CN105336867A - Conductive composite obtained by dispersing poly(3,4-ethylenedioxythiophene) with naphthalenesulfonic acid-formaldehyde condensation compound and preparation method and application thereof - Google Patents
Conductive composite obtained by dispersing poly(3,4-ethylenedioxythiophene) with naphthalenesulfonic acid-formaldehyde condensation compound and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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Abstract
The invention belongs to the technical field of an organic photoelectric material and discloses a conductive composite obtained by dispersing poly(3,4-ethylenedioxythiophene) with naphthalenesulfonic acid-formaldehyde condensation compound and a preparation method and application thereof. The preparation method of the conductive composite is characterized by enabling a naphthalenesulfonic acid-formaldehyde condensation compound to be prepared into a naphthalenesulfonic acid-formaldehyde condensation compound aqueous solution, of which the mass concentration is 1.0%-10.0%, adding the aqueous solution to the monomer poly(3,4-ethylenedioxythiophene) and then, carrying out uniform stirring and mixing; then, enabling an oxidizing agent to be prepared into an aqueous solution, of which the mass concentration is 1.0%-4.0%, adding the aqueous solution to the mixed solution above, and carrying out indoor temperature stirring and reaction for 12-48 hours; and dialyzing the obtained product to remove inorganic salts and unreacted monomers to obtain the conductive composite obtained by dispersing poly(3,4-ethylenedioxythiophene) with the naphthalenesulfonic acid-formaldehyde condensation compound. The naphthalenesulfonic acid-formaldehyde condensation compound is adopted as a disperse carrier, so that the obtained conductive composite is uniform and stable, high in conductivity, high in transparency, helpful for doping and good in application prospect.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, be specifically related to the poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion and preparation and application.
Background technology
Since the later stage eighties 20th century, poly-3,4-ethylene dioxythiophene (PEDOT) is one of the study hotspot in doping type conducting polymer field always.Poly-3,4-ethylenedioxy thiophene has high conductivity, preferably environmental stability, film and, to advantages such as the high transparency rates of visible ray, shows wide application prospect in fields such as photovoltaic cell, electrochromic device, organic electroluminescent LED, organic solar batteries, hybrid solar cell, anti-electrostatic polymers.The poly-3,4-ethylene dioxythiophene of eigenstate is insoluble not molten, and this makes it be difficult to be processed by solwution method.At present, domestic and international researcher has carried out large quantity research to the synthesis of function protonic acid doping PEDOT and performance thereof.Wherein, the most effective way adds organic functions Bronsted acid, such as polystyrolsulfon acid (PSS), DBSA (DBSA) etc., these acid are containing parents' group, the aqueous solution processing of PEDOT can be realized on the one hand as surfactant, the conductivity of PEDOT is improved on the other hand, so selecting organic functions Bronsted acid to prepare PEDOT compound as dopant is the most effectual way improving its combination property by proton doping.
Bayer company of Germany introduces polyanion electrolyte PSS in PEDOT, has prepared water miscible PEDOT/PSS compound (EP0440957).Due to the excellent properties of PEDOT/PSS, domestic and international scientific research circle and industrial circle are grown to even greater heights to its research enthusiasm, main component is that the Patents of PEDOT/PSS emerges in large numbers day by day, aqueous dispersions as non-polystyrolsulfon acids such as US5300575, WO03048227, EP1323763, CN101434770, CN101284927, CN101407575 and poly-3,4-ethylene dioxythiophene/sodium lignin sulfonates (CN102516784B) also possesses some special knowledge.
Naphthalene sulfonic acid-formaldehyde condensation product (NSF) is the earliest as dye diffusion agent application, and oneself has long history.1913, BASF Aktiengesellschaft (BASF) first application naphthalene sulfonic acid-formaldehyde condensation product made the patent of dispersant.At normal temperatures, dispersiveness can be suitable with PSS, and foaming characteristic is little, excellent combination property for naphthalene sulfonic acid-formaldehyde condensation product.Naphthalene sulfonic acid derivant has the fast rate of adsorption, and the naphthalene sulfonic acid-formaldehyde condensation product of HMW, high condensation degree has good dispersiveness, take naphthalene sulfonate as one of high range water reducing agent for cement of the current extensive use of cement dispersants of composition.So far, naphthalene sulfonic acid-formaldehyde condensation product (NSF) still has very large application market as cement dispersants, and its correlative study is also constantly being goed deep into.
