CN106496528A - A kind of method that utilization micro passage reaction prepares PEDOT PSS aqueous liquid dispersions - Google Patents
A kind of method that utilization micro passage reaction prepares PEDOT PSS aqueous liquid dispersions Download PDFInfo
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Abstract
The present invention discloses a kind of method that utilization micro passage reaction prepares PEDOT PSS aqueous liquid dispersions, comprises the steps：(1) aqueous solution of the initiator of 0.1～1Mol/L is preheated to 0～50 DEG C；EDOT/PSS mixed aqueous solutions containing 0.1～0.5Mol/L EDOT, 0.1～3Mol/L PSS are preheated to 0～50 DEG C；(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in micro passage reaction and carry out polyreaction, obtain PEDOT PSS crude product solutions.The present invention can obtain the aqueous dispersion of different molecular weight, different molecular weight dispersion, different nanometer size ranges and concentration by controlling the polymerizing conditions such as micro passage reaction size, temperature, residence time of material, there is provided a kind of efficiently controllable, new mode of production of PEDOT PSS aqueous liquid dispersions that are meeting different field application.
Description
Technical field
The present invention relates to Material Field, and in particular to a kind of using micro passage reaction preparation PEDOT-PSS aqueous dispersions
The method of liquid.
Background technology
PEDOT (poly- 3,4-ethylene dioxythiophene) is the polymer of EDOT (3,4-ethylene dioxythiophene monomer), and which is outside
Power-up field action under can sky blue and transparent between there is reversible color change, be a kind of very excellent electrochromism gather
Condensation material, used as a kind of application future polymeric material widely, PEDOT fusing points are very high, and are almost not dissolved in
Organic solvent, its insoluble insoluble feature make its processing difficulties so as to which application is severely limited.Mixed using dopant
The miscellaneous PEDOT dispersions that prepare are the most important methods for solving PEDOT processing difficulties at present.As macromole dopant has dispersion concurrently
With the function of doping, therefore, some new macromole or copolymer dopant doping PEDOT also result in and widely grind recently
Study carefully interest.The most successful dopant of commercialization at present is polyelectrolyte polystyrolsulfon acid (PSS).Bayer A.G is sent out
Clear PSS doping PEDOT is prepared for stable PEDOT/PSS aqueous dispersions Polyglycolic acid fibre/kayexalate
(PEDOT-PSS).
PEDOT/PSS production technologies be usually adopt kayexalate for raw material, using persulfate, iron salt or its
His peroxide is reacted to prepare PEDOT-PSS with EDOT in aqueous phase system as initiator.(Groenendaal,L.,et
al.,Poly(3,4‐ethylenedioxy thiophene)and Its Derivatives:Past,Present,and
Future.Advanced Materials,2000.12(7):P.481-494.) its reacting quintessence is that a kind of radical polymerization is anti-
Should, as polyreaction for the heat transfer of reactor and is mixed with extra high requirement, the temperature of reaction system, concentration, stirring
The many factors such as hybrid mode have a significant impact for properties such as the molecular weight of polymer, molecular weight distribution.More than reducing
Impact of the factor to PEDOT/PSS properties of product, research worker are attempted preparing using interpolation emulsifying agent or the polymerization of other dopants
PEDOT PSS, main using there is some anion surfactants, such as dodecylbenzene sodium sulfonate (Haba, Y., et al.,
Polymerization of aniline in the presence of DBSA in an aqueous
dispersion.Synthetic Metals,1999.106(1):p.59-66.)、(Choi,J.W.,et al.,Poly(3,4-
ethylenedioxythiophene)nanoparticles prepared in aqueous DBSA
solutions.Synthetic Metals,2004.141(3):p.293-299.).Gemini surface active agent CN102993413
Aqueous polyurethane, polyethers etc. (CN102399416A, CN102443250A).The PEDOT- that these methods are prepared in laboratory
PSS performances have certain polymer molecular weight for improving but still the amplification of batch (-type) tank reactor can not being overcome existing after producing not
The problems such as stable and molecular weight distribution width, it is impossible to solve the property of PEDOT-PSS polymer itself from molecular level, also with regard to nothing
A series of problems, such as method is surveyed bottom and solves PEDOT-PSS poorly conductives in actual applications, processability difference etc..
In order to solve problem present in PEDOT-PSS production processes, polymer molecular weight is controlled from molecular level, is divided
The distribution of son amount and polymeric species, and then obtain, with high conductivity, uniform particle diameter be controllable, high stability product, meeting high
Developed for the performance requirement of PEDOT-PSS by a kind of steady and continuous, efficiently controllable PEDOT-PSS aqueous dispersions for smart pointed collar domain
The liquid mode of production is significant.
