CN104151565A - PEDOT [poly(3,4-ethylenedioxythiophene)] aqueous dispersion with high conductivity and preparation method thereof - Google Patents
PEDOT [poly(3,4-ethylenedioxythiophene)] aqueous dispersion with high conductivity and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a PEDOT [poly(3,4-ethylenedioxythiophene)] aqueous dispersion with high conductivity. The PEDOT aqueous dispersion comprises a polymer PEDOT: PSS-APEG [(poly(styrenesulfonate)-(acrylic polyethers)], a fluoroalcoholic compound and water. The invention further relates to preparation of the PEDOT aqueous dispersion with high conductivity. The preparation method comprises the following steps: firstly, synthesizing a copolymer PSS-APEG; and then, preparing the polymer PEDOT: PSS-APEG aqueous dispersion. The aqueous dispersion provided by the invention has the beneficial effects that on the one hand, a novel template PSS-APEG is introduced into PEDOT, so that the prepared PEDOT dispersion liquid is more stable and good in film forming property; on the other hand, the fluoroalcoholic compound is further introduced, so that the conductivity of the film is greatly improved and the water absorption is greatly reduced under the condition that the light transmittance of the PEDOT:PSS-APEG film is not affected; the prepared PEDOT: PSS-APEG aqueous dispersion is simple in preparation process and suitable for industrialized popularization.
Description
Technical field
The invention belongs to conducting polymer technical field, be specifically related to PEDOT water dispersion of a kind of high conductivity and preparation method thereof.
Background technology
The end of the eighties in last century, Beyer Co., Ltd developed the poly-3,4-ethylene dioxythiophene (PEDOT) of novel polythiofuran derivative.PEDOT has high conductivity (>10
3s/cm), the excellent performance such as film high transparent, better electrochemical stability becomes the study hotspot of conducting polymer.But the insoluble not molten feature limits of PEDOT its industrial application, using water-soluble polymers sodium polystyrene sulfonate (PSS) as template and doping agent overcome this shortcoming, make it be widely used in the fields such as antistatic material, organic light emitting diode and solar cell.
Along with deepening continuously that PEDOT:PSS is studied, the performance of PEDOT:PSS is also proposed to more and more higher requirement.PEDOT:PSS is as the most successful conductive polymers in industrial application, and the conductivity that how further to improve PEDOT:PSS film becomes the focus of research.After the discovery DMSO such as He Zhihong, after doping, the conductivity of PEDOT:PSS film has improved 3 orders of magnitude; Adding of the discovery PEG such as Wang Tiejun makes the energy of carrier transition reduce and the electric conductivity of PEDOT:PSS is improved; The use methyl alcohol aftertreatment PEDOT:PSS films such as Desalegn Alemu make the electric conductivity of PEDOT:PSS film reach 1362 S/cm; Jianyong Quyang etc., by amphipathic fluoride compound treatment PEDOT:PSS film, make its electric conductivity bring up to 1164 S/cm from 0.3 S/cm.But these methods that improve PEDOT:PSS electric conductivity are mainly blend to PEDOT:PSS solution and the aftertreatment of film to be realized.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides one taking PSS-APEG multipolymer as template, high conductivity PEDOT water dispersion that fluorine alkylol cpd is additive and preparation method thereof.The PEDOT:PSS-APEG film that this method makes is good stability, difficult water suction not only, and the transparency is good, electroconductibility is high.
The present invention solves the technical scheme that its technical problem adopts: a kind of PEDOT water dispersion of high conductivity, comprise polymer P EDOT:PSS-APEG, fluorine alkylol cpd and water, and the structural formula of polymer P EDOT:PSS-APEG is:
Wherein, m is that 2～140, n is that 2～240, x is 28.Should be noted that, except special indicating, what in literary composition, PEDOT referred to is poly-3,4-ethylenedioxy thiophene (Poly (3,4-ethylenedioxythiophene)), that PSS refers to is sodium polystyrene sulfonate (Poly (sodium-p-styrenesulfonate)), and that APEG refers to is allyl polyglycol (Acrylic polyethers); What SSNa referred to is Sodium styrene sulfonate, and what EDOT referred to is 3,4-ethylene dioxythiophene, the monomer that SSNa is PSS, the monomer that EDOT is PEDOT.The molecular weight of APEG is 1000, commercially available.