It should be noted that, at organic electronics device as in organic electroluminescent LED and organic heterojunction solar cell, by adding one deck PEDOT:PSS anode modification layer on the surface of tin indium oxide (ITO), the energy barrier height of low hole injection or transport interface can be reduced, improve device efficiency, improve the combination property of device.But, naphthalene sulfonic acid-formaldehyde condensation product (NSF) be applied to the dispersion of poly-3,4-ethylene dioxythiophene (PEDOT) polymer and be applied in device preparation field, not having relevant report so far.
Summary of the invention
Based on above prior art, primary and foremost purpose of the present invention is to provide a kind of naphthalene sulfonic acid-formaldehyde condensation product to disperse poly-3,4-ethylene dioxythiophene electrically conductive composite.
Another object of the present invention is to provide above-mentioned naphthalene sulfonic acid-formaldehyde condensation product to disperse the preparation method of poly-3,4-ethylene dioxythiophene electrically conductive composite.
Another object of the present invention is to provide above-mentioned naphthalene sulfonic acid-formaldehyde condensation product to disperse the poly-application of 3,4-ethylene dioxythiophene electrically conductive composite in organic electro-optic device.
The object of the invention is achieved through the following technical solutions:
The poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion, described compound on naphthalene sulfonic acid-formaldehyde condensation product carrier, is polymerized dispersion by 3,4-ethylene dioxythiophene monomer to obtain.
Described naphthalene sulfonic acid-formaldehyde condensation product preferably has following molecular structural formula:
Wherein n is the integer of 2 ~ 20.
Preferably, in described compound, the dispersion particle diameter of poly-3,4-ethylene dioxythiophene is 50 ~ 350nm.
The schematic arrangement of the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion of the present invention as shown in Figure 1.
The preparation method of the poly-3,4-ethylene dioxythiophene electrically conductive composite of above-mentioned naphthalene sulfonic acid-formaldehyde condensation product dispersion, comprises following preparation process:
(1) naphthalene sulfonic acid-formaldehyde condensation product is dissolved in deionized water is mixed with the naphthalene sulfonic acid-formaldehyde condensation product aqueous solution that mass concentration is 1.0% ~ 10.0%, join in monomer 3,4-ethylene dioxythiophene, be uniformly mixed;
(2) oxidant is dissolved in deionized water is mixed with the aqueous solution that mass concentration is 1.0% ~ 4.0%, be added dropwise in the mixed solution of step (1), stirring at room temperature reaction 12 ~ 48 hours, obtaining take naphthalene sulfonic acid-formaldehyde condensation product as the poly-3,4-ethylene dioxythiophene aqueous dispersions of carrier;
(3) by the aqueous dispersions of step (2) dialysis removing inorganic salts and unreacted monomer, the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion is obtained.
In above-mentioned preparation method, the weight proportion of preferred each component is as follows:
Described oxidant initiator system of ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
Preferably, the stirring described in step (1) refer under the mixing speed of 500 ~ 2000 turns/min stir 10 ~ 40 minutes.
Preferably, the dialysis described in step (4) refers to that the bag filter with molecular cut off is 1000 is dialysed 1 ~ 7 day.
The poly-application of 3,4-ethylene dioxythiophene electrically conductive composite in organic electro-optic device of above-mentioned naphthalene sulfonic acid-formaldehyde condensation product dispersion.