Content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of prepared using micro passage reaction
The method of PEDOT-PSS aqueous liquid dispersions.The present invention is by controlling micro passage reaction size, temperature, residence time of material etc.
Polymerizing condition can obtain the aqueous dispersion of different molecular weight, different molecular weight dispersion, different nanometer size ranges and concentration,
Provide a kind of efficiently controllable, new mode of production of PEDOT-PSS aqueous liquid dispersions that are meeting different field application.
Realize that the purpose of the present invention can be reached by adopting the following technical scheme that：
A kind of method that utilization micro passage reaction prepares PEDOT-PSS aqueous liquid dispersions, comprises the steps：
(1) aqueous solution of the initiator of 0.1～1Mol/L is preheated to 0～50 DEG C；Will be containing 0.1～0.5Mol/L
EDOT, the EDOT/PSS mixed aqueous solutions of 0.1～3Mol/L PSS are preheated to 0～50 DEG C；
(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in micro passage reaction and gathered
Reaction is closed, PEDOT-PSS crude product solutions are obtained.
Preferably, also include step (3) in methods described, step (3) are by the PEDOT- that obtains step (2)
PSS crude product solutions carry out desalination and obtain PEDOT-PSS aqueous liquid dispersions.
Preferably, the desalination described in step (3) be specially by PEDOT-PSS crude product solutions first pass through resin anion (R.A.) or
Resin cation exchange device desalination, then through ultrafiltration apparatuss desalination.
Preferably, the inducing agent described in step (1) is Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate, ferric chloride, sulfur
One kind in sour ferrum, ferric nitrate, p-methyl benzenesulfonic acid ferrum, hydrogen peroxide.
Preferably, the internal diameter of the micro passage reaction described in step (2) is 0.1～20mm.
Preferably, the reaction temperature of step (2) is 10～80 DEG C.
Preferably, the response time of step (2) is 5s-10min.
Preferably, in step (2), the ratio of the amount of the material of inducing agent and EDOT is 1：(0.5～2).
Preferably, in step (2), the ratio of the amount of the material of inducing agent and EDOT is 1：1
Preferably, method provided by the present invention comprises the steps：
(1) aqueous solution of the initiator of 0.6Mol/L is preheated to 20 DEG C；Will be containing 0.15Mol/L EDOT, 0.45Mol/
The EDOT/PSS mixed aqueous solutions of L PSS are preheated to 20 DEG C；The initiator is hydrogen peroxide；
(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in internal diameter be 10mm microchannel
In reactor, under conditions of 35 DEG C, polyreaction is carried out, a length of 30s during reaction obtains PEDOT-PSS crude product solutions；Cause
The volume ratio of the aqueous solution of agent and EDOT/PSS mixed aqueous solutions is 1:4；
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then through super
Filter equipment desalination obtains PEDOT-PSS aqueous liquid dispersions.
Polyglycolic acid fibre/kayexalate (PEDOT-PSS) is the novel conductive that new development in recent years is got up
Polymer, as this doped polymer has transparency after excellent electric conductivity and film property and film forming good, at present more
Promotion and application, such as antistatic field, Organic Light Emitting Diode, OLED, energy-saving illumination field have been obtained come more fields
Deng.For corresponding high quality P EDOT-PSS aqueous liquid dispersion demand is also increasingly increased.
After PEDOT is by adulterating with PSS, the intermiscibility with water is improved, the aqueous dispersion for becoming stable can be made.
The mode of production of such product is all batch production in traditional reactor at present, due to the heat transfer of reactor in production process
With mass transfer energy power restriction, in reaction system, often skewness, local response thing concentration are inconsistent for temperature, cause PEDOT-PSS
Molecular weight is unstable and molecular weight distribution width, and then causing the PEDOT-PSS of each production, to there is particle diameter big, in water phase point
Scattered property is poor, easily reunites and produces precipitation, holding time not long etc. shortcomings.Traditional autoclave production PEDOT-PSS is due to depositing
Cause to exist in actual applications that transmittance is low, covering property is poor, conductivity is low, stretch-resistance is poor etc. lacks in above problems
Point, limits the further genralrlization application in high-grade, precision and advanced field of the product.
