CN102321235B - Preparation method of poly-3,4-ethylene dioxythiophene and compound arrays thereof - Google Patents
Preparation method of poly-3,4-ethylene dioxythiophene and compound arrays thereof Download PDFInfo
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- CN102321235B CN102321235B CN 201110175894 CN201110175894A CN102321235B CN 102321235 B CN102321235 B CN 102321235B CN 201110175894 CN201110175894 CN 201110175894 CN 201110175894 A CN201110175894 A CN 201110175894A CN 102321235 B CN102321235 B CN 102321235B
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Abstract
The invention relates to a preparation method of poly-3,4-ethylene dioxythiophene and compound arrays thereof. Porous materials capable of being easily obtained are adopted as templates, poly-3,4-ethylene dioxythiophene and monomers or oxidizing agents of the compound of the poly-3,4-ethylene dioxythiophene are enriched in pores through chemical engineering reinforcement measures such as supergravity fields, vacuum filtration, surface treatment and the like, the templates are removed after the polymerization reaction, arrays consisting of fibers or pipes are obtained, the density, the thickness, the fiber diameter, the pipe diameter, the pipe wall, the pipe distribution, the structure, the appearance and the like of polymer arrays are regulated through controlling template pore structure parameters and reinforcement technological parameters, and the controllable preparation of polymer array materials is realized. The preparation method has the advantages that the interphase mass transfer process is enhanced, the contact between reactant precursors is enhanced, the filling rate of the template pore inside the template holes is improved, the array defects are few, the surface is flat and smooth, the pipe wall is easy to control, the preparation efficiency of the array materials is high, the array density is high, the reaction is easy to operate, the preparation method process is simple, the cost is low, the investment is little, the benefits are good, the industrial production is easy, and the preparation method is suitable for the scale low-cost production of three-dimensional array materials with few defects and high density.
Description
Technical field
The present invention relates to the preparation method of poly-3,4-ethylene dioxythiophene and mixture array thereof, coupling chemical industry enhancements original position in the casement plate forms array, and filling ratio is high in the hole, belongs to high performance three-dimensional array material preparation field.
Background technology
Poly-3, the 4-ethylenedioxy thiophene, also claim poly-3,4-ethene dioxythiophene, English are 3,4-ethylenedioxythiophene, abbreviation PEDOT or PEDT, be a kind of polythiofuran derivative of indissoluble, with polypyrrole, Polythiophene etc. the conjugated link(age) structure arranged, have high (the about 300 S cm under the room temperature of specific conductivity
-1), the advantage such as low, the good stability of energy gap (being subjected to ambient moisture to affect little, facile hydrolysis, fast light, high temperature resistant etc. not), optical transparence be good, synthetic easy, receive much concern in fields such as sensor, solar cell, solid-state capacitor, ultracapacitor, lithium ion battery, catalyzing manufacturing of hydrogen, liquid crystal display device, antistatic coating, Combined Electromagnetic Shielding Materials, soft-touch controls as a kind of organic functions electronic material.Poly-3, the monomer EDOT of 4-ethylenedioxy thiophene or EDT pass through in 3 of thiphene ring, the electron density of 4 the inferior ethylene dioxy bridge increase of introducing aromatic nucleus reduces the oxidizing potential of monomer and polymkeric substance, improve reactive behavior, the stability of polymkeric substance is improved, caused people's very big research interest since finding from 1938.The EDOT monomer is reductive agent, need to could polymerization form poly-3 through peroxidation, the 4-ethylenedioxy thiophene, different according to the acceptor that gets electronics, the preparation method who gathers 3,4-ethylene dioxythiophene can be divided into chemical polymerization and electrochemical polymerization, the former obtains electronics by oxygenant, the latter obtains electronics by electric field action, obtains product thereby make monomer lose electronics generation oxypolymerization.In the polymerization process, the EDOT monomer loses electronics and becomes the high reactivity intermediate that comprises radical cation under oxygenant or electric field action, through repeatedly obtaining the PEDOT product after the polymerization, so oxygenant kind and preparation technology parameter are larger on the electric conductivity impact of polymkeric substance.Because the electron delocalization scarce capacity of pure PEDOT, conductive capability can not get demonstrating fully, and can strengthen by mixing electron delocalization ability in the large π key in this intrinsic conduction polymer, improves electric conductivity.In order to solve the relatively poor problem of PEDOT solvability, adopt water miscible PSS PSS that it is carried out the charge balance doping vario-property and form the PEDOT/PSS composite membrane, can obtain by the aqueous solution polymerization of PEDOT/PSS, caused people's very big research interest in fields such as antistatic coating, super or solid capacitor electrode, photoactive electrode, organic photic devices.The aqueous solution of PEDOT/PSS is transparent, easily spin coating, and the commercially produced product kind is more, has been widely used in synthetic PEDOT/PSS.Yet the affiliation that adds of PSS causes the electroconductibility of polymkeric substance to decrease, and can improve electroconductibility [J. Mater. Chem., 2010,20,9740 – 9747] by add different amphoteric ion high polymer materials in the solution of PSS.
