CN102532892A - Conductive polymer film and preparation method thereof - Google Patents
Conductive polymer film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive polymer film and the preparation method thereof. The preparation method comprises the following steps: (1) dissolving polymer monomers in an organic solvent to obtain a solution A; (2) dissolving an oxidizer in water to obtain a solution B; and (3) mixing the solution A and the solution B to obtain a mixture C, and freezing the mixture C to form a crystal interface on which the monomers are polymerized to form the final product of conductive polymer film. The method has the advantages that the preparation technique is simple and convenient, the method has good controllability and wide application range and system, can be adapted to large-scale production, and is low in cost and great in economic benefit potential, and the conductive polymer film product is superior in electrical property.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of conducting polymer thin film and preparation method thereof.
Background technology
Conductive polymers has metal or semi-conductive characteristic electron, the advantage that is easy to process and the peculiar mechanical property of polymkeric substance, is the macromolecular material that integrates many specific performances therefore.The combination of these specific performances makes conductive polymers become a kind of special material, thereby enjoys scientific research person's favor.Common conductive polymers has: polyacetylene, polyaniline, polypyrrole, Polythiophene etc.Conducting polymer nano material has all showed outstanding advantage in many technical applications: high conductivity, high-specific surface area, charge transfer path weak point etc., these properties derive from its nano-scale.Summarize, the compound method of special construction conductive polymers mainly is divided into two types: template and no template.
Template is the important method of preparation conducting polymer composite and conductive polymer composite.Template can be divided into soft template (like tensio-active agent, liquid crystal molecule etc.) and hard template (like aluminum oxide porous film) according to the difference of its kind, also can be divided into the inorganics template (like SiO
2, conductor oxidate, nano metal particles etc.) and organic template (like porous polycarbonate film etc.).The conducting polymer composite that can prepare various patterns in conjunction with methods such as oxidative polymerization, doped in situ polyreaction, electrochemical reaction, letex polymerizations.Adopting the advantage of template is that the product size can be controlled through template size; Shortcoming is the aftertreatment work that preparation section is complicated, need loaded down with trivial details removing template, is difficult to realize producing in batches, and some template price is expensive in addition.
No template is exactly through adopting specific experiment condition directly to obtain conducting polymer under the help that does not have extraneous template; That this method has is simple, need not tensio-active agent and template aftertreatment, the output advantages of higher; But also there is certain shortcoming; Like sample topography and the difficult control of size, specific conductivity is low etc.Patent CN102020845A discloses a kind of method for making of electrically conductive polyaniline composite polypyrrole film; Promptly adopt the electrochemical method of no template between liquid-liquid interface, to obtain conductive composite film; But,, but can't adopt this method to obtain single polyaniline film like aniline for hydrophilic monomer.Patent CN101735468A discloses a kind of method for making of self-supporting conductive polymer film, but this method need be used the higher ionic liquid of cost, and is uneconomical on economic benefit.
In view of existing templates method and the deficiency that no template exists, press for a kind of better preparing method's the existing technology that substitutes.
Summary of the invention
The present invention aims to provide a kind of conducting polymer thin film and preparation method thereof,, sample topography low with the specific conductivity that solves the conducting polymer thin film that exists in the prior art and difficult control of size and preparation complicated technology problem.
To achieve these goals, according to an aspect of the present invention, a kind of preparation method of conducting polymer thin film is provided, has may further comprise the steps: 1) monomer to be gathered has been dissolved in the organic solvent, obtains solution A; 2) oxygenant is soluble in water, obtain mixing solutions B; 3) solution A is mixed with solution B obtain mixture C,, wait to gather monomer, obtain conducting polymer thin film in the crystal interface polymerization with the freezing formation crystal interface of mixture C.
Further, with solution A with before solution B is mixed, solution B is freezing.
Further, in step 2) in, in solution B, add doping agent.
Further, doping agent is one or more in the group formed of acids, surfactant-based, dye class, Schardinger dextrins and derivatives class thereof.Acids is selected from one or more in the group that hydrochloric acid, tosic acid, perchloric acid, Witco 1298 Soft Acid, beta-naphthalenesulfonic-acid, 5-dibutyl naphthalene sulfonic acid, camphorsulfonic acid, anthraquinone sulfonic acid forms.