Further, polymer P EDOT:PSS-APEG is taking copolymer p SS-APEG as template, and the weight of polymer P EDOT:PSS-APEG is 1～10% of water dispersion gross weight, and the weight of fluorine alkylol cpd is 0.1～10% of water dispersion gross weight.
Further, fluorine alkylol cpd is one or more in trifluoroethanol, C3-Fluoroalcohol, hexafluoro butanols.
A preparation method for the PEDOT water dispersion of high conductivity, concrete steps are as follows:
(1) copolymer p SS-APEG's is synthetic:
In reactor, add SSNa, APEG and deionized water, at N
2protection is lower dissolves, and while being heated to 80～90 DEG C, slowly splashes into oxygenant, after dropping finishes, is warming up to 90～100 DEG C; After reaction 4～6h, by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry.The structure of copolymer p SS-APEG is as follows:
Wherein, m is that 2～140, x is 28.
(2) preparation of polymer P EDOT:PSS-APEG water dispersion:
Copolymer p SS-APEG, EDOT, fluorine alkylol cpd and deionized water that step (1) is made add in reaction flask, 30～45 DEG C of stirring and dissolving, after dissolving completely, add oxygenant, catalyzer and Virahol (IPA), reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency, obtains water dispersion; Water dispersion is filtered to purifying by anion-cation exchange resin; By centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, finally, by ultrasonic dispersion 1h after precipitate with deionized water dilution, must contain the mazarine water dispersion of PEDOT:PSS-APEG.The structural formula of polymer P EDOT:PSS-APEG is:
Wherein, m is that 2～140, n is that 2～240, x is 28.
Further, in step (1), oxygenant is one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
Further, mol ratio=(1～50) of SSNa and APEG in step (1): 1, mol ratio=(100～300) of oxygenant and SSNa: 1.
Further, in step (2), fluorine alkylol cpd is one or more in trifluoroethanol, C3-Fluoroalcohol, hexafluoro butanols, oxygenant is one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, and catalyzer is one or more in ferric sulfate, iron nitrate, iron(ic) chloride or tosic acid iron.
Further, mass ratio=(0.5～10) of copolymer p SS-APEG and EDOT in step (2): 1, fluorine alkylol cpd and mass ratio=(0.1～1) (PSS-APEG+EDOT): 1, mol ratio=(0.5～4) of oxygenant and EDOT: 1, mol ratio=(0.001～0.005) of catalyzer and EDOT: 1, mass ratio=1:1 of IPA and EDOT, the solid content of water dispersion is: 1～10%.
The invention has the beneficial effects as follows: one aspect of the present invention has been introduced new template PSS-APEG in PEDOT, make the PEDOT dispersion liquid that makes more stable, film-forming properties is better; On the other hand, introduce again fluorine alkylol cpd, do not affected under the condition of PEDOT:PSS-APEG film transmittance, improve greatly the conductivity of film and reduced water-absorbent, made high conductivity PEDOT:PSS-APEG water dispersion, and preparation technology is simple, is applicable to industry and promotes.
Brief description of the drawings
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is under same template, the square resistance figure of the PEDOT:PSS-APEG film before and after hexafluoro butanols adds, wherein, mol ratio=48:1 of SSNa and APEG, mass ratio=3:1 of copolymer p SS-APEG and EDOT;
Fig. 2 is under same template, the ultraviolet spectrogram of the PEDOT:PSS-APEG film before and after hexafluoro butanols adds, wherein, mol ratio=48:1 of SSNa and APEG, mass ratio=3:1 of copolymer p SS-APEG and EDOT, hexafluoro butanols and mass ratio=0%, 10%, 20%, 40%, 50%, 100% (EDOT+PSS-APEG).
