; The recurrence interval of the described pulse power is 10 ~ 100ms, and dutycycle is 0.5 ~ 0.9.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, carries out cross directional stretch or longitudinal stretching to metal/polyaniline/Plastic conductive composite membrane; Tensile stress is 0.5-1MPa; The specific conductivity of composite membrane is made to improve 10 ~ 35%.
A kind of electrochemical in-situ polymerization of the present invention is prepared in the method for polyaniline/plastic/metal composite membrane, metal/polyaniline/Plastic conductive composite membrane is heated to 50-180 DEG C, after being incubated 3-6 hour under vacuum or argon gas, nitrogen atmosphere, cool to room temperature with the furnace, make composite membrane specific conductivity improve 5%-55%.
The present invention is owing to adopting above-mentioned processing method, polyaniline and metal is made to form three-dimensional network conductive path, transverse direction to a certain degree or longitudinal stretching are carried out to composite membrane, or composite membrane is carried out at air, vacuum or nitrogen, carry out thermal treatment to a certain degree under the environment of argon gas, further increase composite membrane specific conductivity.The conductive plastics composite membrane specific conductivity of preparation is high, thermally-stabilised good, excellent in mechanical performance, cost performance is high, light weight, practical, solve polyaniline unworkability, the defects such as the conductive composite film specific conductivity prepared is low, achieve the combination of conducting polymer and metallics, first, because on cellular plastic film, the PANI of electropolymerization is conducting polymer, therefore give whole composite membrane and be provided with electroconductibility as metal, therefore just possibility is become the enterprising row metal galvanic deposit (plating) of PANI of conduction again, and there is certain chemical bond between the metal of this galvanic deposit and the PANI of conduction, therefore bonding force is very firm, secondly owing to being carry out metal deposition under the electric field, therefore metal is all identical in any one deposition of composite membrane, this is just avoided having occurred that the phenomenon of layering appears in metal and polymer compound because density is different, the last galvanic deposit due to metal not only comprises the growth of crystal grain, also have growing up of crystal grain, as long as electricity is enough, metal enters the another side that can grow from the one side of composite membrane, make whole composite membrane electroconductibility everywhere even.Therefore the present invention has expanded the range of application of conducting polymer. and present method is simple, and the composite membrane obtained can be used as opto-electronic device, detects and the numerous areas such as sensing, electromagnetic shielding.
Embodiment
The composite membrane prepared of the embodiment of the present invention adopts sheet resistance instrument DMR-1C(Nanjing to reach bright) resistance of test compound film, at least measure 10 different points, average.By formula Κ=1/ (R
□wF) specific conductivity Κ (R is calculated
□for square resistance, Ω; W is film thickness, cm; F is instrument correction factor).
Be described below in detail embodiments of the invention, described embodiment is exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.Certainly, those skilled in the art according to following description scheme, may propose corresponding modify or change, and these amendments or change all should be included in of the present invention comprising within scope.
Embodiment 1
Be that the PVA parcel of 5 ~ 10 microns is on stainless steel as anode using aperture.Be the aniline of 0.75 mol/L containing concentration, adding the sulphosalicylic acid of 0.2 mole in the sulphuric acid soln of 1.5 mol/L, electrolyzer immerses in constant water bath box, negative electrode stainless steel plate, power supply carries out the continuous current electrochemical synthesis of polyaniline, temperature controls at 40 DEG C, time 10min, current density 15mAcm
-2, take off anode after polymerization completely and soak to remove the solution be attached on film in clear water, then drying PVA-PANI film on stainless steel plate, take off.The PVA-PANI composite membrane electricity smooth surface obtained, different with the height of current density according to dopant acid concentration, the specific conductivity of composite membrane can reach 20Scm
-1; Preparation PVA-PANI film on continue galvanostatic deposition silver, now with polyaniline composite film as negative electrode, graphite is anode, and electrolytic solution is 35g/L Silver Nitrate+50g/L Seignette salt, pH=2, liquid temperature 30 DEG C, time 3min, current density 50mAcm
-2, take out anode after deposition and soak to remove the solution be attached on film in clear water, drying, take off and obtain PVA-PANI-Ag composite membrane.The composite membrane specific conductivity that the method obtains comparatively PVA-PANI is greatly improved, and the average conductivity of composite membrane is 1250Scm
-1; PVA-PANI, PVA-PANI-Ag composite membrane of above-mentioned acquisition is carried out slow stretching, and tensile stress is 1MPa, and the specific conductivity of composite membrane can be made to significantly improve 20% and 35% respectively; By the PVA-PANI-Ag composite membrane of above-mentioned acquisition under vacuum 50 DEG C insulation 3 ~ 6 hours, furnace cooling, can make composite membrane specific conductivity improve 5%.