Further, doping agent is (0: 1)～(10: 1) with waiting to gather monomeric mol ratio.
Further, monomer to be gathered is one or more in the group formed of aniline, pyrroles and thiophene and verivate thereof; Organic solvent is benzene, hexanaphthene, p-Xylol and 1, one or more in the group that the 4-dioxane is formed; Waiting to gather monomeric concentration in the solution A is 0.014mol/L～2.42mol/L.
Further, oxygenant is one or more in the group formed of ferric compound, persulphate, superoxide, transition metal salt and Nitrates; Wherein ferric compound is an iron(ic)chloride; Persulphate is an ammonium persulphate.
Further, oxygenant and monomeric mol ratio are (10: 1)～(1: 10) in the solution C.
According to a further aspect in the invention, a kind of conducting polymer thin film is provided, has been prepared from above-mentioned each preparation method.
Further, the specific conductivity of conducting polymer thin film is 50～3000S/cm.
Beneficial effect of the present invention:
(1) adopting the solvent crystal is template, only needs to melt just can template be removed, and has simplified the complicated process of removing template;
(2) can control film thickness and pattern effectively through changing monomer concentration, reaction times and freezing temp, effectively regulate and control the height of specific conductivity, have excellent controllability and large-scale suitability through changing dopant species or consumption;
(3) the present technique preparation method is easy, and cost of material is cheap, has huge economic efficient latent;
(4) conducting polymer thin film of preparing through technical scheme of the present invention has big area output, advantage such as snappiness preferably, makes things convenient for scale operation, has tempting application prospect in fields such as optics, electronic industries.
Description of drawings
Figure of description is used to provide further understanding of the present invention, constitutes a part of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, does not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 shows the change curve of the thickness of the conducting polymer thin film of exemplary embodiments preparation according to the present invention with the reaction times;
Fig. 2 shows the change curve of the thickness of the conducting polymer thin film of exemplary embodiments preparation according to the present invention with monomer concentration; And
Fig. 3 shows the film of poly pyrrole specific conductivity of the exemplary embodiments according to the present invention with doping agent and monomeric mol ratio change curve.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the application can make up each other.Below with reference to accompanying drawing and combine embodiment to specify the present invention.
According to a kind of exemplary embodiment of the present invention, the preparation method of conducting polymer thin film may further comprise the steps: 1) monomer to be gathered is dissolved in the organic solvent, obtains solution A; 2) oxygenant is soluble in water, obtain solution B, 3) solution A is mixed with solution B obtain mixture C, with the freezing formation crystal interface of mixture C, wait to gather monomer in the crystal interface polymerization, obtain conducting polymer thin film.Here saidly place the constant temperature refrigerator to carry out the freezing interface polymerization reaction mixture C freezing being meant of mixture C.This preparation technology is through under coldcondition; Making the organic solvent crystallization will wait to gather monomer discharges; Water crystallization is discharged the oxygenant ion, and waiting of being discharged from gathered monomer oxidized dose of ionic oxide formation and in-situ polymerization formation polymkeric substance takes place on the crystal interface that organic solvent and water form.So-called crystal interface refers to the interface of organic solvent crystallization and water crystallization formation, and selected organic solvent is and the inconsistent compound of water that the two is crystallization formation interface separately.Also be that said employing solvent crystal is that template in-situ polymerization between crystal interface prepares conducting polymer thin film.After thawing, crystal melts, thereby obtains one deck self-supporting polymeric film.This preparation method has simplified the complicated process of removing template because solvent crystallization can be removed template after melting.In addition, method of the present invention also has advantages such as the applicable system scope is wide, cost is low, economic efficient latent is big.
