CN102321235A - 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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- CN102321235A CN102321235A CN201110175894A CN201110175894A CN102321235A CN 102321235 A CN102321235 A CN 102321235A CN 201110175894 A CN201110175894 A CN 201110175894A CN 201110175894 A CN201110175894 A CN 201110175894A CN 102321235 A CN102321235 A CN 102321235A
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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 gather 3, the preparation method of 4-enedioxy thiophene 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
Gather 3,4-enedioxy thiophene is also claimed to gather 3; 4-ethene dioxythiophene, English are 3,4-ethylenedioxythiophene; Abbreviation PEDOT or PEDT; Be a kind of polythiofuran derivative of indissoluble, the conjugated link(age) structure all arranged, have specific conductivity height (about 300 S cm under the room temperature with polypyrrole, Polythiophene etc.
-1), advantage such as low, the good stability of energy gap (receiving ambient moisture to influence little, facile hydrolysis, fast light, high temperature resistant etc. not), optical transparence be good, synthetic easy, receive much concern in fields such as transmitter, solar cell, solid-state capacitor, ultracapacitor, lithium ion battery, catalyzing manufacturing of hydrogen, liquid crystal display device, antistatic coating, novel electromagnetic shielding material, soft-touch controls as a kind of organic functions electronic material.Gather 3; The monomer EDOT of 4-enedioxy 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 a reductive agent, need could polymerization formation gather 3,4-enedioxy thiophene through peroxo-; Different according to the acceptor that gets electronics; Can be with gathering 3, the preparation method of 4-enedioxy thiophene is divided into chemical polymerization and electrochemical polymerization, and the former obtains electronics through oxygenant; The latter obtains electronics through 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 midbody 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 bigger to the electric conductivity influence of polymkeric substance.Because the electron delocalization scarce capacity of pure PEDOT, conductive capability can not get demonstrating fully, and can strengthen electron delocalization ability in the big π key in this intrinsic conduction polymer through mixing, and improves electric conductivity.In order to solve the relatively poor problem of PEDOT solvability; Adopt water miscible polystyrolsulfon acid ester PSS that it is carried out the charge balance doping vario-property and form the PEDOT/PSS composite package; Can obtain through 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, spin coating easily, 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] through in the solution of PSS, adding different amphoteric ion high polymer materials.
Super gravity field is to be used to alternate isolating centrifuge field; Mainly be to obtain through rotating machinery integral body or parts; Strengthen between phase and phase speed of relative movement be in contact with one another, and " g " is big more, △ (ρ g) is big more; The fluid relative sliding velocity is also big more, thereby realizes mass-and heat-transfer process and chemical reaction process efficiently.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 the contrast down of 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, and huge shear-stress has overcome surface tension of liquid, and liquid crushing is nano level drop, brin, liquid film and forms new phase interface; Make liquid stretch out huge phase border contact interface; Improved rate of mass transfer (about 1 ~ 3 one magnitude) and mass transfer coefficient (about 10 ~ 1000 times), strengthened microcosmic and mixed and mass transfer process, helped reactant solution and get in the pattern hole.Vacuum filtration makes fully enrichment in the hole of solution through the pressure of relative increase reactant solution side, and is similar with super gravity field, also can effectively improve the filling ratio in the hole.The method that material surface is handled is a lot, need improve the filling ratio of reactant solution in the hole through adding measures such as tensio-active agent or plasma treatment according to the character of hole surface and reactant solution.
That reports at present gathers 3, and 4-enedioxy thiophene and mixture pattern thereof have forms such as powder, film, fiber and nanotube, does not see preparing method's report of its array material as yet.Array material has the three-dimensional structure of high specific area; The abundant contact and the mass transfer that help the differential responses phase; Be the desirable elementary cell of nanometer superminiature device, many at present employing galvanic deposit, electroless deposition craft (electroless plating) or self-assembly prepare in pattern hole, under the chemical industry enhancements, carry out; It is loose that array material contacts with hole surface, has that filling ratio material density not high, preparation the hole in is poor, surfaceness height, tube wall be difficult to problems such as control, poor reproducibility.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art in order to address the above problem, creationary proposition is a kind of to gather 3; 4-enedioxy thiophene and the brand-new process method of mixture array synthetic thereof, adopting the hole material that obtains easily is template, utilizes the abundant enrichment in the hole of chemical industry enhancements such as super gravity field, vacuum filtration, surface treatment to gather 3; The monomer of 4-enedioxy thiophene and mixture thereof or oxygenant are removed template and are obtained the product array after chemistry or electrochemical polymerization reaction, simplified the synthesis technique flow process of array material; And can utilize density, distribution and the pattern of different template size parameters and reinforcing process parameter array to control effectively, and filling ratio is high in the pattern hole, and the array caliber is easy to control; The preparation efficiency of array material and density are high, react easy to operate, and preparing method's technology is simple; Cost is low; Less investment, profitable, be prone to suitability for industrialized production.