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to illustrate the present invention instead of limitation of the invention further.
Embodiment mono-
Taking PSS-APEG (mol ratio is as 2:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of trifluoroethanol.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 2:1, (NH
4)
2s
2o
8with the mol ratio of SSNa be 100:1.
Concrete preparation method is as follows:
Take 5gSSNa, 12.27gAPEG and 87gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.0553g (NH with syringe
4)
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 9.2327g, productive rate is 53.46%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of trifluoroethanol, wherein: trifluoroethanol is 0.1:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 0.5:1, (NH
4)
2s
2o
8with the mol ratio of EDOT be 0.5:1, Fe
2(SO
4)
3with the mol ratio of EDOT be 0.001:1, the solid content of water dispersion is 1%.
Concrete preparation method is as follows:
Take 0.5gPSS-APEG, 1gEDOT, 0.15g trifluoroethanol and 80gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 0.9024g (NH after dissolving completely
4)
2s
2o
8, 0.0281gFe
2(SO
4)
3, 1gIPA and 85
gh
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of trifluoroethanol.
Embodiment bis-
Taking PSS-APEG (mol ratio is as 6:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of trifluoroethanol.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 6:1, Na
2s
2o
8with the mol ratio of SSNa be 150:1.
Concrete preparation method is as follows:
Take 10gSSNa, 8.09gAPEG and 91gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.0771gNa with syringe
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 11.2641g, productive rate is 62.26%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of trifluoroethanol, wherein: trifluoroethanol is 0.3:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 3:1, Na
2s
2o
8with the mol ratio of EDOT be 1:1, Fe
2(SO
4)
3with the mol ratio of EDOT be 0.0015:1, the solid content of water dispersion is 2%.
Concrete preparation method is as follows:
Take 0.6gPSS-APEG, 0.2gEDOT, 0.12g trifluoroethanol and 20gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 0.3211gNa after dissolving completely
2s
2o
8, 0.0008gFe
2(SO
4)
3, 0.2gIPA and 29gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of trifluoroethanol.
Embodiment tri-
Taking PSS-APEG (mol ratio is as 12:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of C3-Fluoroalcohol.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 12:1, (NH
4)
2s
2o
8with the mol ratio of SSNa be 200:1.
Concrete preparation method is as follows:
Take 15gSSNa, 6.06gAPEG and 105gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.083g (NH with syringe
4)
2s
2o
8; Adjust the temperature to 80 DEG C～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 14.9627g, productive rate is 71.54%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of C3-Fluoroalcohol, wherein: C3-Fluoroalcohol is 0.5:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 3:1, (NH
4)
2s
2o
8with the mol ratio of EDOT be 1.5:1, Fe (NO
3)
3with the mol ratio of EDOT be 0.005:1, the solid content of water dispersion is 4%.
Concrete preparation method is as follows:
Take 0.6gPSS-APEG, 0.2gEDOT, 0.4g C3-Fluoroalcohol and 15gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 0.4815g (NH after dissolving completely
4)
2s
2o
8, 0.0017gFe (NO
3)
3, 0.2gIPA and 15gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of C3-Fluoroalcohol.
Embodiment tetra-
Taking PSS-APEG (mol ratio is as 20:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of C3-Fluoroalcohol.
(1) preparing solid content is 20% PSS-APEG multipolymer, and wherein the mol ratio of SSNa and APEG is 20:1, K
2s
2o
8with the mol ratio of SSNa be 222:1.
Concrete preparation method is as follows:
Take 20gSSNa, 4.86gAPEG and 124gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.1182gK with syringe
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 17.5624g, productive rate is 70.65%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of C3-Fluoroalcohol, wherein: C3-Fluoroalcohol is 0.6:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 1:1, K
2s
2o
8with the mol ratio of EDOT be 2:1, Fe (NO
3)
3with the mol ratio of EDOT be 0.004:1, the solid content of water dispersion is 6%.