According to of the present invention preferred embodiment a kind of, with solution A with before solution B is mixed, solution B is freezing.With respect to above-mentioned direct freezing mode; This embodiment is directed freezing in liquid nitrogen with solution B earlier; Then solution A is joined in the crystalline solution B, again reaction mixture is placed under-40 ℃～-10 ℃ the low temperature and carry out freezing interface polymerization reaction, obtain conducting polymer thin film.It is good that this preparation method and above-mentioned direct mixing back refrigerated method are compared controllability, and the conducting polymer thin film that obtains is relatively complete, uniform in thickness, specific conductivity height and controllable process, but big area production.It promptly is the product that can obtain having the rule orientating structure that directed cold method also has an outstanding advantage.Oxygenant duct along crystal region in the process of water crystallographic orientation is directed discharge, waits to gather monomer then along the oxidized dose of oxidation generation in interface, the duct in-situ polymerization of crystallographic orientation, thereby obtains the long conductive polymers of conjugated chain.
According to a kind of exemplary embodiment of the present invention, in step 2) in, in solution B, add doping agent.Through adding the specific conductivity that doping agent can be regulated final product.Preferably, the doping agent of interpolation is one or more in the group formed of acids, surfactant-based, dye class, Schardinger dextrins and derivatives class thereof; Preferably, acids is selected from one or more in the group that hydrochloric acid, tosic acid, perchloric acid, Witco 1298 Soft Acid, beta-naphthalenesulfonic-acid, 5-dibutyl naphthalene sulfonic acid, camphorsulfonic acid, anthraquinone sulfonic acid forms.The doping agent that adds is not limited to the above-mentioned type, can regulate the height of the specific conductivity of final product through the kind and the quantity of regulating doping agent.In general, with respect to mineral acid, interpolation organic acid effect is better; Because organic acid molecular weight and volume are big; Sterically hindered effect is big, and it is crosslinked to stop monomer on other unnecessary positions, to take place effectively, makes monomer that polymerization take place on crystal interface better; And can induce the degree that improves crystallization, obtain the longer conducting polymer thin film of conjugated chain.
Further preferably, doping agent and monomeric mol ratio are 0: 1～10: 1.The consumption of doping agent and the specific conductivity of film are closely related, are not add The more the better, have just begun the increase along with the doping agent consumption; The specific conductivity of polymeric film is in rising trend; But along with increasing of doping agent addition, specific conductivity reach the highest after, present downtrending again.
According to preferred implementation of the present invention, monomer to be gathered is one or more in the group formed of aniline, pyrroles and thiophene and verivate thereof; Organic solvent is benzene, hexanaphthene, p-Xylol and 1, one or more in the group that the 4-dioxane is formed; Monomer concentration is 0.014mol/L～2.42mol/L in the solution A.Monomer used in the present invention includes but not limited to above several kinds; As long as this monomer can be separated out at low temperatures and in-situ polymerization, using aniline, pyrroles or thiophene is because these monomers can obtain the ideal conducting polymer thin film at the plane of crystal polymerization reaction take place.Use benzene, hexanaphthene, p-Xylol, 1,4 dioxane as organic solvent, in fact select for use inorganic solvent water also passable, but need make monomer concentration be less than or equal to the solvent degree in its water.Select these solvents for use, main because their fusing point is higher, can crystallization in the time of-40 ℃～-10 ℃ and monomer discharged, make it that home position polymerization reaction take place.But consider technique effect and toxicity size, preferred hexanaphthene is made solvent.Regulate the specific conductivity except adding doping agent; Can also control the thickness of film and the height of size and specific conductivity through the size of control monomer concentration, oxidant concentration, monomer and oxidant ratio, doping agent consumption and reaction vessel, make the preparation process have good controllability.
Preferably; Monomeric concentration in the solution A is controlled between 0.014mol/L～2.42mol/L; Monomer in this concentration range can be separated out under-40 ℃～-10 ℃ and the further polymerization reaction take place at the interface smoothly, can obtain outward appearance and thickness uniform conductive polymeric film.The low excessively film that obtains of monomer concentration is too thin, intensity is low and imperfect; The film of the too high formation of concentration is too thick and internal layer is coarse.According to exemplary embodiment of the present invention, oxygenant is one or more in ferric compound, persulphate, superoxide, transition metal salt, the Nitrates composition group; Wherein ferric compound is an iron(ic)chloride; Persulphate is an ammonium persulphate.The present invention is preferred but be not limited to above-mentioned listed oxygenant, as long as can be with waiting that gathering the monomer oxidation makes it in interfacial polymerization.Preferably, oxygenant and monomeric mol ratio are (10: 1)～(1: 10).If the amount and the monomeric mol ratio of the oxygenant that adds are lower than at 1: 10 o'clock, can not the monomer complete oxidation also be can not get complete conducting polymer thin film; If the oxygenant and the monomeric mol ratio of adding are higher than 10: 1, then cause polymerization velocity too fast, heat of polymerization is big, causes assembling, and product electric conductivity is reduced.