[0006] basic design of the present invention is: the present invention utilizes chemical industry enhancements such as super gravity field, vacuum filtration, surface treatment will gather 3; The monomer of 4-enedioxy thiophene and mixture thereof or oxygenant be fully enrichment in pattern hole; After polyreaction, remove template and obtain the product array; Through thickness, density, distribution and the pattern etc. of control template dimensional parameters and reinforcing process parameter adjustment polymer array, realize the controlled preparation of polymer array material.
According to the inventionly gather 3, the preparation method of 4-enedioxy thiophene and mixture array thereof, concrete process step is following;
The employing aperture is that the hole material of 10 ~ 2000 nm is a template; To gather 3; Enhancements enrichment in pattern hole that the monomer of 4-enedioxy thiophene and mixture thereof or oxygenant are handled through super gravity field, vacuum filtration, hole surface; After-50 ~ 150 oC polyreactions, remove template formation and gather 3,4-enedioxy thiophene and mixture array thereof.
Among the present invention, described polymerization refers to add the chemical polymerization and the electrochemical polymerization that applies electric field action of oxygenant.
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, ydrogen peroxide 50.
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, ceramic foam, 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 through 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 handled and is meant hydrophilic, oleophylic or the plasma treatment that helps reactant enrichment in the hole.
Among the present invention; The array of preparation is made up of fiber or pipe; Can realize the controlled preparation of polymer array material through thickness, density, Fibre diameter, caliber, tube wall, pipe distribution, structure and the pattern etc. of control template pore structure parameter and reinforcing process parameter adjustment polymer array.
The present invention compared with prior art; The invention solves and gather 3; The series technique difficult problem of 4-enedioxy thiophene and the controlled preparation of mixture array thereof; Problems such as filling ratio is low in the hole when having overcome electrochemical deposition method or chemical electroless deposition processes under the nonreinforcement measure and preparing, the array material space is many, density difference and surfaceness height have been eliminated reactant precursor and pattern hole surface and contacts loose deficiency, have creationaryly proposed to utilize chemical industry enhancements enhancings such as super gravity field, vacuum filtration, surface treatment to gather 3; 4-enedioxy 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: improve the tamped density of reactant precursor in pattern hole through adopting enhancements such as super gravity field, vacuum filtration, surface treatment; The exposure phase interface 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 realize that easily cost is low; Can realize the controlled preparation of polymer array material through density, thickness, Fibre diameter, caliber, tube wall, pipe distribution, structure and the pattern etc. of control template pore structure parameter and reinforcing process parameter adjustment polymer array; Technology is simple, and is easy to operate, lower to the requirement of equipment; The reactant full contact, the contact area is big between reacting phase, and the molecule contact is closely reacted easily and is taken place, 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
Below in conjunction with embodiment and accompanying drawing the present invention is described further; Said content is merely 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 through in-situ polymerization in the hole; With p-methyl benzenesulfonic acid iron is oxygenant, and process flow sheet is as shown in Figure 1, and 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,, take out the hole aluminum alloy pattern plate of dipping reactant solution with speed rotation 1 ~ 5 min of 20000 ~ 30000 rpm/min; 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 obtain 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 process step to accomplish; That is: the hole aluminum alloy pattern plate that adheres to PEDOT of preceding first drying is put into reactant solution once more and strengthen the enrichment of reactant in the hole with super gravity field, dry back is dissolved and is gone template to 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 through gas-solid reaction; With the cupric chloride is 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, with speed rotation 2 ~ 6 min of 5000 ~ 10000 rpm/min; Take out the AAO casement plate of oxide impregnation agent; Place the monomeric steam of EDOT to react 2 ~ 10 min, take out dry 100 ~ 150 min of the baking oven of putting into 70 ~ 120 oC, 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 process step to accomplish; That is: the AAO casement plate that adheres to PEDOT of preceding first drying is put into cupric chloride high purity water solution once more, with super gravity field strengthen oxidizing agent solution in the hole enrichment and gas-solid reaction takes place in the monomeric steam of EDOT, dry back is dissolved and is gone template to obtain the product array.
Embodiment 3
Adopting the vacuum filtration method to prepare the PEDOT/PSS array through the in-situ chemical polymerization, is oxygenant with styrene sulfonate SS, toward PEDOT/PSS monomer (EDOT: SS=1: (2 ~ 6) of 0.01 ~ 0.04 M; Mass ratio) adds Virahol and tetrahydrofuran solvent and stirring fast in the solution; Amount through the adjustment Virahol makes soltion viscosity reach 100 ~ 300 mP s, is transferred to the bottom and is lined with in the suction funnel of 300 ~ 600 nm porous silica templates, and 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 dry 5 ~ 50 min of 100 ~ 160 oC, remove silica template with 20 ~ 30% hot sodium carbonate solution; Use the deionized water wash after drying, obtain the PEDOT/PSS array.