Concrete preparation method is as follows:
Take 0.6gPSS-APEG, 0.6gEDOT, 0.72g C3-Fluoroalcohol and 15gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 2.2832gK after dissolving completely
2s
2o
8, 0.0041gFe (NO
3)
3, 0.6gIPA and 17gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of C3-Fluoroalcohol.
Embodiment five
Taking PSS-APEG (mol ratio is as 32:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of hexafluoro butanols.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 32:1, (NH
4)
2s
2o
8with the mol ratio of SSNa be 150:1.
Concrete preparation method is as follows:
Take 20gSSNa, 3.03gAPEG and 115gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.1476g (NH with syringe
4)
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 18.3524g, productive rate is 75.34%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of hexafluoro butanols, wherein: hexafluoro butanols is 0.4:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 2:1, (NH
4)
2s
2o
8with the mol ratio of EDOT be 3:1, Fe
2(SO
4)
3with the mol ratio of EDOT be 0.002:1, the solid content of water dispersion is 2%.
Concrete preparation method is as follows:
Take 0.6gPSS-APEG, 0.3gEDOT, 0.36g hexafluoro butanols and 30gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 1.4443g (NH after dissolving completely
4)
2s
2o
8, 0.0014gFe
2(SO
4)
3, 0.6gIPA and 33gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of hexafluoro butanols.
Embodiment six
Taking PSS-APEG (mol ratio is as 48:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of hexafluoro butanols.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 48:1, Na
2s
2o
8with the mol ratio of SSNa be 215:1.
Concrete preparation method is as follows:
Take 25gSSNa, 3.79gAPEG and 144gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.1344gNa with syringe
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 19.5634g, productive rate is 67.96%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of hexafluoro butanols, wherein: hexafluoro butanols is 0.8:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 3:1, Na
2s
2o
8with the mol ratio of EDOT be 4:1, Fe (NO
3)
3with the mol ratio of EDOT be 0.004:1, the solid content of water dispersion is 2%.
Concrete preparation method is as follows:
Take 0.6gPSS-APEG, 0.2gEDOT, 0.64g hexafluoro butanols and 30gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 1.3407gNa after dissolving completely
2s
2o
8, 0.0014gFe (NO
3)
3, 0.2gIPA and 42gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of hexafluoro butanols.
Embodiment seven
Taking PSS-APEG (mol ratio is as 50:1) as template, preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of hexafluoro butanols.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 50:1, K
2s
2o
8with the mol ratio of SSNa be 300:1.
Concrete preparation method is as follows:
Take 25gSSNa, 2.42gAPEG and 137gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.1093gK with syringe
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 22.4635g, productive rate is 81.92%.
(2) preparation is containing the high conductivity PEDOT:PSS-APEG water dispersion of hexafluoro butanols, wherein: hexafluoro butanols is 1:1 with mass ratio (PSS-APEG+EDOT), and the mass ratio of PSS-APEG and EDOT is 10:1, K
2s
2o
8with the mol ratio of EDOT be 4:1, Fe (OTS)
3, H
2o
2with the mol ratio of EDOT be 0.004:4:1, the solid content of water dispersion is 10%.
Concrete preparation method is as follows:
Take 2gPSS-APEG, 0.2gEDOT, 2.2g hexafluoro butanols and 22gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 1.5221g K after dissolving completely
2s
2o
8, 0.0032gFe (OTS)
3, 0.1915gH
2o
2, 0.2gIPA and 22gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the high conductivity PEDOT:PSS-APEG of hexafluoro butanols.
Embodiment eight (comparative example)
Taking PSS-APEG (mol ratio is as 48:1) as template, preparation PEDOT:PSS-APEG water dispersion.
(1) preparing solid content is 20% PSS-APEG multipolymer, wherein: the mol ratio of SSNa and APEG is 48:1, (NH
4)
2s
2o
8with the mol ratio of SSNa be 222:1.