According to a further aspect in the invention, a kind of conducting polymer thin film is provided, this conducting polymer thin film is prepared from above-mentioned any preparation method.Preferably, the specific conductivity 50～3000S/cm of conducting polymer thin film, and thickness and size adjustable make things convenient for big area production.Adopt the self-supporting conductive polymer film of the present invention's preparation can use any substrate to take out, even can not need substrate, unsettled drying gets final product, and overcome the harsh requirement of common templates to the substrate aspect.
Below in conjunction with embodiment beneficial effect of the present invention is described.
Embodiment 1:
The preparation of solution A: pyrrole monomer 0.18mmol is dissolved in the 3ml hexanaphthene, and obtaining monomer concentration is 0.06mol/L.
The preparation of solution B: ammonium persulphate 0.18mmol is dissolved in the deionized water of 5ml, adds the 0.60mmol concentrated hydrochloric acid then, mix and obtain settled solution.
Solution B added in the test tube fill solution A stir a moment, put into temperature then immediately and carry out the freezing interface polymerization reaction for-17 ℃ constant temperature refrigerator.Behind the reaction 12h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain the film of poly pyrrole of bright-coloured metalluster, thickness is 240nm, and specific conductivity is 580S/cm.
Embodiment 2:
The preparation of solution A: pyrrole monomer 0.72mmol is dissolved in the 3ml hexanaphthene, and obtaining monomer concentration is 0.24mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 1.45mmol is dissolved in the deionized water of 4ml, adds the 2.90mmol para Toluic Acid then and mix and obtain settled solution.
Solution B added in the test tube fill solution A stir a moment, quick freezing in liquid nitrogen atmosphere is immediately then immediately then put into temperature and is carried out freezing interface polymerization reaction for-17 ℃ constant temperature refrigerator after the freezing completion.Behind the reaction 24h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain ferrous metal glossy film of poly pyrrole, thickness is 220nm, and specific conductivity is 2010S/cm.
The preparation of solution A: pyrrole monomer 7.24mmol is dissolved in the 3ml hexanaphthene, and obtaining monomer concentration is 2.42mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 1.45mmol is dissolved in the deionized water of 4ml, adds the 2.90mmol para Toluic Acid then and mix and obtain settled solution.
Solution B added in the test tube fill solution A stir a moment, quick freezing in liquid nitrogen atmosphere is immediately then immediately then put into temperature and is carried out freezing interface polymerization reaction for-17 ℃ constant temperature refrigerator after the freezing completion.Behind the reaction 24h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain ferrous metal glossy film of poly pyrrole, thickness is 500nm, and specific conductivity is 730S/cm.
Embodiment 4:
The preparation of solution A: pyrrole monomer 5.80mmol is dissolved in the hexanaphthene of 40ml, obtaining monomer concentration is 0.14mol/L.
The preparation of solution B: in the crystallizing dish of diameter 125mm, Anhydrous Ferric Chloride 5.80mmol is dissolved in the deionized water of 40ml, adds para Toluic Acid 11.6mmol then, mix obtaining settled solution.
At first solution B being placed temperature is that-17 ℃ refrigerator is directly freezing, adds solution A then in crystalline solution B, and it is that-25 ℃ of constant temperature refrigeratores carry out freezing interface polymerization reaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain the film of poly pyrrole that area is the crystallizing dish caliber size, thickness is 400nm, and specific conductivity is 1480S/cm.