Preferably, described organic electro-optic device refers to organic electroluminescence device, solar cell device etc.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) naphthalene sulfonic acid-formaldehyde condensation product is used for the dispersion of poly-3,4-ethylene dioxythiophene by the present invention, and naphthalene sulfonic acid-formaldehyde condensation product raw material sources are extensive, and cost of material is lower;
(2) naphthalene sulfonic acid-formaldehyde condensation product is used for the dispersion of poly-3,4-ethylene dioxythiophene by the present invention, gained electrically conductive composite stable homogeneous, conductance is high, transparency is high and be conducive to its doping;
(3) naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 of the present invention, the transformation efficiency that the energy conversion efficiency that 4-ethylenedioxy thiophene electrically conductive composite is applied in organic electroluminescence device compares poly-3,4-ethylene dioxythiophene/kayexalate composite transparent electrode is quite even more excellent.
Accompanying drawing explanation
Fig. 1 is the schematic arrangement of the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product of the present invention dispersion;
Fig. 2 is the naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 of the embodiment of the present invention 2,4-ethylenedioxy thiophene electrically conductive composite, commercially produced product poly-3, the infrared spectrogram of 4-ethylenedioxy thiophene/kayexalate compound (PEDOT:PSS) and monomer 3,4-ethylene dioxythiophene;
Fig. 3 is the naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 of the embodiment of the present invention 3,4-ethylenedioxy thiophene electrically conductive composite, commercially produced product poly-3, the ultraviolet spectrogram of 4-ethylenedioxy thiophene/kayexalate compound (PEDOT:PSS) and monomer 3,4-ethylene dioxythiophene;
Fig. 4 is the grain size distribution of the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion of the embodiment of the present invention 4;
Fig. 5 is the luminance-voltage-current density characteristics curve chart of the electroluminescent device that the embodiment of the present invention 5 and embodiment 6 obtain;
Fig. 6 is the luminance-current efficiency-power efficiency characteristic curve chart of the electroluminescent device that the embodiment of the present invention 5 and embodiment 6 obtain.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 5g naphthalene sulfonic acid-formaldehyde condensation product is dissolved in deionized water is mixed with the naphthalene sulfonic acid-formaldehyde condensation product aqueous solution that mass concentration is 10.0%, join 5g monomer 3, in 4-ethylenedioxy thiophene, stir under the mixing speed of 1500 turns/min and mix for 30 minutes;
(2) 5g sodium peroxydisulfate is dissolved in deionized water is mixed with the aqueous solution that mass concentration is 1.0%, be added dropwise in the mixed solution of step (1), stirring at room temperature reacts 24 hours, obtaining take naphthalene sulfonic acid-formaldehyde condensation product as poly-(3,4-ethylene dioxythiophene) aqueous dispersions of carrier;
(3) bag filter being 1000 by the aqueous dispersions molecular cut off of step (2) is dialysed 3 days, removing inorganic salts and unreacted monomer, obtains the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion.
Embodiment 2
(1) 5g naphthalene sulfonic acid-formaldehyde condensation product is dissolved in deionized water is mixed with the naphthalene sulfonic acid-formaldehyde condensation product aqueous solution that mass concentration is 10.0%, join 2.5g monomer 3, in 4-ethylenedioxy thiophene, stir under the mixing speed of 1500 turns/min and mix for 30 minutes;
(2) 2.5g sodium peroxydisulfate is dissolved in deionized water is mixed with the aqueous solution that mass concentration is 1.0%, be added dropwise in the mixed solution of step (1), stirring at room temperature reacts 24 hours, obtaining take naphthalene sulfonic acid-formaldehyde condensation product as poly-(3,4-ethylene dioxythiophene) aqueous dispersions of carrier;
(3) bag filter being 1000 by the aqueous dispersions molecular cut off of step (2) is dialysed 1 day, removing inorganic salts and unreacted monomer, obtains the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion.
The naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 of the present embodiment, 4-ethylenedioxy thiophene electrically conductive composite adopts AutosystemXL/I-series/Spectrum2000 infrared spectrometer, IR Characterization is carried out with pellet technique, and gather 3 with commercially produced product, 4-ethylenedioxy thiophene/kayexalate compound (PEDOT:PSS) and monomer 3,4-ethylenedioxy thiophene (EDOT) compares, and result as shown in Figure 2.3050 ~ 3125cm in figure
-1the characteristic spikes at place is the stretching vibration peak of C-H in monomer thiphene ring, 892cm
-1the spike at place is the flexural vibrations of C-H in monomer thiphene ring, 1510,1400 and 760cm
-1the absworption peak at place is characteristic peak on thiophene skeleton, 1200 and 1100cm
-1the absworption peak at place is the characteristic peak of the oxygen-containing substituents of 3,4-ethylene dioxythiophene.The infrared spectrum display of the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion of the present embodiment, 3050 ~ 3125cm
-1and 892cm
-1two characteristic spikes at place disappear, and illustrate that thiophene monomer reacts completely, and have occurred the characteristic peak of the oxygen-containing substituents of thiophene skeleton and 3,4-ethylene dioxythiophene, illustrate that successful polymerization obtains poly-3,4-ethylene dioxythiophene.
Embodiment 3
(1) 8g naphthalene sulfonic acid-formaldehyde condensation product is dissolved in deionized water is mixed with the naphthalene sulfonic acid-formaldehyde condensation product aqueous solution that mass concentration is 10.0%, join 2g monomer 3, in 4-ethylenedioxy thiophene, stir under the mixing speed of 1500 turns/min and mix for 30 minutes;
(2) 2g sodium peroxydisulfate is dissolved in deionized water is mixed with the aqueous solution that mass concentration is 1.0%, be added dropwise in the mixed solution of step (1), stirring at room temperature reacts 24 hours, obtaining take naphthalene sulfonic acid-formaldehyde condensation product as poly-(3,4-ethylene dioxythiophene) aqueous dispersions of carrier;
(3) bag filter being 1000 by the aqueous dispersions molecular cut off of step (2) is dialysed 1 day, removing inorganic salts and unreacted monomer, obtains the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion.
The naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 of the present embodiment, 4-ethylenedioxy thiophene electrically conductive composite adopts UV-2450 ultraviolet specrophotometer (Japanese Shimadzu) to carry out ultra-violet absorption spectrum test, and gather 3 with commercially produced product, 4-ethylenedioxy thiophene/kayexalate compound (PEDOT:PSS) and monomer 3,4-ethylenedioxy thiophene (EDOT) compares, and result as shown in Figure 3.As seen from Figure 3, the ultraviolet characteristic absorption peak of poly-3,4-ethylene dioxythiophene is the broad peak of 500 ~ 950nm, and the region that 3,4-ethylene dioxythiophene monomer is 500 ~ 950nm at wavelength does not absorb.The naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 of the present embodiment, obviously absorption is there is in 4-ethylenedioxy thiophene electrically conductive composite in the region of 500 ~ 950nm, illustrate that poly-3,4-ethylene dioxythiophene/naphthalene sulfonic acid-formaldehyde condensation product (PEDOT:NSF) is successfully prepared.Poly-3,4-ethylene dioxythiophene is linear pi-conjugated polymer, and its conjugate length is longer, then the red shift degree of ultraviolet spectra is more obvious, and energy gap is lower.Compared with business-like poly-3,4-ethylene dioxythiophene/kayexalate compound, the ultraviolet spectra red shift degree of PEDOT:NSF is suitable, embodies both potential electric conductivities suitable.
Embodiment 4
(1) 6g naphthalene sulfonic acid-formaldehyde condensation product is dissolved in deionized water is mixed with the naphthalene sulfonic acid-formaldehyde condensation product aqueous solution that mass concentration is 10.0%, join 1g monomer 3, in 4-ethylenedioxy thiophene, stir under the mixing speed of 1500 turns/min and mix for 30 minutes;
(2) 1g sodium peroxydisulfate is dissolved in deionized water is mixed with the aqueous solution that mass concentration is 1.0%, be added dropwise in the mixed solution of step (1), stirring at room temperature reacts 24 hours, obtaining take naphthalene sulfonic acid-formaldehyde condensation product as poly-(3,4-ethylene dioxythiophene) aqueous dispersions of carrier;
(3) bag filter being 1000 by the aqueous dispersions molecular cut off of step (2) is dialysed 7 days, removing inorganic salts and unreacted monomer, obtains the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion.
The poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion of the present embodiment adopts ZetaPALS (U.S. Brookhaven) to carry out domain size distribution test, and result as shown in Figure 4.As seen from Figure 4, the domain size distribution of the electrically conductive composite dispersion that the present invention obtains is 50 ~ 350nm, and dispersion stabilization is good.
Embodiment 5
The poly-application of 3,4-ethylene dioxythiophene electrically conductive composite in organic electroluminescence device of naphthalene sulfonic acid-formaldehyde condensation product dispersion that embodiment 1 obtains, detailed process is as follows:
Tin indium oxide (ITO) glass uses deionized water, acetone and EtOH Sonicate 15min successively, heats 20min, UV ozone process 10min afterwards in triplicate with being placed in 120 DEG C of baking ovens.Then by solution spin-coating method, the electrically conductive composite solution of spin coating embodiment 1 under the rotating speed of 2000rpm, and the 20min that anneals at 120 DEG C obtains the electrically conductive composite film that thickness is 15nm.Subsequently ito glass is transferred to 5 × 10
-4in the high vacuum chamber of Pa, with emitting layer material mCP:FIrPic (25nm), electron transport layer materials TmPyPb (35nm) and electron injecting layer material LiF (1nm) that the speed of 0.1nm/s successively evaporation hole transport layer material TAPC (30nm), electronic blocking layer material mCP (8nm), FIrpic doping content are 10%, last with speed evaporation metal negative electrode aluminium (100nm) of 1nm/s, obtain organic electroluminescence device.The structure of this device is: ITO/ embodiment 1 compound (15nm)/TAPC (30nm)/mCP (8nm)/mCP:FIrPic (10wt%, 25nm)/TmPyPb (35nm)/LiF (1nm)/Al (100nm).
Embodiment 6
The poly-application of 3,4-ethylene dioxythiophene electrically conductive composite in organic electroluminescence device of naphthalene sulfonic acid-formaldehyde condensation product dispersion in embodiment 3, detailed process is as follows:
Tin indium oxide (ITO) glass uses deionized water, acetone and EtOH Sonicate 15min successively, heats 20min, UV ozone process 10min afterwards in triplicate with being placed in 120 DEG C of baking ovens.Then by solution spin-coating method, the electrically conductive composite solution of spin coating embodiment 3 under the rotating speed of 2000rpm, and the 20min that anneals at 120 DEG C obtains the electrically conductive composite film that thickness is 15nm.Subsequently ito glass is transferred to 5 × 10
-4in the high vacuum chamber of Pa, with emitting layer material mCP:FIrPic (25nm), electron transport layer materials TmPyPb (35nm) and electron injecting layer material LiF (1nm) that the speed of 0.1nm/s successively evaporation hole transport layer material TAPC (30nm), electronic blocking layer material mCP (8nm), FIrpic doping content are 10%, last with speed evaporation metal negative electrode aluminium (100nm) of 1nm/s, obtain organic electroluminescence device.The structure of this device is: ITO/ embodiment 3 compound (15nm)/TAPC (30nm)/mCP (8nm)/mCP:FIrPic (10wt%, 25nm)/TmPyPb (35nm)/LiF (1nm)/Al (100nm).
By Keithley2400 type programme-controlled dc power and PR-650, performance characterization is carried out to the electroluminescent device that embodiment 5 and 6 obtains, luminance-voltage-current density and luminance-current efficiency-power efficiency curve of obtaining device are distinguished as illustrated in Figures 5 and 6, and correlated performance data is enumerated in table 1.
The correlated performance data of table 1 electroluminescent device
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion, is characterized in that: described compound on naphthalene sulfonic acid-formaldehyde condensation product carrier, is polymerized dispersion by 3,4-ethylene dioxythiophene monomer to obtain.
2. the poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion according to claim 1, is characterized in that: described naphthalene sulfonic acid-formaldehyde condensation product has following molecular structural formula:
Wherein n is the integer of 2 ~ 8.