Embodiment 2
Be that the PSF covering of 5 ~ 10 microns is on stainless steel as anode using aperture.Be the aniline of 0.25 mol/L containing concentration, adding the sulphosalicylic acid of 0.1 mole in the sulphuric acid soln of 1 mol/L, electrolyzer immerses in constant water bath box, negative electrode stainless steel plate, power supply carries out the continuous current electrochemical synthesis of polyaniline, temperature controls at 40 DEG C, time 10min, current density 12mAcm
-2, take off anode after polymerization completely and soak to remove the solution be attached on film in clear water, then drying PSF-PANI film on stainless steel plate, take off.The PSF-PANI composite membrane electricity smooth surface obtained, the specific conductivity of composite membrane can at 5Scm
-1left and right; Preparation PSF-PANI film on continue galvanostatic deposition silver, now with polyaniline composite film as negative electrode, graphite is anode, and electrolytic solution is 35g/L Silver Nitrate+50g/L Seignette salt, pH=2, liquid temperature 30 DEG C, time 1min, current density 50mAcm
-2, take out anode and soak to remove the solution be attached on film in clear water, drying, take off and obtain PSF-PANI-Ag composite plastic film.The composite membrane specific conductivity that the method obtains comparatively PSF-PANI film is greatly improved, and the average conductivity of composite membrane is 1000Scm
-1.Carry out slow stretching to above-mentioned PSF-PANI, PSF-PANI-Ag composite membrane, tensile stress is 0.5MPa, and the specific conductivity of composite membrane can be made to significantly improve 15% and 5% respectively; To the 120 DEG C of insulations 3 ~ 6 hours under vacuum of the PSF-PANI-Ag composite membrane of above-mentioned acquisition, furnace cooling, can make composite membrane specific conductivity improve 5%.
Embodiment 3
Be the polytetrafluoroethylporous porous membrane of 3 ~ 5 microns by aperture be basement membrane, parcel does anode on stainless steel, negative electrode is stainless steel plate, electrochemical deposition polyaniline prepares PTFE-PANI composite plastic film, and electrolytic solution is be the aniline of 0.5 mol/L containing concentration, add the sulphosalicylic acid of 0.2 mole, constant temperature water bath in the sulphuric acid soln of 1 mol/L, galvanostatic deposition polyaniline, temperature controls at 50 DEG C, time 10min, current density 20mAcm
-2, take off anode after polymerization completely and soak to remove the solution be attached on film in clear water, then dry the PTFE-PANI composite plastic film taken off on stainless steel plate, the specific conductivity of composite membrane is at 55.90Scm
-1, PTFE-PANI composite membrane ammeter face is smooth.Electrodeposited Silver is continued on this composite membrane basis, and method as described in Example 1, obtains PTFE-PANI-Ag composite plastic film, and the average conductivity of composite membrane is 8552Scm
-1.PTFE-PANI, PTFE-PANI-Ag composite membrane of above-mentioned acquisition is carried out slow stretching, and tensile stress is 1MPa, and the specific conductivity of composite membrane can be made to significantly improve 20% and 35% respectively; By the PTFE-PANI-Ag composite membrane of above-mentioned acquisition under vacuum 120 DEG C insulation 3 ~ 6 hours, furnace cooling, can make composite membrane specific conductivity significantly improve 55%.
