CN110922810B - Conductive polymer 3D printing ink and preparation method thereof - Google Patents

Conductive polymer 3D printing ink and preparation method thereof Download PDF

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CN110922810B
CN110922810B CN201911258299.XA CN201911258299A CN110922810B CN 110922810 B CN110922810 B CN 110922810B CN 201911258299 A CN201911258299 A CN 201911258299A CN 110922810 B CN110922810 B CN 110922810B
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polystyrene sulfonate
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ethylenedioxy
ethylenedioxythiophene
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CN110922810A (en
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卢宝阳
赵奇
徐景坤
薛羽
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Jiangxi Science and Technology Normal University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D11/52—Electrically conductive inks

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Abstract

The invention discloses conductive polymer 3D printing ink and a preparation method thereof, belonging to the technical field of new 3D printing materials, and the preparation method comprises the following steps of: freezing and drying the polystyrene sulfonate (PSS) aqueous dispersion under a low-temperature condition to obtain a conductive polymer nano fibrous foam structure; and mixing the conductive polymer nano fibrous foam structure by using a binary solvent, and grinding and homogenizing to obtain the series of poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs) -polystyrene sulfonate (PSS) inks. The invention utilizes the freeze drying, redispersion and post-treatment modes and the like to treat the conductive polymer aqueous solution to obtain the high-performance conductive polymer ink for 3D printing, the ink shows excellent 3D printability, can be seamlessly integrated with various materials for printing and other 3D printable materials to form an elastomer, and can be further promoted to the preparation of various high-density flexible electronic devices.

Description

Conductive polymer 3D printing ink and preparation method thereof
Technical Field
The invention relates to the technical field of new 3D printing materials, in particular to conductive polymer 3D printing ink and a preparation method thereof.
Background
Conductive polymers have been widely used in the fabrication of energy storage, flexible electronic and bioelectronic devices by virtue of high electrical conductivity, good stability and biocompatibility and processability. The fabrication of optoelectronic, bioelectronic devices based on conductive polymers currently relies mainly on some conventional techniques, such as inkjet printing, screen printing and photolithography. However, these techniques typically produce conductive polymer devices with low resolution (> 100 μm), complicated fabrication processes (calibration in clean room, masking, etching, post-assembly, etc.), and high processing costs, which greatly hinder the widespread use of conductive polymers. Unlike these conventional methods, three-dimensional (3D) printing provides an extraordinary ability to be freely designed in 3D space, and has the advantages of programmability, portability, flexible way, etc. to design micro-scale structures. Some new materials developed recently that can be 3D printed, such as metals, liquid metals, hydrogels, cell-filled bio-inks, glasses, liquid crystal polymers, and ferromagnetic elastomers, offer more options for 3D printing technologies.
Although great efforts have been made in 3D printing ink materials, the current 3D printing inks are mainly made by mixing materials having different functions (conductive agents, adhesives, solvents, etc.), for example, the inks for 3D printing can be obtained only by mixing a plurality of substances such as ink-based inks, suspending agents, dispersing agents, and ink oils, and the components are complicated, and it is difficult to achieve high-precision printing (CN107312377A, CN110436873A, CN 109316630A).
PEDOT: PSS, as a water-dispersible conductive polymer, has high conductivity, good environmental stability and transparency, and is increasingly gaining attention in the fields of solar cells, antistatic coatings, OLED displays, electrocatalysis, and the like. PEDOT and PSS molecules are mutually combined through electrostatic acting force, and the performance of the polymer is easily regulated and controlled through doping. However, PEDOT: the high rheological properties of PSS itself make it difficult to process untreated aqueous dispersions by means of 3D printing or the like. Currently, some foreign company has developed the information about PEDOT: PSS conductive polymer inks, such as PEDOT-PSS A1 (viscosity-35 cPs), PEDOT-P1900 (viscosity-40 cPs), PEDOT-JET40 (viscosity-8 cPs) and PEDOT-ESD5000 (viscosity-10 cPs), are difficult to be used for high-precision equipment processing such as 3D printing due to the problems of high cost, complex preparation process, insufficient material properties and the like.