Concrete preparation method is as follows:
Take 20gSSNa, 2.02gAPEG and 110gH
2o, in the four-hole boiling flask of 250ml, includes magneton; The in the situation that of stirring at normal temperature, vacuum nitrogen filling gas; Be warming up to 80 DEG C, and after SSNa dissolves completely, add oxygenant 0.1g (NH with syringe
4)
2s
2o
8; Adjust the temperature to 80～90 DEG C, reaction 4～6h.Then by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry, output is 19.3125g, productive rate is 87.70%.
(2) prepare PEDOT:PSS-APEG water dispersion, wherein: the mass ratio of PSS-APEG and EDOT is 3:1, (NH
4)
2s
2o
8with the mol ratio of EDOT be 4:1, Fe
2(SO
4)
3with the mol ratio of EDOT be 0.004:1, the solid content of water dispersion is 2%.
Concrete preparation method is as follows:
Take 0.6gPSS-APEG, 0.2gEDOT, 20gH
2o is in reaction flask, and stirring and dissolving at 30～45 DEG C, adds 1.2838g (NH after dissolving completely
4)
2s
2o
8, 0.0023gFe
2(SO
4)
3, 0.2gIPA and 20gH
2o, reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency; Then water dispersion reaction being made filters by anion-cation exchange resin; Finally by centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, by ultrasonic dispersion 1h after precipitate with deionized water dilution, obtain the mazarine water dispersion containing the PEDOT:PSS-APEG of amphiphilic cpds.
The evaluation of PEDOT-PSS electrical conductivity of solution:
Major equipment and model: the digital four point probe tester of RTS-8 type
Measuring method: solution to be measured is uniformly coated on polypropylene screen, film forming after dry 5～8h at 50～90 DEG C, thickness is 100～250 μ m, adopts four probe method to measure the square resistance of film.
Measure the square resistance of the PEDOT:PSS-APEG water dispersion that makes of embodiment mono-～eight, result is as following table:
| Solution to be measured | Square resistance (K Ω/) |
| The PEDOT:PSS-APEG water dispersion that embodiment mono-makes | 0.17 |
| The PEDOT:PSS-APEG water dispersion that embodiment bis-makes | 9.74 |
| The PEDOT:PSS-APEG water dispersion that embodiment tri-makes | 6.24 |
| The PEDOT:PSS-APEG water dispersion that embodiment tetra-makes | 0.26 |
| The PEDOT:PSS-APEG water dispersion that embodiment five makes | 2.48 |
| The PEDOT:PSS-APEG water dispersion that embodiment six makes | 68.99 |
| The PEDOT:PSS-APEG water dispersion that embodiment seven makes | 164.24 |
| The PEDOT:PSS-APEG water dispersion that embodiment eight makes | 135.85 |
As can be seen here, the PEDOT:PSS-APEG water dispersion that the present invention makes fluoridize alkylol cpd has improved 22 times than the specific conductivity of the PEDOT:PSS-APEG water dispersion not adding.
On the basis of embodiment six, change hexafluoro butanols and quality (PSS-APEG+EDOT) than experiment condition, detect the impact of fluorine alkylol cpd on PEDOT:PSS-APEG film conductivity, obtain graphic representation as shown in Figure 1.
Under the condition that Fig. 1 is is 3:1 at the mass ratio of PSS-APEG and EDOT, the square resistance figure of the PEDOT:PSS-APEG film of the add-on of different hexafluoro butanols.As shown in Figure 1, the square resistance that does not add the PEDOT:PSS-APEG film of hexafluoro butanols is 135.85K Ω/, and when hexafluoro butanols is when (PSS-APEG+EDOT) mass ratio is 0.5:1, the square resistance of PEDOT:PSS-APEG film is 6.24K Ω/, has reduced by 22 times.The square resistance that can reduce PEDOT:PSS-APEG film that adds of fluorine alkylol cpd is described, has improved greatly the electric conductivity of film.