Embodiment 5:
The preparation of solution A: pyrrole monomer 0.72mmol is dissolved in the hexanaphthene of 10ml, obtaining monomer concentration is 0.072mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 2.48mmol is dissolved in the deionized water of 40ml, adds para Toluic Acid 2.48mmol then, mix obtaining settled solution.
At first B solution being placed temperature is that-17 ℃ refrigerator is directly freezing, then solution A is joined in the crystalline solution B, and it is that-20 ℃ of constant temperature refrigeratores carry out freezing interface polymerization reaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain the film of poly pyrrole that area is the crystallizing dish caliber size, thickness is 300nm, and specific conductivity is 3000S/cm.
Embodiment 6:
The preparation of solution A: pyrrole monomer 5.80mmol is dissolved in the hexanaphthene of 15ml, obtaining monomer concentration is 0.39mol/L.
The preparation of solution B: in the crystallizing dish of diameter 100mm, hydrogen peroxide 2.90mmol is dissolved in the deionized water of 15ml, mixes obtaining settled solution.
At first B solution being placed temperature is that-17 ℃ refrigerator is directly freezing, adds A solution then in crystalline B, and it is that-25 ℃ of constant temperature refrigeratores carry out freezing interface polymerization reaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain the film of poly pyrrole that area is the crystallizing dish caliber size, thickness is 600nm, and specific conductivity is 50S/cm.
Embodiment 7:
The preparation of solution A: pyrrole monomer 0.29mmol is dissolved in the p-Xylol of 10ml, obtains the solution that monomer concentration is 0.03mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 1.45mmol is dissolved in the deionized water of 30ml, the sulfonic acid 1.45mmol that camphorates then mixes obtaining settled solution.
At first get solution B 10ml and be immersed in the liquid nitrogen atmosphere directed freezingly with the speed of 2mm/min, then it is immersed in solution A, it is that-40 ℃ constant temperature refrigerator carries out polyreaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, the double-deck film of poly pyrrole that obtains having oriented structure, thickness in monolayer are 150nm, and specific conductivity is 1630S/cm.
Embodiment 8:
The preparation of solution A: pyrrole monomer 0.145mmol is dissolved in the hexanaphthene of 10ml, obtains the solution that monomer concentration is 0.014mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 1.45mmol is dissolved in the deionized water of 30ml, adds hydroiodic acid HI 1.45mmol then, mix obtaining settled solution.
At first get solution B 10ml and be immersed in the liquid nitrogen atmosphere directed freezingly with the speed of 2mm/min, then it is immersed in solution A, it is that-10 ℃ constant temperature refrigerator carries out polyreaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain film of poly pyrrole, thickness in monolayer is 50nm, and specific conductivity is 200S/cm.
Embodiment 9:
The preparation of solution A: thiophene monomer 0.75mmol is dissolved in the 10ml hexanaphthene, obtains the solution that monomer concentration is 0.07mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 3.00mmol is dissolved in the deionized water of 20ml, adds the 3.00mmol tosic acid then, mix and obtain settled solution.
At first get solution B 10ml and be immersed in the liquid nitrogen atmosphere directed freezingly with the speed of 2mm/min, then it is immersed in the A solution, it is that-20 ℃ constant temperature refrigerator carries out polyreaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain polythiophene film, thickness is 260nm, and specific conductivity is 890S/cm.
Embodiment 10:
The preparation of solution A: aniline monomer 0.80mmol is dissolved in the 10ml hexanaphthene, obtains the solution that monomer concentration is 0.08mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 4.00mmol is dissolved in the deionized water of 20ml, adds the 3.20mmol tosic acid then, mix and obtain settled solution.
Be immersed in the liquid nitrogen directed freezingly with getting the speed of solution B 10ml with 2mm/min, then it immersed in solution A, it is that-10 ℃ constant temperature refrigerator carries out polyreaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain polyaniline film, thickness is 300nm, and specific conductivity is 370S/cm.
Embodiment 11:
The preparation of solution A: aniline monomer 3.80mmol is dissolved in the 10ml hexanaphthene, obtains the solution that monomer concentration is 0.08mol/L.
The preparation of solution B: ammonium persulphate 0.38mmol is dissolved in the deionized water of 20ml, adds the 3.20mmol Witco 1298 Soft Acid then, mix and obtain settled solution.