Based on this, the development of novel conductive polymer ink capable of being used for 3D printing and the development of novel conductive polymer mode capable of 3D printing have great practical significance, and great help is provided for further promoting the commercial transformation of conductive polymers.
Disclosure of Invention
In order to solve the technical problems, the invention provides conductive polymer 3D printing ink and a preparation method thereof, wherein a conductive polymer aqueous solution is processed by freeze drying, redispersion, post-processing and the like to obtain the high-performance conductive polymer ink for 3D printing, the ink shows excellent 3D printability, can be seamlessly integrated with various materials for printing and other 3D printable materials to form an elastomer, and can be further promoted to the preparation of various high-density flexible electronic devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of conductive polymer 3D printing ink comprises the following steps:
(1) mixing a poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOT): freezing and drying the polystyrene sulfonate (PSS) aqueous dispersion under a low-temperature condition to obtain a conductive polymer nano fibrous foam structure;
(2) and mixing the conductive polymer nano fibrous foam structure by using a binary solvent, and grinding and homogenizing to obtain the series of poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs) -polystyrene sulfonate (PSS) inks.
Preferably, the poly (3, 4-ethylenedioxythiophene) based conductive Polymer (PEDOT) in the step (1): an aqueous polystyrene sulfonate (PSS) dispersion comprising:
poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS); and:
PEDOT: PSS derivatives: poly (3, 4-ethylenedioxythiophene-hydroxymethyl): polystyrene sulfonate (PEDOT-MeOH: PSS), poly (3, 4-ethylenedioxythiophene-aminomethyl): polystyrene sulfonate (PEDOT-MeNH 2: PSS), poly (3, 4-ethylenedioxythiophene-chloromethyl): polystyrene sulfonate (PEDOT-MeCl: PSS), poly (3, 4-ethylenedioxythiophene-azidomethyl): polystyrene sulfonate (PEDOT-N3: PSS), poly (3, 4-ethylenedioxythiophene-methyl acetate): polystyrene sulfonate (PEDOT-MeOAc: PSS), poly (3, 4-ethylenedioxythiophene-acrylic acid group): polystyrene sulfonate (PEDOT-AA: PSS), (3, 4-ethylenedioxythiophene-2- (methoxymethyl) epoxyethyl): polystyrene sulfonate (PEDOT-M0: PSS), poly (3, 4-ethylenedioxythiophene-4-methoxy-4-oxobutanoic acid): polystyrene sulfonate (PC 4-EDOT-COOH: PSS), poly (ethyl 3, 4-dioxyethylenethiophene-4-methoxybenzoate): polystyrene sulfonate (PEDOT-Ph-C00C2H 5: PSS), (3, 4-dioxyethylenethiophene-4- (methoxymethyl) benzoic acid): polystyrene sulfonate (PEDOT-Ph-COOH: PSS), poly (3, 4-ethylenedioxythiophene-Boc (t-butyloxycarbonyl) protected phenylalanine): polystyrene sulfonate (PEDOT-Boc-Phe: PSS), (3, 4-ethylenedioxythiophene-phenylalanine): polystyrene sulfonate (PEDOT-Phe: PSS), (3, 4-ethylenedioxythiophene-leucine): polystyrene sulfonate (PEDOT-Leu: PSS), (3, 4-ethylenedioxythiophene-Boc (t-butyloxycarbonyl) protected leucine): polystyrene sulfonate (PEDOT-Boc-Leu: PSS), (3, 4-ethylenedioxythiophene-Boc (t-butyloxycarbonyl) protected α -linolenic acid): polystyrene sulfonate (PEDOT-Boc-Ala: PSS).