On the basis of embodiment six, change hexafluoro butanols and quality (PSS-APEG+EDOT) than experiment condition, detect the impact of fluorine alkylol cpd on PEDOT:PSS-APEG film transmittance, obtain graphic representation as shown in Figure 2.
Fig. 2 is the ultraviolet spectrogram of the PEDOT:PSS-APEG water dispersion before and after hexafluoro butanols adds, wherein the experiment condition of each curve is: under the condition that is 3:1 at the mass ratio of PSS-APEG and EDOT, and the ultraviolet spectrogram obtaining by changing the add-on of hexafluoro butanols.As shown in Figure 2, in visible wavelength range (400～900nm), add the transmissivity of the PEDOT:PSS-APEG water dispersion after hexafluoro butanols than the height of pure PEDOT:PSS-APEG, illustrate and contribute to improve the transmittance of PEDOT:PSS-APEG film adding of hexafluoro butanols.Therefore, can think that the introducing of fluorine alkylol cpd does not affect the transmittance of polymkeric substance.
To sum up, do not affecting under the condition of PEDOT:PSS-APEG transmittance, adding of fluorine alcohol compound can make the conductivity of PEDOT:PSS-APEG film obviously improve.
In PEDOT, introduced new template PSS-APEG, made on the one hand the PEDOT dispersion liquid that makes more stable, place for a long time not stratified, and when the ratio of template and EDOT compared with hour, do not add unstable, the easy layering of polymkeric substance of APEG; On the other hand, the film-forming properties of PEDOT:PSS-APEG water dispersion is better, can form smooth smooth film.
Claims (8)
1. a PEDOT water dispersion for high conductivity, is characterized in that: comprise polymer P EDOT:PSS-APEG, fluorine alkylol cpd and water, the structural formula of polymer P EDOT:PSS-APEG is:
Wherein, m is that 2～140, n is that 2～240, x is 28.
2. the PEDOT water dispersion of a kind of high conductivity according to claim 1, it is characterized in that: described polymer P EDOT:PSS-APEG is taking copolymer p SS-APEG as template, the weight of polymer P EDOT:PSS-APEG is 1～10% of water dispersion gross weight, and the weight of fluorine alkylol cpd is 0.1～10% of water dispersion gross weight.
3. the PEDOT water dispersion of a kind of high conductivity according to claim 1, is characterized in that: described fluorine alkylol cpd is one or more in trifluoroethanol, C3-Fluoroalcohol, hexafluoro butanols.
4. the preparation method of the PEDOT water dispersion of a kind of high conductivity claimed in claim 1, is characterized in that: concrete steps are as follows:
(1) copolymer p SS-APEG's is synthetic:
In reactor, add SSNa, APEG and deionized water, at N
2protection is lower dissolves, and while being heated to 80～90 DEG C, slowly splashes into oxygenant, after dropping finishes, is warming up to 90～100 DEG C; After reaction 4～6h, by dehydrated alcohol precipitation, white depositions is put into vacuum drying oven after repeating to precipitate 3 times dry;
(2) preparation of polymer P EDOT:PSS-APEG water dispersion:
Copolymer p SS-APEG, EDOT, fluorine alkylol cpd and deionized water that step (1) is made add in reaction flask, 30～45 DEG C of stirring and dissolving, after dissolving completely, add oxygenant, catalyzer and Virahol (IPA), reaction 12～24h, in reaction process, timing sampling is surveyed transformation efficiency, obtains water dispersion; Water dispersion is filtered to purifying by anion-cation exchange resin; By centrifugal water dispersion rear removal upper strata liquid, get dispersing and dissolving again after distilled water diluting for precipitation, centrifugal rear removal upper strata liquid in the same way again, repeatedly after three above-mentioned centrifugally operateds, finally, by ultrasonic dispersion 1h after precipitate with deionized water dilution, must contain the mazarine water dispersion of PEDOT:PSS-APEG.