Embodiment 4
Prepare the PEDOT array through electrochemical polymerization in surface-treated casement plate; Adopting the cyclic voltammetry of three-electrode system, is anode with silane surface-treated 700 ~ 1200 nm Porous Stainless Steels, and platinized platinum is a negative electrode; Saturated calomel SCE is a reference electrode; EDOT solution with 0.005 ~ 0.015 M is electrolytic solution, adds certain sodium lauryl sulphate tensio-active agent, uses H
2SO
4Adjustment 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 dissolve in the chloroazotic acid and go part stainless steel template, with deionized water repeatedly clean to pH value of solution near 7; Dry through 70 ~ 110 oC, obtain the PEDOT array.
Claims (8)
1. gather 3; The preparation method of 4-enedioxy thiophene and mixture array thereof is characterized in that: the employing aperture is that the hole material of 10 ~ 2000 nm is a template, will gather 3; Enhancements enrichment in pattern hole that the monomer of 4-enedioxy thiophene and mixture thereof or oxygenant are handled through super gravity field, vacuum filtration, hole surface; After-50 ~ 150 oC polyreactions, remove template formation and gather 3,4-enedioxy thiophene and mixture array thereof.
According to claim 1 gather 3, the preparation method of 4-enedioxy thiophene and mixture array thereof describes, and it is characterized in that: described polymerization refers to add the chemical polymerization and the electrochemical polymerization that applies electric field action of oxygenant.
3. gather 3 according to claim 1; The preparation method of 4-enedioxy thiophene and mixture array thereof describes, and it is characterized in that: 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, ydrogen peroxide 50.
4. gather 3 according to claim 1; The preparation method of 4-enedioxy thiophene and mixture array thereof describes, and it is characterized in that: described hole material refers to etched hole aluminium, anodised aluminium, porous silicon, POROUS TITANIUM, nickel porous, porous carbon, Porous Stainless Steel, porous silica, ceramic foam, molecular sieve, polycarbonate, cetyltriethylammonium bromide CTAB.
According to claim 1 gather 3, the preparation method of 4-enedioxy thiophene and mixture array thereof describes, it is characterized in that: described aperture is 50 ~ 1500 nm.
6. gather 3 according to claim 1 and claim 2; The preparation method of 4-enedioxy thiophene and mixture array thereof describes; It is characterized in that: described super gravity field refers to that rotating speed is not less than 500 rpm/min through the centrifuge field of rotating machinery integral body or parts formation.
7. gather 3 according to claim 1 and claim 2; The preparation method of 4-enedioxy thiophene and mixture array thereof describes; It is characterized in that: 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, and vacuum tightness is not less than 0.02 MPa.
According to claim 1 and claim 2 gather 3, the preparation method of 4-enedioxy thiophene and mixture array thereof describes, and it is characterized in that: described hole surface is handled and is meant hydrophilic, oleophylic or the plasma treatment that helps reactant enrichment in the hole.
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Cited By (3)
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| CN104167386A (en) * | 2014-08-04 | 2014-11-26 | 苏州科阳光电科技有限公司 | Re-wiring manufacturing process for wafer-level chip |
| CN104167387A (en) * | 2014-08-04 | 2014-11-26 | 苏州科阳光电科技有限公司 | Wafer level chip packaging technology |
| CN105862071A (en) * | 2016-04-15 | 2016-08-17 | 武汉工程大学 | Preparation method for pore diameter-controlled poly(3,4-ethylenedioxythiophene) thin film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167386A (en) * | 2014-08-04 | 2014-11-26 | 苏州科阳光电科技有限公司 | Re-wiring manufacturing process for wafer-level chip |
| CN104167387A (en) * | 2014-08-04 | 2014-11-26 | 苏州科阳光电科技有限公司 | Wafer level chip packaging technology |
| CN104167386B (en) * | 2014-08-04 | 2017-02-15 | 苏州科阳光电科技有限公司 | Re-wiring manufacturing process for wafer-level chip |
| CN104167387B (en) * | 2014-08-04 | 2017-05-17 | 苏州科阳光电科技有限公司 | Wafer level chip packaging technology |
| CN105862071A (en) * | 2016-04-15 | 2016-08-17 | 武汉工程大学 | Preparation method for pore diameter-controlled poly(3,4-ethylenedioxythiophene) thin film |
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