Micro passage reaction inside dimensions are little, specific surface area is big, and heat and mass ability is strong, the mixing efficiency of reactant and anti-
The thousands of times for answering speed to be traditional tank reactor, is particularly well-suited to the application of polyreaction.The present invention is for existing process
Deficiency, has invented a kind of technique for preparing PEDOT-PSS aqueous liquid dispersions in continuous micro passage reaction.
Compared to existing technology, the beneficial effects of the present invention is：
1st, the present invention can be obtained by controlling the polymerizing conditions such as micro passage reaction size, temperature, residence time of material
The aqueous dispersion of different molecular weight, different molecular weight dispersion, different nanometer size ranges and concentration, there is provided one kind efficiently may be used
Control, meet the new mode of production of the PEDOT-PSS aqueous liquid dispersions of different field application.
2nd, compared with the currently conventionally produced PEDOT-PSS aqueous liquid dispersions for obtaining, provided by the present invention
PEDOT-PSS aqueous liquid dispersions have the advantages that molecular weight is controllable, dispersion is little, high conductivity, uniform particle diameter are controllable.
3rd, technique provided by the present invention is compared with traditional handicraft, with low cost, energy consumption is little, the three wastes are few, continuously controllable,
The advantages of without enlarge-effect, while have can be according to needs of production, the simple advantage waited than amplifying.
Description of the drawings
Fig. 1 is present invention process flow chart.
Fig. 2 is the production equipment schematic diagram used by the present invention.
In Fig. 2, S1, initiator solution；S2, PSS, EDOT monomer solution；P1, dosing pump 1；P2, dosing pump 2；M1、
Micro-mixer；B1, calorstat；R1, micro passage reaction；C, ultrafiltration demineralization plant.
Specific embodiment
Below, in conjunction with accompanying drawing and specific embodiment, the present invention is described further：
Embodiment 1：
As shown in Figure 1, 2, a kind of using micro passage reaction preparation PEDOT-PSS (being expressed as PEDOT/PSS in Fig. 1) water
The method of property dispersion liquid, comprises the steps：
(1) aqueous solution of the initiator of 0.1Mol/L is preheated to 0 DEG C；Will be containing 0.1Mol/LEDOT, 0.1Mol/L
The EDOT/PSS mixed aqueous solutions of PSS are preheated to 0 DEG C；The initiator is ferric chloride.
(2) by preheating after the aqueous solution of initiator be added in dosing pump 1, by preheating after EDOT/PSS mixing water-soluble
Liquid is added in dosing pump 2, and after the aqueous solution of initiator is mixed in micro-mixer with EDOT/PSS mixed aqueous solutions, stream enters
During internal diameter is for the micro passage reaction of 0.1mm, micro passage reaction is located in calorstat, adjusts reaction temperature, in 10 DEG C of bar
Polyreaction is carried out under part, a length of 5s during reaction obtains PEDOT-PSS crude product solutions；The material of initiator and EDOT chargings
Amount ratio 1:0.5.
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then through super
Filter equipment demineralization plant carries out desalination and obtains PEDOT-PSS aqueous liquid dispersions.
Embodiment 2：
As shown in Figure 1, 2, a kind of method that utilization micro passage reaction prepares PEDOT-PSS aqueous liquid dispersions, including such as
Lower step：
(1) aqueous solution of the initiator of 1Mol/L is preheated to 50 DEG C；By containing 0.5Mol/LEDOT, 3Mol/L PSS's
EDOT/PSS mixed aqueous solutions are preheated to 50 DEG C；The initiator is ferric nitrate.
(2) by preheating after the aqueous solution of initiator be added in dosing pump 1, by preheating after EDOT/PSS mixing water-soluble
Liquid is added in dosing pump 2, and after the aqueous solution of initiator is mixed in micro-mixer with EDOT/PSS mixed aqueous solutions, stream enters
During internal diameter is for the micro passage reaction of 20mm, micro passage reaction is located in calorstat, adjusts reaction temperature, in 80 DEG C of condition
Under carry out polyreaction, a length of 10min during reaction obtains PEDOT-PSS crude product solutions；The material of initiator and EDOT chargings
Amount ratio 1:2.
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then through super
Filter equipment demineralization plant carries out desalination and obtains PEDOT-PSS aqueous liquid dispersions.
Embodiment 3：
As shown in Figure 1, 2, a kind of method that utilization micro passage reaction prepares PEDOT-PSS aqueous liquid dispersions, including such as
Lower step：
(1) aqueous solution of the initiator of 1Mol/L is preheated to 25 DEG C；Will be containing 0.35Mol/LEDOT, 3Mol/L PSS
EDOT/PSS mixed aqueous solutions be preheated to 50 DEG C；The initiator is potassium peroxydisulfate.