Super gravity field is the centrifuge field that is used to alternate separation, mainly be to obtain by rotating machinery integral body or parts, strengthen speed of relative movement between phase and phase and be in contact with one another, and " g " is larger, △ (ρ g) is larger, the fluid relative sliding velocity is also larger, thereby realizes efficient mass-and heat-transfer process and chemical reaction process.High-gravity technology is considered to strengthen a disruptive technology of transmission and heterogeneous reaction process, is described as " transistor of chemical industry " and " cross-centennial technology ".With contrast under the normal gravity field, molecular diffusion under super gravity field and interphase mass transfer process have obtained very big reinforcement, the mobile contact of homophase in porous medium do not strengthen, huge shear-stress has overcome surface tension of liquid, be nano level drop, brin, liquid film with liquid crushing and form new phase interface, make liquid stretch out huge phase border contact interface, rate of mass transfer (approximately 1 ~ 3 order of magnitude) and mass transfer coefficient (approximately 10 ~ 1000 times) have been improved, strengthened microcosmic and mixed and mass transfer process, be conducive to reactant solution and enter in the pattern hole.Vacuum filtration makes fully enrichment in the hole of solution by the pressure of relative increase reactant solution side, and is similar with super gravity field, the filling ratio in also can the Effective Raise hole.The method that material surface is processed is a lot, need to improve the filling ratio of reactant solution in the hole by adding the measures such as tensio-active agent or Cement Composite Treated by Plasma according to the character of hole surface and reactant solution.
Poly-3,4-ethylene dioxythiophene and the mixture pattern thereof of report have the forms such as powder, film, fiber and nanotube at present, there is not yet preparation method's report of its array material.Array material has the three-dimensional structure of specific area, the abundant contact and the mass transfer that are conducive to the differential responses phase, it is the desirable elementary cell of nanometer superminiature device, at present many employing galvanic deposit, electroless deposition craft (electroless plating) or self-assembly prepares in pattern hole, under the chemical industry enhancements, do not carry out, it is loose that array material contacts with hole surface, has that filling ratio material density not high, that the prepare hole in is poor, surfaceness is high, tube wall is difficult to the problems such as control, poor reproducibility.
Summary of the invention
The objective of the invention is in order to address the above problem, overcome the deficiencies in the prior art, creationary proposition a kind of poly-3, the brand-new processing method that 4-ethylenedioxy thiophene and mixture array thereof are synthetic, adopting the facile hole of appearance material is template, utilize super gravity field, vacuum filtration, the chemical industry enhancements such as surface treatment are fully enrichment poly-3 in the hole, the monomer of 4-ethylenedioxy thiophene and mixture thereof or oxygenant, after chemistry or electrochemical polymerization reaction, remove template and obtain the product array, simplified the synthesis technique flow process of array material, and can utilize the density of different template size parameters and reinforcing process parameter pair array, distribution and pattern control effectively, filling ratio is high in the pattern hole, and the array caliber is easy to control, and preparation efficiency and the density of array material are high, react easy to operate, preparation method's technique is simple, and cost is low, less investment, profitable, easy suitability for industrialized production.