PEDOT: PSS analogs: poly (3, 4-ethylenedioxyfuran): polystyrene sulfonate (PEDOF: PSS), poly (3, 4-ethylenedithiofuran): polystyrene sulfonate (PEDTF: PSS), poly (3, 4-dihydro-2H-thieno [3,4-b ] pyran): polystyrene sulfonate (PEDTP: PSS), poly (thieno [3,4-b ] -1, 4-xanthene): polystyrene sulfonate (PEOTT: PSS), poly (3, 4-ethylenedithiothiophene): polystyrene sulfonate (PEDTT: PSS), poly (3, 4-ethylene dithiopyrrole): polystyrene sulfonate (PEDTPy: PSS), poly (3, 4-ethylenedioxypyrrole): polystyrene sulfonate PEDOPy: PSS, poly (3, 4-ethylenedithioselenophene): polystyrene sulfonate (PEDTS: PSS), (PEOTS: PSS), poly (seleno [3,4-b ] -1, 4-xanthene): polystyrene sulfonate (PEDOS: PSS), poly (3, 4-ethanedithiophos): polystyrene sulfonate (PEDPP: PSS), poly (3, 4-ethylenedioxytellurophene): polystyrene sulfonate (PEDOTe: PSS).
The structure of the conductive polymer is simply as follows:
Figure BDA0002311342680000031
preferably, the freezing conditions in the step (1) are as follows: the freezing temperature is lower than-40 ℃, and the freezing medium is any one of liquid nitrogen, liquid helium, solid carbon dioxide, low-temperature ethanol and low-temperature acetonitrile; the drying conditions were: the temperature is less than-20 ℃.
Preferably, the binary solvent system in step (2) is a polar solvent-water mixed solution, the polar solvent is any one of dimethyl sulfoxide (DMSO), Ethylene Glycol (EG), N-Dimethylformamide (DMF), Tetrahydrofuran (THF), glycerol, hexitol, ethylene glycol monomethyl ether, diethylene glycol, dimethyl sulfate, erythritol, xylitol, concentrated sulfuric acid, quaternary ammonium salt ionic liquid, and choline eutectic solvent, and the volume fraction of water is 75% to 95%.
Preferably, the poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs) -polystyrene sulfonate (PSS) ink prepared in the step (2), wherein the mass concentration of the poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs) -polystyrene sulfonate (PSS) is 5 to 9 wt%.
The invention also comprises conductive polymer 3D printing ink which is prepared by the preparation method for the conductive polymer ink for 3D printing.
The beneficial technical effects of the invention are as follows:
(1) with PEDOT: PSS and derivatives and analogues thereof, and conducting polymer aqueous solution is processed by freeze drying, redispersion and post-processing to obtain high-performance conducting polymer ink for 3D printing, and the obtained pure conducting polymer ink shows excellent 3D printability, can realize high resolution (more than 30 μm), high aspect ratio (more than 20) and highly reproducible conducting polymer manufacturing, and can seamlessly integrate elastomers with various material printing and other 3D printable materials (such as insulating materials);
(2) the convenience based on 3D printing is further demonstrated, the manufacturing method of the high-density flexible electronic circuit and the soft nerve probe is greatly simplified, the existing challenges in the 3D printing of the conductive polymer are overcome, and a promising new manufacturing strategy is provided for the conductive polymer in flexible electronics, wearable equipment and bioelectronics besides the existing electronic manufacturing technology.
Drawings
Figure 1 shows PEDOT prepared according to the invention at different mass concentrations: a photographic schematic of the PSS conductive polymer 3D printing ink;
figure 2 is a graph of PEDOT: SEM images of 3D printed conductive polymer mesh of PSS conductive polymer 3D printed ink: nozzle diameters of 200 μm (a), 100 μm (b), 50 μm (c) and 30 μm (d);
figure 3 is a graph of PEDOT prepared according to the invention: characterization of the properties of the PSS conductive polymer 3D printing ink: different mass concentrations of PEDOT: PSS conductive polymer 3D printing ink apparent viscosity and shear rate relation diagram (a); apparent viscosity of conductive polymer ink compared to PEDOT: (ii) relation (b) of PSS conductive polymer 3D printing ink mass concentration; different mass concentrations of PEDOT: 3D printing a relation graph (c) of the shear storage modulus and the shear stress of the ink by using the PSS conductive polymer; shear yield stress of conductive polymer ink compared to PEDOT: (ii) a graph (D) of the relationship between the mass concentration of the PSS conductive polymer 3D printing ink;
figure 4 is a graph of PEDOT: PSS conductive polymer ink 3D printed device and performance schematic diagram: with PEDOT: (ii) high density flexible electronic circuits printed with PSS conductive polymer inks (a); driving an led on a 3D printed conductive polymer circuit (b); (ii) a bend-free failure of the 3D printed conductive polymer circuit (c); a 3D printed soft nerve probe (D) with 9 channels assembled from conductive polymer ink and PDMS matrix; 3D printed soft nerve probe magnified view (e); implanting 3D printed soft nerve probes and mice with implanted probes (f); representative electrophysiological recordings of 3D-printed soft neuroprobes in mouse dhcs: a Local Field Potential (LFP) trace (0.5 to 250Hz) (g) under free motion conditions, a continuous extracellular Action Potential (AP) trace (300 to 40K Hz) (h) under free motion conditions; (ii) principal component analysis (i) from the individual cell potentials recorded in (h); the average two unit spike waveforms recorded over time correspond to cluster (j) in (i).