(2) by preheating after the aqueous solution of initiator be added in dosing pump 1, by preheating after EDOT/PSS mixing water-soluble
Liquid is added in dosing pump 2, and after the aqueous solution of initiator is mixed in micro-mixer with EDOT/PSS mixed aqueous solutions, stream enters
During internal diameter is for the micro passage reaction of 20mm, micro passage reaction is located in calorstat, adjusts reaction temperature, in 80 DEG C of condition
Under carry out polyreaction, a length of 10min during reaction obtains PEDOT-PSS crude product solutions.
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then through super
Filter equipment demineralization plant carries out desalination and obtains PEDOT-PSS aqueous liquid dispersions.
Embodiment 4
A kind of method that utilization micro passage reaction prepares PEDOT-PSS aqueous liquid dispersions, comprises the steps：
(1) aqueous solution of the initiator of 0.6Mol/L is preheated to 20 DEG C；Will be containing 0.15Mol/L EDOT, 0.45Mol/
The EDOT/PSS mixed aqueous solutions of L PSS are preheated to 20 DEG C；The initiator is hydrogen peroxide；
(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in internal diameter be 10mm microchannel
In reactor, under conditions of 35 DEG C, polyreaction is carried out, a length of 30s during reaction obtains PEDOT-PSS crude product solutions；Cause
The volume ratio of the aqueous solution of agent and EDOT/PSS mixed aqueous solutions is 1:4；
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then through super
Filter equipment desalination obtains PEDOT-PSS aqueous liquid dispersions.
Embodiment 5
A kind of method that utilization micro passage reaction prepares PEDOT-PSS aqueous liquid dispersions, comprises the steps：
(1) aqueous solution of the initiator of 0.4Mol/L is preheated to 25 DEG C；Will be containing 0.3Mol/L EDOT, 0.8Mol/L
The EDOT/PSS mixed aqueous solutions of PSS are preheated to 20 DEG C；The initiator is p-methyl benzenesulfonic acid ferrum；
(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in internal diameter be 10mm microchannel
In reactor, under conditions of 35 DEG C, polyreaction is carried out, a length of 30s during reaction obtains PEDOT-PSS crude product solutions；Cause
The amount ratio 1 of the material of agent and EDOT chargings:2.
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then through super
Filter equipment desalination obtains PEDOT-PSS aqueous liquid dispersions.
Checking embodiment
By the PEDOT-PSS aqueous liquid dispersions for being obtained, polymer number-average molecular weight, molecular weight dispersity, average grain is carried out
Footpath, the detection of solid content；Four-point probe method testing conductive rate is adopted under the conditions of 20 degree；The reunion that observes after room temperature is placed 60 days
Sedimentation.Testing result is as shown in table 1 below.Knowable to testing result, the PEDOT-PSS aqueous liquid dispersions provided by embodiment 1～5,
Number-average molecular weight 60000-90000, molecular weight dispersity 1.1～1.4, mean diameter 80-100nm.The aqueous liquid dispersion contains admittedly
Amount 1.3-1.7%.The aqueous liquid dispersion places 60 using 20 degree of lower testing conductivity 100-600S/CM of four-point probe method, room temperature
Without many merits such as sedimentation of substantially reuniting after it.
Table 1, PEDOT-PSS aqueous liquid dispersion performance test results
For a person skilled in the art, technical scheme that can be as described above and design, make other each
Plant corresponding change and deform, and all these changes and deforms the protection model that should all belong to the claims in the present invention
Within enclosing.
Claims (10)
1. a kind of method that utilization micro passage reaction prepares PEDOT-PSS aqueous liquid dispersions, it is characterised in that including following step
Suddenly：
(1) aqueous solution of the initiator of 0.1～1Mol/L is preheated to 0～50 DEG C；Will containing 0.1～0.5Mol/L EDOT,
The EDOT/PSS mixed aqueous solutions of 0.1～3Mol/L PSS are preheated to 0～50 DEG C；
(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in micro passage reaction carry out being polymerized anti-
Should, obtain PEDOT-PSS crude product solutions.
2. the method that utilization micro passage reaction according to claim 1 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：Also include step (3) in methods described, step (3) are by the PEDOT-PSS crude product solutions that obtain step (2)
Carry out desalination and obtain PEDOT-PSS aqueous liquid dispersions.