Get B solution 10mL and be immersed in the liquid nitrogen directed freezingly with the speed of 2mm/min, then it is immersed in solution A, it is that-10 ℃ constant temperature refrigerator carries out polyreaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain polyaniline film, thickness is 300nm, and specific conductivity is 350S/cm.
Embodiment 12:
The preparation of solution A: 1.26mmol is dissolved in the 10ml benzene with N-methylpyrrole monomer, obtains the solution that monomer concentration is 0.13mol/L.
The preparation of solution B: Anhydrous Ferric Chloride 3.20mmol is dissolved in the deionized water of 20ml, adds the 3.20mmol tosic acid then, mix and obtain settled solution.
Be immersed in the liquid nitrogen directed freezingly with getting the speed of solution B 10ml with 2mm/min, then it immersed in solution A, it is that-20 ℃ constant temperature refrigerator carries out polyreaction that reaction mixture is placed temperature.Behind the reaction 48h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain gathering N-methylpyrrole film, thickness is 600nm, and specific conductivity is 130S/cm.
Embodiment 13:
The preparation of solution A: pyrrole monomer 0.72mmol is dissolved in the 3ml hexanaphthene, and obtaining monomer concentration is 0.24mol/L.
The preparation of solution B: cupric nitrate 1.45mmol is dissolved in the deionized water of 4ml, adds the 2.90mmol para Toluic Acid then and mix and obtain settled solution.
Solution B added in the test tube fill solution A stir a moment, quick freezing in liquid nitrogen atmosphere is immediately then put into temperature and is carried out freezing interface polymerization reaction for-25 ℃ constant temperature refrigerator after the freezing completion.Behind the reaction 24h, with product suction filtration after methyl alcohol, acetone, water clean repeatedly, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain ferrous metal glossy film of poly pyrrole, thickness is 300nm, and specific conductivity is 2600S/cm.
In conjunction with below embodiment furtherly prescribed reaction time and monomer concentration to the influence of film thickness.
Pyrrole monomer 0.36mmol is dissolved in the hexanaphthene of 10ml, obtaining monomer concentration is the A solution of 0.036mol/L; The Anhydrous Ferric Chloride of 1.8mmol is dissolved in the deionized water of 10ml, adds para Toluic Acid 1.8mmol then, mix and obtain clarifying B solution; At first that B solution is freezing in orientation at liquid nitrogen with the speed of 2mm/min, then it is immersed in the A solution, reaction mixture is placed-17 ℃ constant temperature refrigerator carry out the freezing interface polymerization reaction.After reaction times was respectively 0.5,1,2,3,4 day,, place 60 ℃ the dry 24h of vacuum drying oven at last, obtain a series of film of poly pyrrole, see Fig. 1 with different thickness with product suction filtration after methyl alcohol, acetone, water clean repeatedly.Fig. 1 can find out that the film thickness that obtains increases gradually along with the reaction times increases, and behind the certain hour, tends to balance, and no longer increases.
Pyrrole monomer 0.01,0.02,0.04,0.06,0.10,0.20,0.30,0.40,0.60ml are dissolved in respectively in the hexanaphthene of 8ml, obtain monomer and be concentration and be 0.018,0.036,0.072,0.11,0.18,0.36,0.48,0.72, the solution A of 0.96mol/L; It is 0.18mol/L that configuration contains the chlorination concentration of iron, and tosic acid concentration is the solution B of 0.36mol/L; It is directed freezing in liquid nitrogen with the speed of 2mm/min at first will to get the 10ml solution B, then it is immersed in the solution A, reaction mixture is placed-17 ℃ constant temperature refrigerator carry out the freezing interface polymerization reaction.After the reaction 48h,, place 60 ℃ the dry 24h of vacuum drying oven at last, obtain a series of film of poly pyrrole, see Fig. 2 with different thickness with product suction filtration after methyl alcohol, acetone, water clean repeatedly.As can be seen from Figure 2, along with the increase of monomer concentration, the thickness of the conducting polymer thin film that obtains increases gradually, but is limited to the restriction of interface shape size, and thickness can infinitely not increase.