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A PEDOT: the preparation method of the PSS conductive polymer 3D printing ink comprises the following steps:
(1) and (3) mixing PEDOT: and (3) freezing the PSS aqueous dispersion in liquid nitrogen at a low temperature of less than-40 ℃, and drying at a low temperature of less than-20 ℃ to obtain PEDOT: PSS conductive polymer nanofibrous foam structures;
(2) and (3) mixing the PEDOT: the PSS conductive polymer nano fibrous foam structure is prepared by mixing a polar solvent-water mixed solution (DMSO: water 25: 75v/v) by using a binary mixed solvent system, grinding and homogenizing, and preparing a mixture with the concentration of 5 wt% PEDOT: PSS conductive polymer 3D printing inks.
The PEDOT: PSS conductive polymer 3D printing ink performance exploration:
the concentration obtained by the above preparation was 5 wt% PEDOT: the PSS conductive polymer ink is a paste elastic fluid, has excellent rheological properties such as shear thinning and shear yield, has good 3D printing performance, and can be used for direct writing 3D printing and realizing high-precision, high-flux, high-aspect-ratio and rapid 3D printing technology of conductive polymer materials or conductive polymer hydrogels. Using the prepared PEDOT: the PSS conductive polymer inks print high density multi-electrode arrays, the printed electrodes exhibit excellent conductivity in both the dry or hydrogel state.
PEDOT prepared by the method of this example: the PSS conductive polymer 3D printing ink is subjected to performance characterization and applied to a 3D printing device, as shown in figures 1-4, and as can be seen from figure 1, the conductive polymer 3D printing ink is a pasty elastic fluid. Figure 2 shows that the conductive polymer 3D printing ink has excellent rheological properties such as shear thinning, yield, etc., has good 3D printability and can be used for direct writing 3D printing, and in order to demonstrate high resolution printing, we printed a grid of conductive polymer ink (7 wt% PEDOT: PSS) through 200, 100, 50 and 30 μm nozzles. FIG. 3 is a rheological test of conductive polymer inks, transition from low viscosity liquid (low concentration PEDOT: PSS conductive polymer 3D printing ink) to physical gel (high concentration PEDOT: PSS conductive polymer 3D printing ink) having shear thinning and shear yield rheology of 3D printable inks. Fig. 4 is a 3D printing of a conductive polymer device demonstrating convenient streamlined fabrication examples of functional conductive polymer structures and devices, including high density flexible electronic circuits, soft neural electrodes, by 3D printing functions.
Example 2
A PEDOT-MeCl: the preparation method of the PSS conductive polymer 3D printing ink comprises the following steps:
(1) PEDOT-MeCl: directly freezing the PSS aqueous dispersion in solid carbon dioxide at a low temperature of less than-40 ℃, and drying at a low temperature of less than-20 ℃ to obtain PEDOT-MeCl: PSS conductive polymer nanofibrous foam structures;
(2) the PEDOT-MeCl: the PSS conductive polymer nano fibrous foam structure is prepared by mixing a polar solvent-water mixed solution (EG: water 25: 75v/v) by using a binary mixed solvent system, grinding and homogenizing, and preparing PEDOT-MeCl with the concentration of 5 wt%: PSS conductive polymer 3D printing inks.