[0006] basic conception of the present invention is: the present invention utilizes the chemical industry enhancements such as super gravity field, vacuum filtration, surface treatment will gather 3, the monomer of 4-ethylenedioxy thiophene and mixture thereof or oxygenant be fully enrichment in pattern hole, after polyreaction, remove template and obtain the product array, by thickness, density, distribution and the pattern etc. of control template size parameter and reinforcing process parameter adjustment polymer array, realize the controlled preparation of polymer array material.
The preparation method of poly-3,4-ethylene dioxythiophene of the present invention and mixture array thereof, the concrete technology step is as follows;
The employing aperture is that the hole material of 10 ~ 2000 nm is template, to gather 3, enhancements enrichment in pattern hole that the monomer of 4-ethylenedioxy thiophene and mixture thereof or oxygenant are processed by super gravity field, vacuum filtration, hole surface, after-50 ~ 150 oC polyreactions, remove template and form poly-3,4-ethylene dioxythiophene and mixture array thereof.
Among the present invention, the electrochemical polymerization that described polymerization refers to add the chemical polymerization of oxygenant and applies electric field action.
Among the present invention, described oxygenant refers to p-methyl benzenesulfonic acid iron, styrene sulfonate, p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid ammonium, p-methyl benzenesulfonic acid sodium, iron(ic) chloride, ferric sulfate, cupric chloride, ammonium peroxydisulfate, hydrogen peroxide.
Among the present invention, described hole material refers to etched hole aluminium, anodised aluminium, porous silicon, POROUS TITANIUM, nickel porous, porous carbon, Porous Stainless Steel, porous silica, porous ceramics, molecular sieve, polycarbonate, cetyltriethylammonium bromide CTAB.
Among the present invention, described aperture is 50 ~ 1500 nm.
Among the present invention, described super gravity field refers to that rotating speed is not less than 500 rpm/min by the centrifuge field of rotating machinery integral body or parts formation.
Among the present invention, described vacuum filtration refers to that reactant solution is lower than the operation of the pressure before the via hole material through the pressure behind the via hole material, utilize the pressure difference on solution both sides that oxidizing agent solution is pressed in the pattern hole, similar with super gravity field, strengthen the enrichment of reaction soln in the hole, vacuum tightness is not less than 0.02 MPa.
Among the present invention, described hole surface is processed hydrophilic, oleophylic or the Cement Composite Treated by Plasma that refers to be conducive to reactant enrichment in the hole.
Among the present invention, the array of preparation is comprised of fiber or pipe, can by thickness, density, Fibre diameter, caliber, tube wall, pipe distribution, structure and the pattern etc. of control pattern hole structural parameter and reinforcing process parameter adjustment polymer array, realize the controlled preparation of polymer array material.
The present invention compared with prior art, the invention solves poly-3, the series technique difficult problem of 4-ethylenedioxy thiophene and the controlled preparation of mixture array thereof, when having overcome electrochemical deposition method under the nonreinforcement measure or chemical electroless deposition processes and having prepared in the hole filling ratio low, the array material space is many, the problems such as the poor and surfaceness height of density, eliminated the loose deficiency of reactant precursor and pattern hole Surface Contact, creationaryly proposed to utilize super gravity field, vacuum filtration, the chemical industry enhancements such as surface treatment strengthen poly-3,4-ethylenedioxy thiophene and mixture monomer thereof or oxidizing agent solution are practised physiognomy with contacting of pattern hole surface, strengthen the mass transfer process of precursor in pattern hole, improve tamped density in the hole, have the following advantages and the high-lighting effect: by adopting super gravity field, vacuum filtration, the enhancements such as surface treatment improve the tamped density of reactant precursor in pattern hole, the phase interface that contacts on augmenting response thing solution and pattern hole surface, strengthen the mass transfer of reactant solution in the hole and with fully the contacting of hole wall, enhancements and reaction conditions easily realize, cost is low; Can by density, thickness, Fibre diameter, caliber, tube wall, pipe distribution, structure and the pattern etc. of control pattern hole structural parameter and reinforcing process parameter adjustment polymer array, realize the controlled preparation of polymer array material; Technique is simple, and is easy to operate, lower to the requirement of equipment; The reactant contact is abundant, and reacting phase Contact area is large, and the molecule contact is tight, and reaction easily occurs, and product yield is high, and resource utilization is high; Reaction raw materials is single, and is cheap and easy to get, and production cost is low, and less investment is profitable.