5. the preparation method of the PEDOT water dispersion of a kind of high conductivity according to claim 4, is characterized in that: in described step (1), oxygenant is one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
6. the preparation method of the PEDOT water dispersion of a kind of high conductivity according to claim 4, it is characterized in that: mol ratio=(1～50) of SSNa and APEG in described step (1): 1, mol ratio=(100～300) of oxygenant and SSNa: 1.
7. the preparation method of the PEDOT water dispersion of a kind of high conductivity according to claim 4, it is characterized in that: in described step (2), fluorine alkylol cpd is one or more in trifluoroethanol, C3-Fluoroalcohol, hexafluoro butanols, oxygenant is one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, and catalyzer is one or more in ferric sulfate, iron nitrate, iron(ic) chloride or tosic acid iron.
8. the preparation method of the PEDOT water dispersion of a kind of high conductivity according to claim 4, it is characterized in that: mass ratio=(0.5～10) of copolymer p SS-APEG and EDOT in described step (2): 1, fluorine alkylol cpd and mass ratio=(0.1～1) (PSS-APEG+EDOT): 1, mol ratio=(0.5～4) of oxygenant and EDOT: 1, mol ratio=(0.001～0.005) of catalyzer and EDOT: 1, mass ratio=1:1 of IPA and EDOT, the solid content of water dispersion is: 1～10%.
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| CN105602347A (en) * | 2015-12-22 | 2016-05-25 | 江南大学 | PEDOT [poly(3,4-ethylenedioxythiophene)] aqueous dispersion liquid capable of performing ultraviolet dimerization and preparation method thereof |
| CN107129584A (en) * | 2017-05-12 | 2017-09-05 | 宁波智锐新材料有限公司 | A kind of preparation method of PEDOT/PSS aqueous dispersions and the antistatic coating prepared with the aqueous dispersion |
| CN108148185A (en) * | 2018-01-13 | 2018-06-12 | 常州大学 | It is a kind of using amphipathic nature block polymer PSS-b-PBA as PEDOT aqueous dispersions of template and preparation method thereof |
| CN108258122A (en) * | 2018-01-16 | 2018-07-06 | 浙江师范大学 | A kind of transparent conductive material and preparation method thereof |
| WO2018164641A1 (en) * | 2017-03-07 | 2018-09-13 | Agency For Science, Technology And Research | A method of synthesizing a water-dispersible conductive polymeric composite |
| CN113201181A (en) * | 2021-05-19 | 2021-08-03 | 哈尔滨理工大学 | Preparation method of field enhanced nonlinear conductive polyethylene composite insulating material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105602347A (en) * | 2015-12-22 | 2016-05-25 | 江南大学 | PEDOT [poly(3,4-ethylenedioxythiophene)] aqueous dispersion liquid capable of performing ultraviolet dimerization and preparation method thereof |
| WO2018164641A1 (en) * | 2017-03-07 | 2018-09-13 | Agency For Science, Technology And Research | A method of synthesizing a water-dispersible conductive polymeric composite |
| CN107129584A (en) * | 2017-05-12 | 2017-09-05 | 宁波智锐新材料有限公司 | A kind of preparation method of PEDOT/PSS aqueous dispersions and the antistatic coating prepared with the aqueous dispersion |
| CN108148185A (en) * | 2018-01-13 | 2018-06-12 | 常州大学 | It is a kind of using amphipathic nature block polymer PSS-b-PBA as PEDOT aqueous dispersions of template and preparation method thereof |
| CN108148185B (en) * | 2018-01-13 | 2020-06-26 | 常州大学 | PEDOT aqueous dispersion with amphiphilic block copolymer PSS-b-PBA as template and preparation method thereof |
| CN108258122A (en) * | 2018-01-16 | 2018-07-06 | 浙江师范大学 | A kind of transparent conductive material and preparation method thereof |
| CN113201181A (en) * | 2021-05-19 | 2021-08-03 | 哈尔滨理工大学 | Preparation method of field enhanced nonlinear conductive polyethylene composite insulating material |
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