PEDOT-MeCl as described above: PSS conductive polymer 3D printing ink performance exploration:
the concentration prepared above was 5 wt% PEDOT-MeCl: the PSS conductive polymer 3D printing ink is a paste elastic fluid, has excellent rheological properties such as shear thinning and shear yield, has good 3D printing performance, and can be used for direct writing 3D printing and realizing high-precision, high-flux, high-aspect-ratio and rapid 3D printing technology of conductive polymer materials or conductive polymer hydrogel. Using the prepared PEDOT-MeCl: the PSS conductive polymer ink prints a nerve probe that can successfully record the continuous neural activity of mice over two weeks. Furthermore, a 3D printed soft neural probe can record the signal of a single cell isolated from a single channel of the probe.
Example 3
A PEDOT-MeOH: the preparation method of the PSS conductive polymer 3D printing ink comprises the following steps:
(1) PEDOT-MeOH: directly freezing the PSS aqueous dispersion in liquid helium at a low temperature of less than-40 ℃, and drying at a low temperature of less than-20 ℃ to obtain PEDOT-MeOH: PSS conductive polymer nanofibrous foam structures;
(2) the PEDOT-MeOH: the PSS conductive polymer nano fibrous foam structure is prepared by mixing a polar solvent-water mixed solution (EG: water 20: 80v/v) by using a binary mixed solvent system, grinding and homogenizing, and preparing a mixture with the concentration of 6 wt% PEDOT-MeOH: PSS conductive polymer 3D printing inks.
PEDOT-MeOH described above: PSS conductive polymer 3D printing ink performance exploration:
the concentration prepared above was 6 wt% PEDOT-MeOH: the PSS conductive polymer 3D printing ink is a paste elastic fluid, has excellent rheological properties such as shear thinning and shear yield, has good 3D printing performance, and can be used for direct writing 3D printing and realizing high-precision, high-flux, high-aspect-ratio and rapid 3D printing technology of conductive polymer materials or conductive polymer hydrogel. Using prepared PEDOT-MeOH: the PSS conductive polymer inks print high density multi-electrode arrays, the printed electrodes exhibit excellent conductivity in both the dry or hydrogel state.
Example 4
A method of preparing a PEDTT: the preparation method of the PSS conductive polymer 3D printing ink comprises the following steps:
(1) and (3) adding PEDTT: directly freezing the PSS aqueous dispersion in low-temperature ethanol at the freezing temperature of-40 ℃, and drying at low temperature at the temperature of-20 ℃ to obtain PEDTT: PSS conductive polymer nanofibrous foam structures;
(2) and (3) mixing the PEDTT: the PSS conductive polymer nano fibrous foam structure is prepared by mixing a polar solvent-water mixed solution (DMSO: water 20: 80v/v) by using a binary mixed solvent system, grinding and homogenizing, and preparing PEDTT with the concentration of 7 wt%: PSS conductive polymer 3D printing inks.
The PEDTT: PSS conductive polymer 3D printing ink performance exploration:
the concentration prepared above was 7 wt% PEDTT: the PSS conductive polymer 3D printing ink is a paste elastic fluid, has excellent rheological properties such as shear thinning and shear yield, has good 3D printing performance, and can be used for direct writing 3D printing and realizing high-precision, high-flux, high-aspect-ratio and rapid 3D printing technology of conductive polymer materials or conductive polymer hydrogel. Using the prepared PEDTT: the PSS conductive polymer ink prints a nerve probe that can successfully record the continuous neural activity of mice over two weeks. Furthermore, a 3D printed soft neural probe can record the signal of a single cell isolated from a single channel of the probe.
Example 5
A PEDOS: the preparation method of the PSS conductive polymer 3D printing ink comprises the following steps:
(1) and (3) mixing the PEDOS: directly freezing the PSS aqueous dispersion in low-temperature acetonitrile at the freezing temperature of-40 ℃, and drying at low temperature at the temperature of-20 ℃ to obtain PEDOS: PSS conductive polymer nanofibrous foam structures;
(2) and (3) mixing the PEDOS: the PSS conductive polymer nanofibrous foam structure is prepared by mixing a polar solvent-water mixed solution (THF: water 15: 85v/v) by using a binary mixed solvent system, grinding and homogenizing, and preparing PEDOS with the concentration of 8 wt%: PSS conductive polymer 3D printing inks.