In conjunction with below embodiment further specify the influence of doping agent and monomer different mol ratio to the polymer thin membrane conductivity.
Pyrrole monomer 0.72mmol is dissolved in obtains the solution A that monomer concentration is 0.24mol/L in the 3ml hexanaphthene; Anhydrous Ferric Chloride 1.45mmol is dissolved in the deionized water of 4ml, add respectively then with monomer mole ratio be that 0,0.5,1,2,4,6,8,10 tosic acid mixes and obtains a series of settled solution B; Solution B added fill in the test tube of solution A, stir a moment, quick freezing in liquid nitrogen atmosphere immediately then, freezing completion is placed on temperature and carries out the freezing interface polymerization reaction in-17 ℃ the constant temperature refrigerator.Behind the reaction 24h,, place dry 24h in 60 ℃ the vacuum drying oven at last, obtain a series of film of poly pyrrole, see Fig. 3 with different electric conductance with product suction filtration after methyl alcohol, acetone, water clean repeatedly.As can beappreciated from fig. 3; The addition of doping agent has bigger influence to the specific conductivity of polymeric film; Along with increasing of doping agent tosic acid addition, the specific conductivity of the polymeric film that obtains increases gradually, reach certain numerical value after; Add doping agent again, the specific conductivity of polymeric film reduces gradually.
Can find out from the foregoing description; Preparing method of the present invention has excellent controllability; Can control the thickness of synthetic conducting polymer thin film through controlling reaction time and monomer concentration; Prepare the conducting polymer thin film of high conductivity through controlled doping agent and monomeric adding proportion, this preparation method removes that template is convenient, thickness and controllable size.The conducting polymer thin film specific conductivity of utilizing technical scheme of the present invention to prepare is high, can be mass-produced.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a conducting polymer thin film is characterized in that, may further comprise the steps:
1) monomer to be gathered is dissolved in the organic solvent, obtains solution A;
2) oxygenant is soluble in water, obtain solution B;
3) said solution A is mixed with said solution B obtain mixture C,, saidly wait to gather monomer, obtain said conducting polymer thin film in said crystal interface polymerization with the freezing formation crystal interface of said mixture C.
2. preparation method according to claim 1 is characterized in that, with said solution A with before said solution B is mixed, said solution B is freezing.
3. preparation method according to claim 1 and 2 is characterized in that, in said step 2) in, in said solution B, add doping agent.
4. preparation method according to claim 3 is characterized in that, said doping agent is one or more in the group formed of acids, surfactant-based, dye class, Schardinger dextrins and derivatives class thereof; Said acids is to be selected from the group that hydrochloric acid, tosic acid, perchloric acid, Witco 1298 Soft Acid, beta-naphthalenesulfonic-acid, 5-dibutyl naphthalene sulfonic acid, camphorsulfonic acid, anthraquinone sulfonic acid forms one or more.
5. preparation method according to claim 4 is characterized in that, said doping agent and saidly wait to gather monomeric mol ratio for (0: 1)～(10: 1).
6. preparation method according to claim 1 and 2 is characterized in that, monomer said to be gathered is one or more in the group formed of aniline, pyrroles and thiophene and verivate thereof; Said organic solvent is benzene, hexanaphthene, p-Xylol and 1, one or more in the group that the 4-dioxane is formed; Waiting to gather monomeric concentration in the said solution A is 0.014mol/L～2.42mol/L.
7. preparation method according to claim 1 and 2 is characterized in that, said oxygenant is one or more in the group formed of ferric compound, persulphate, superoxide, transition metal salt and Nitrates; Said ferric compound is an iron(ic)chloride; Said persulphate is an ammonium persulphate.
8. preparation method according to claim 7 is characterized in that, said oxygenant and saidly wait to gather monomeric mol ratio for (10: 1)～(1: 10).
9. a conducting polymer thin film is characterized in that, is prepared from each described preparation method among the claim 1-8.
10. according to the said conducting polymer thin film of claim 9, it is characterized in that the specific conductivity of said conducting polymer thin film is 50～3000S/cm.
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