Description of drawings
Fig. 1 hypergravity prepares a kind of process flow diagram of PEDOT.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing; described content only is the basic explanation of the present invention under conceiving; but the present invention is not limited to following example, and any equivalent transformation according to technical scheme of the present invention is done all belongs to protection scope of the present invention.
Embodiment 1
Adopt the super gravity field enhancements to prepare the PEDOT array by in-situ polymerization in the hole, take p-methyl benzenesulfonic acid iron as oxygenant, process flow sheet as shown in Figure 1, p-methyl benzenesulfonic acid iron butanol solution and the 0.01 M EDOT monomer of 35 ~ 65 wt.% are pressed p-methyl benzenesulfonic acid iron: EDOT=(2.0 ~ 2.5): fully stir under 1 the mol ratio room temperature, putting into the liner aperture after mixing is the Plastic Bottle of the harsh pit aluminium of 500 ~ 1500 nm, bottle is put into whizzer and fixing, speed rotation 1 ~ 5 min with 20000 ~ 30000 rpm/min, take out the hole aluminum alloy pattern plate of impregnation thing solution, be transferred to dry 30 ~ 60 min in the baking oven of 60 ~ 100 oC, dissolve part hole aluminum alloy pattern plate with 8 wt.%NaOH solution, washing, drying obtains the PEDOT array.In this reaction process, for thickness and the density that makes array layer increases, can adopt the way that repeatedly repeats above-mentioned processing step to finish, that is: the hole aluminum alloy pattern plate that adheres to PEDOT of front first drying is put into again reactant solution and strengthened reactant in the enrichment in hole with super gravity field, dissolve template after the drying and obtain product.This reaction utilizes super gravity field that the phase-contact surface of reactant is increased, and the molecule contact is tightr, and it is easier to react.
Embodiment 2
Adopt the super gravity field enhancements to prepare the PEDOT array by gas-solid reaction, take cupric chloride as oxygenant, the cupric chloride high purity water solution of 0.005 ~ 0.02 M is put into the Plastic Bottle of the anodised aluminium that the liner aperture is 50 ~ 200 nm (AAO) template, bottle is put into whizzer and fixing, speed rotation 2 ~ 6 min with 5000 ~ 10000 rpm/min, take out the AAO casement plate of oxide impregnation agent, place the steam of EDOT monomer to react 2 ~ 10 min, dry 100 ~ 150 min of baking oven of 70 ~ 120 oC are put in taking-up, with 0.25 M Cr
2O
3H
3PO
4AAO casement plate is removed in the solution dissolving, obtains the PEDOT array.In this reaction process, for thickness and the density that makes array layer increases, can adopt the way that repeatedly repeats above-mentioned processing step to finish, that is: the AAO casement plate that adheres to PEDOT of front first drying is put into cupric chloride high purity water solution again, with super gravity field oxidation agent solution in the hole enrichment and gas-solid reaction occurs in the steam of EDOT monomer, dissolve template after the drying and obtain the product array.
Embodiment 3
Adopt the vacuum filtration method to prepare the PEDOT/PSS array by the in-situ chemical polymerization, take styrene sulfonate SS as oxygenant, PEDOT/PSS monomer (EDOT: SS=1: (2 ~ 6) toward 0.01 ~ 0.04 M, mass ratio) adds Virahol and tetrahydrofuran solvent and rapid stirring in the solution, make soltion viscosity reach 100 ~ 300 mP s by the amount of adjusting Virahol, being transferred to the bottom is lined with in the suction funnel of 300 ~ 600 nm porous silica templates, vacuum tightness is 0.02 ~ 0.08 MPa, suction filtration 30 ~ 60 min, improve the filling ratio of reactant solution in the silica template hole, behind 100 ~ 160 oC dryings, 5 ~ 50 min, hot sodium carbonate solution with 20 ~ 30% is removed silica template, with dry behind the deionized water wash, obtain the PEDOT/PSS array.