3. the poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion according to claim 1, is characterized in that: in described compound, the dispersion particle diameter of poly-3,4-ethylene dioxythiophene is 50 ~ 350nm.
4. the preparation method of the poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion described in any one of claims 1 to 3, is characterized in that comprising following preparation process:
(1) naphthalene sulfonic acid-formaldehyde condensation product is dissolved in deionized water is mixed with the naphthalene sulfonic acid-formaldehyde condensation product aqueous solution that mass concentration is 1.0% ~ 10.0%, join in monomer 3,4-ethylene dioxythiophene, be uniformly mixed;
(2) oxidant is dissolved in deionized water is mixed with the aqueous solution that mass concentration is 1.0% ~ 4.0%, be added dropwise in the mixed solution of step (1), stirring at room temperature reaction 12 ~ 48 hours, obtaining take naphthalene sulfonic acid-formaldehyde condensation product as the poly-3,4-ethylene dioxythiophene aqueous dispersions of carrier;
(3) by the aqueous dispersions of step (2) dialysis removing inorganic salts and unreacted monomer, the poly-3,4-ethylene dioxythiophene electrically conductive composite of naphthalene sulfonic acid-formaldehyde condensation product dispersion is obtained.
5. the preparation method of the poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion according to claim 4, is characterized in that the weight proportion of each component is as follows:
6. the preparation method of the poly-3,4-ethylene dioxythiophene electrically conductive composite of a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion according to claim 4 or 5, is characterized in that: described oxidant refers to ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
7. a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 according to claim 4, the preparation method of 4-ethylenedioxy thiophene electrically conductive composite, is characterized in that: the stirring described in step (1) refer under the mixing speed of 500 ~ 2000 turns/min stir 10 ~ 40 minutes.
8. a kind of naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 according to claim 4, the preparation method of 4-ethylenedioxy thiophene electrically conductive composite, is characterized in that: the dialysis described in step (4) refers to that the bag filter with molecular cut off is 1000 is dialysed 1 ~ 7 day.
9. the poly-application of 3,4-ethylene dioxythiophene electrically conductive composite in organic electro-optic device of naphthalene sulfonic acid-formaldehyde condensation product dispersion described in any one of claims 1 to 3.
10. naphthalene sulfonic acid-formaldehyde condensation product dispersion poly-3 according to claim 9, the application of 4-ethylenedioxy thiophene electrically conductive composite in organic electro-optic device, is characterized in that: described organic electro-optic device refers to organic electroluminescence device or solar cell device.
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| CN105575462A (en) * | 2016-02-23 | 2016-05-11 | 华南理工大学 | Conductive compound prepared by scattering and polymerizing 3,4-ethylenedioxythiophene on sulfonated acetone-formaldehyde condensate as well as preparation method and application of conductive compound |
| CN107163600A (en) * | 2017-07-06 | 2017-09-15 | 华南理工大学 | A kind of sulfomethylated lignin acid doping dopamine and 3,4 ethylenedioxy thiophene copolymers and preparation method and application |
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| CN201516784U (en) * | 2009-06-18 | 2010-06-30 | 义乌市安冬电器有限公司 | Panoramic light-emitting relief painting |
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| US5300575A (en) * | 1990-02-08 | 1994-04-05 | Bayer Aktiengesellschaft | Polythiophene dispersions, their production and their use |
| CN101516784A (en) * | 2006-09-28 | 2009-08-26 | 沃雷科有限责任公司 | Vortex generator |
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| CN105575462A (en) * | 2016-02-23 | 2016-05-11 | 华南理工大学 | Conductive compound prepared by scattering and polymerizing 3,4-ethylenedioxythiophene on sulfonated acetone-formaldehyde condensate as well as preparation method and application of conductive compound |
| CN107163600A (en) * | 2017-07-06 | 2017-09-15 | 华南理工大学 | A kind of sulfomethylated lignin acid doping dopamine and 3,4 ethylenedioxy thiophene copolymers and preparation method and application |
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| CN105336867B (en) | 2017-12-01 |
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