Claims (7)
1. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization, comprises the following steps:
The first step: the preparation of polyaniline/Plastic conductive composite membrane
With the stainless steel plate of cellular plastic film parcel for anode, stainless steel plate is negative electrode, and with aniline-acid solution for electrolytic solution, polyaniline/Plastic conductive composite membrane is prepared in electrooxidation polymerization; Described electrooxidation polymerization technique parameter is: temperature; 10 DEG C-80 DEG C; Current density is 5-20 mAcm
-2; The aperture of described cellular plastic film is 1-10 micron;
Second step: the preparation of metal/polyaniline/Plastic conductive composite membrane
The first step gained is enclosed with the stainless steel plate of polyaniline/Plastic conductive composite membrane as negative electrode, graphite is as anode, and electrolytic solution is silver ion solution, at polyaniline/Plastic conductive composite membrane substrates silver, obtains metal/polyaniline/Plastic conductive composite membrane; Described galvanic deposit parameter is: silver ion solution ph is 0.5-4; Temperature; 10 DEG C-80 DEG C; Current density 5-20 mAcm
-2;
3rd step:
Second step gained metal/polyaniline/Plastic conductive composite membrane is heated to 50-120 DEG C, after being incubated 3-6 hour under vacuum or argon gas, nitrogen atmosphere, cooling to room temperature with the furnace and take out, make composite membrane specific conductivity improve 5%-55%.
2. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization according to claim 1, it is characterized in that: described cellular plastic film is selected from the one in polyvinyl alcohol, polysulfones, polyimide, polyvinylidene difluoride (PVDF), tetrafluoroethylene.
3. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization according to claim 1, it is characterized in that: the solute of described aniline-acid solution is made up of aniline, mineral acid, organic acid mixture; Solvent is distilled water; In described aniline-acid solution, aniline, mineral acid, organic acid mol ratio are 1:1:9-5:10:10, and containing aniline in often liter of aniline-acid solution is 0.25 ~ 0.8 mole, and being 1 ~ 2 mole containing mineral acid, is 0.05 ~ 0.2 mole containing organic acid; Described mineral acid is selected from the one in described sulfuric acid, hydrochloric acid, perchloric acid; Described organic acid is selected from the one in sulphosalicylic acid, tosic acid, camphorsulfonic acid.
4. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization according to claim 1, it is characterized in that: described electrooxidation polymerization time is 1-30min.
5. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization according to claim 1, it is characterized in that: the solute of described silver ion solution is the mixture of Silver Nitrate and tartrate or tartrate; Or be the mixture of Silver Nitrate and citric acid or Citrate trianion, solvent is distilled water; In described silver ion solution, the mol ratio of silver ions and citrate or tartrate ion is 1 ~ 2:1, and containing Silver Nitrate in often liter of silver ion solution is 0.1 ~ 0.3 mole, is 0.05 ~ 0.15 mole containing citrate or tartrate ion.
6. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization according to claim 5, it is characterized in that: described tartrate is selected from the one in Seignette salt, sodium tartrate, soluble tartrate; Described Citrate trianion is selected from the one in Trisodium Citrate, Tripotassium Citrate.
7. the method for metal/polyaniline/composite plastic film is prepared in electrochemical in-situ polymerization according to claim 4, it is characterized in that: the power supply of described electrooxidation polymerization is direct supply or the pulse power; Described direct supply is constant voltage or constant-current dc power supply; The recurrence interval of the described pulse power is 10 ~ 100ms, and dutycycle is 0.5 ~ 0.9.
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| CN109853025B (en) * | 2019-01-08 | 2020-01-14 | 北京化工大学 | Composite film and preparation method and application thereof |
| CN110282715B (en) * | 2019-07-16 | 2021-08-31 | 闽江学院 | Preparation and application of polyquaternium in-situ composite modified polymeric ferric sulfate |
| CN112076635B (en) * | 2020-07-29 | 2022-08-23 | 南京工业大学 | Conductive polymer separation membrane, preparation method and application in dye separation |
| CN112592511A (en) * | 2020-12-16 | 2021-04-02 | 华东师范大学 | Sponge with electromagnetic shielding function and preparation method thereof |
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