Embodiment 4
Prepare the PEDOT array by electrochemical polymerization in surface-treated casement plate, adopt the cyclic voltammetry of three-electrode system, take 700 ~ 1200 nm Porous Stainless Steels of silane surface treatment as anode, platinized platinum is negative electrode, saturated calomel SCE is reference electrode, take the EDOT solution of 0.005 ~ 0.015 M as electrolytic solution, add certain sodium lauryl sulphate tensio-active agent, use H
2SO
4Adjusting pH is 0.5 ~ 2.0, adopt 5 ~ 100 mV/s to sweep speed and between-0.5 ~ 2.5 V, circulate 10 ~ 30 times, be transferred to and dissolve the part Stainless Molding Board in the chloroazotic acid, with deionized water repeatedly clean to pH value of solution near 7, dry through 70 ~ 110 oC, obtain the PEDOT array.
Claims (3)
1. gather 3, the preparation method of 4-ethylenedioxy thiophene array, it is characterized in that: adopt the super gravity field enhancements to prepare the PEDOT array by in-situ polymerization in the hole, take p-methyl benzenesulfonic acid iron as oxygenant, p-methyl benzenesulfonic acid iron butanol solution and the 0.01 M EDOT monomer of 35 ~ 65 wt.% are pressed p-methyl benzenesulfonic acid iron: EDOT=(2.0 ~ 2.5): fully stir under 1 the mol ratio room temperature, putting into the liner aperture after mixing is the Plastic Bottle of the harsh pit aluminium of 500 ~ 1500 nm, bottle is put into whizzer and fixing, speed rotation 1 ~ 5 min with 20000 ~ 30000 rpm, take out the hole aluminum alloy pattern plate of impregnation thing solution, be transferred to dry 30 ~ 60 min in the baking oven of 60 ~ 100 oC, dissolve part hole aluminum alloy pattern plate with 8 wt.% NaOH solution, washing, drying obtains the PEDOT array.
2. gather 3, the preparation method of 4-ethylenedioxy thiophene array, it is characterized in that: adopt the super gravity field enhancements to prepare the PEDOT array by gas-solid reaction, take cupric chloride as oxygenant, the cupric chloride high purity water solution of 0.005 ~ 0.02 M is put into the Plastic Bottle that the liner aperture is the anodised aluminium AAO template of 50 ~ 200 nm, bottle is put into whizzer and fixing, speed rotation 2 ~ 6 min with 5000 ~ 10000 rpm, take out the AAO casement plate of oxide impregnation agent, place the steam of EDOT monomer to react 2 ~ 10 min, dry 100 ~ 150 min of baking oven of 70 ~ 120 oC are put in taking-up, with 0.25 M Cr
2O
3H
3PO
4AAO casement plate is removed in the solution dissolving, obtains the PEDOT array.
3. gather 3, the preparation method of 4-ethylenedioxy thiophene mixture array, it is characterized in that: adopt the vacuum filtration method to prepare the PEDOT/PSS array by the in-situ chemical polymerization, take styrene sulfonate SS as oxygenant, mass ratio toward EDOT: SS is 1: add Virahol and tetrahydrofuran solvent and rapid stirring in the solution of the PEDOT/PSS monomer of 0.01 ~ 0.04 M of (2 ~ 6), make soltion viscosity reach 100 ~ 300 mPas by the amount of adjusting Virahol, being transferred to the bottom is lined with in the suction funnel of 300 ~ 600 nm porous silica templates, vacuum tightness is 0.02 ~ 0.08 MPa, suction filtration 30 ~ 60 min, improve the filling ratio of reactant solution in the silica template hole, behind 100 ~ 160 oC dryings, 5 ~ 50 min, hot sodium carbonate solution with 20 ~ 30% is removed silica template, with dry behind the deionized water wash, obtain the PEDOT/PSS array.
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