The PEDOS: PSS conductive polymer 3D printing ink performance exploration:
the concentration prepared above was 8 wt% of PEDOS: the PSS conductive polymer 3D printing ink is a paste elastic fluid, has excellent rheological properties such as shear thinning and shear yield, has good 3D printing performance, and can be used for direct writing 3D printing and realizing high-precision, high-flux, high-aspect-ratio and rapid 3D printing technology of conductive polymer materials or conductive polymer hydrogel. Using the prepared PEDOS: the PSS conductive polymer inks print high density multi-electrode arrays, the printed electrodes exhibit excellent conductivity in both the dry or hydrogel state.
Example 6
A PEOTT: the preparation method of the PSS conductive polymer 3D printing ink comprises the following steps:
(1) mixing PEOTT: directly freezing the PSS aqueous dispersion in liquid nitrogen at a low temperature of less than-40 ℃, and drying at a low temperature of less than-20 ℃ to obtain a PEOTT: PSS conductive polymer nanofibrous foam structures;
(2) mixing the above PEOTT: the PSS conductive polymer nano fibrous foam structure is prepared by mixing a polar solvent-water mixed solution (DMF: water 10: 90v/v) by using a binary mixed solvent system, grinding and homogenizing, and preparing a 9 wt% PEOTT: PSS conductive polymer 3D printing inks.
The above PEOTT: PSS conductive polymer 3D printing ink performance exploration:
the concentration prepared above was 9 wt% PEOTT: the PSS conductive polymer 3D printing ink is a paste elastic fluid, has excellent rheological properties such as shear thinning and shear yield, has good 3D printing performance, and can be used for direct writing 3D printing and realizing high-precision, high-flux, high-aspect-ratio and rapid 3D printing technology of conductive polymer materials or conductive polymer hydrogel. Using the prepared PEOTT: the PSS conductive polymer ink prints a nerve probe that can successfully record the continuous neural activity of mice over two weeks. Furthermore, a 3D printed soft neural probe can record the signal of a single cell isolated from a single channel of the probe.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and variations which do not require inventive efforts and are made by those skilled in the art are still within the scope of the present invention.

Claims (4)

1. The preparation method of the conductive polymer 3D printing ink is characterized in that the conductive polymer 3D printing ink is prepared from poly (3, 4-ethylenedioxythiophene) conductive Polymers (PEDOTs): the polystyrene sulfonate (PSS) aqueous dispersion and a binary solvent are composed, and the method comprises the following steps:
(1) preparing a poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs): freezing and drying the aqueous dispersion of polystyrene sulfonate (PSS) at low temperature to obtain a conductive polymer nanofiber foam structure, wherein the poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs): polystyrene sulfonates (PSS) include poly (3, 4-ethylenedioxythiophene): any one of polystyrene sulfonate (PEDOT: PSS), PEDOT: PSS derivatives, PEDOT: PSS analogues;
(2) mixing the conductive polymer nano fibrous foam structure by using a binary solvent, and grinding and homogenizing to obtain the poly (3, 4-ethylenedioxythiophene) conductive Polymer (PEDOTs): polystyrene sulfonate (PSS) ink, wherein poly (3, 4-ethylenedioxythiophene) based conductive Polymers (PEDOTs): the mass concentration of the polystyrene sulfonate (PSS) is 5-9 wt%;