3. the method that utilization micro passage reaction according to claim 2 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：Desalination described in step (3) is specially and for PEDOT-PSS crude product solutions to first pass through resin anion (R.A.) or cationic resin
Exchanger desalination, then through ultrafiltration apparatuss desalination.
4. the method that utilization micro passage reaction according to claim 1 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：Inducing agent described in step (1) is Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate, ferric chloride, iron sulfate, nitric acid
One kind in ferrum, p-methyl benzenesulfonic acid ferrum, hydrogen peroxide.
5. the method that utilization micro passage reaction according to claim 1 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：The internal diameter of the micro passage reaction described in step (2) is 0.1～20mm.
6. the method that utilization micro passage reaction according to claim 1 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：The reaction temperature of step (2) is 10～80 DEG C.
7. the method that utilization micro passage reaction according to claim 1 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：The response time 5s-10min of step (2).
8. the method that utilization micro passage reaction according to claim 1 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：In step (2), the ratio of the amount of the material of inducing agent and EDOT is 1:(0.5～2).
9. the method that utilization micro passage reaction according to claim 8 prepares PEDOT-PSS aqueous liquid dispersions, its feature
It is：In step (2), the ratio of the amount of the material of inducing agent and EDOT is 1：1.
10. the method that utilization micro passage reaction according to claim 2 prepares PEDOT-PSS aqueous liquid dispersions, its are special
Levy and be to comprise the steps：
(1) aqueous solution of the initiator of 0.6Mol/L is preheated to 20 DEG C；Will be containing 0.15Mol/L EDOT, 0.45Mol/L
The EDOT/PSS mixed aqueous solutions of PSS are preheated to 20 DEG C；The initiator is hydrogen peroxide；
(2) by preheating after initiator aqueous solution and EDOT/PSS mixed aqueous solutions be placed in internal diameter be 10mm microchannel plate should
In device, under conditions of 35 DEG C, polyreaction is carried out, a length of 30s during reaction obtains PEDOT-PSS crude product solutions；Initiator
The volume ratio of aqueous solution and EDOT/PSS mixed aqueous solutions is 1:4；
(3) PEDOT-PSS crude product solutions are first passed through resin anion (R.A.) or resin cation exchange device desalination, then is set through ultrafiltration
Standby desalination obtains PEDOT-PSS aqueous liquid dispersions.
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| CN108380150A (en) * | 2018-03-21 | 2018-08-10 | 上海交通大学 | Prepare the multichannel microreactor system and method for low-molecular-weight polystyrene |
| CN116751321A (en) * | 2023-08-17 | 2023-09-15 | 山东理工大学 | Method for preparing electronic grade sodium polystyrene sulfonate aqueous solution by photocatalysis continuous controllable method |
| US11796362B2 (en) * | 2017-03-03 | 2023-10-24 | Schlumberger Technology Corporation | Conductivity probe fluid property measurement systems and related methods |
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| CN103709417A (en) * | 2013-12-24 | 2014-04-09 | 深圳新宙邦科技股份有限公司 | Polythiophene derivative aqueous dispersion and preparation method thereof |
| CN104672786A (en) * | 2015-03-11 | 2015-06-03 | 中国科学院理化技术研究所 | Water-soluble PEDOT-PSS dispersion liquid and homogeneous polymerization preparation method thereof |
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| CN103709417A (en) * | 2013-12-24 | 2014-04-09 | 深圳新宙邦科技股份有限公司 | Polythiophene derivative aqueous dispersion and preparation method thereof |
| CN104672786A (en) * | 2015-03-11 | 2015-06-03 | 中国科学院理化技术研究所 | Water-soluble PEDOT-PSS dispersion liquid and homogeneous polymerization preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11796362B2 (en) * | 2017-03-03 | 2023-10-24 | Schlumberger Technology Corporation | Conductivity probe fluid property measurement systems and related methods |
| CN108380150A (en) * | 2018-03-21 | 2018-08-10 | 上海交通大学 | Prepare the multichannel microreactor system and method for low-molecular-weight polystyrene |
| CN116751321A (en) * | 2023-08-17 | 2023-09-15 | 山东理工大学 | Method for preparing electronic grade sodium polystyrene sulfonate aqueous solution by photocatalysis continuous controllable method |
| CN116751321B (en) * | 2023-08-17 | 2023-10-20 | 山东理工大学 | Method for preparing electronic grade sodium polystyrene sulfonate aqueous solution by photocatalysis continuous controllable method |
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