the PEDOT PSS derivatives include poly (3, 4-ethylenedioxythiophene-hydroxymethyl) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-aminomethyl) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-chloromethyl) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-azidomethyl) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-methyl acetate) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-acrylic acid) polystyrene sulfonate, (3, 4-ethylenedioxythiophene-2- (methoxymethyl) oxiranyl) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-4-methoxy-4-oxobutanoic acid) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-2- (methoxymethyl) oxiranyl) polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-hydroxymethyl) ethylene sulfonate, poly (3, 4-ethylenedioxy-ethylthiophene-4-oxobutanoic acid) polystyrene sulfonate, poly (3, poly (ethylenedioxythiophene-methyl) ethylene sulfonate, poly (ethylenedioxy-4-ethyl-methyl) styrene sulfonate, poly (ethylenedioxy-2-ethyl-2-hydroxy-butanoic acid) styrene sulfonate, poly (ethylenedioxy-ethyl-2-ethyl-2-one, poly (ethylenedioxybutanoic acid) styrene sulfonate, poly (ethylenedioxy-2-methyl-ethylenedioxy-ethyl-2-one, poly (ethylenedioxy-4-one, poly (ethylenedioxy-4-one, poly (ethylenedioxy-4) styrene sulfonate, poly (ethylenedioxy-one, poly (ethylenedioxy) styrene, poly (ethylenedioxy-one, poly (ethylenedioxy-2) styrene), Poly (ethyl 3, 4-dioxoethylene-thiophene-4-methoxybenzoate): polystyrene sulfonate, (3, 4-dioxyethylenethiophene-4- (methoxymethyl) benzoic acid): polystyrene sulfonate, poly (3, 4-ethylenedioxythiophene-Boc (tert-butyloxycarbonyl) protected phenylalanine): polystyrene sulfonate, (3, 4-ethylenedioxythiophene-phenylalanine): polystyrene sulfonate, (3, 4-ethylenedioxythiophene-leucine): polystyrene sulfonate, (3, 4-ethylenedioxythiophene-Boc (tert-butyloxycarbonyl) protected leucine): polystyrene sulfonate, (3, 4-ethylenedioxythiophene-Boc (tert-butyloxycarbonyl) protected α -linolenic acid): any one of polystyrene sulfonate;
the PEDOT PSS analogs include poly (3, 4-ethylenedioxyfuran), polystyrene sulfonate, poly (3, 4-ethylenedithiofuran), polystyrene sulfonate, poly (3, 4-dihydro-2H-thieno [3,4-b ] pyran), polystyrene sulfonate, poly (thieno [3,4-b ] -1, 4-xanthene), polystyrene sulfonate, poly (3, 4-ethylenedithiothiophene), polystyrene sulfonate, poly (3, 4-ethylenedithiopyrrole), polystyrene sulfonate, poly (3, 4-ethylenedioxypyrrole), polystyrene sulfonate, poly (3, 4-ethylenedithioselenophene), poly (3, 4-ethylenedioxyselenophene), polystyrene sulfonate, poly (3, 4-ethylenedioxy-selenophene), polystyrene sulfonate, poly (3, 4-ethylenedioxy-dithiophene, poly (3, 4-selenophene), poly (3, poly (ethylenedioxy-dithio-selenophene), poly (1, poly (ethylenedioxy-selenophene), poly (3, poly (ethylenedioxy-p-selenophene), poly (1, poly (ethylenedioxy) salts, poly (ethylenedioxy) salts, poly (ethylenedithio), poly (ethylenedioxy, poly (ethylenedithio, poly (ethylenedioxy, etc.), poly (ethylenedioxy, etc.), poly (ethylenedioxy, etc.), poly (ethylenedioxy, poly, Poly (seleno [3,4-b ] -1, 4-xanthene), polystyrene sulfonate, poly (3, 4-ethyldithio-phosphine), polystyrene sulfonate, poly (3, 4-ethylenedioxy tellurium-thiophene) and polystyrene sulfonate.
2. The method for preparing the conductive polymer 3D printing ink according to claim 1, wherein the freezing condition in the step (1) is as follows: the freezing temperature is lower than-40 deg.C, and the freezing medium is any one of liquid nitrogen, liquid helium, solid carbon dioxide, low temperature ethanol, and low temperature acetonitrile; the drying conditions were: the temperature is lower than-20 ℃.
3. The method for preparing a conductive polymer 3D printing ink according to claim 1, wherein the binary solvent system in the step (2) is a polar solvent-water mixed solution, the polar solvent is any one of dimethyl sulfoxide (DMSO), Ethylene Glycol (EG), N-Dimethylformamide (DMF), Tetrahydrofuran (THF), glycerol, hexanetriol, ethylene glycol monomethyl ether, diethylene glycol, dimethyl sulfate, erythritol, xylitol, concentrated sulfuric acid, quaternary ammonium salt ionic liquid and choline eutectic solvent, and the volume fraction of water is 75-95%.
4. A conductive polymer 3D printing ink, characterized in that it is prepared by the method of any one of claims 1-3.
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