WO2012129805A1 - 导电聚合物及其合成方法、表面覆盖有所述导电聚合物的电活性电极 - Google Patents

导电聚合物及其合成方法、表面覆盖有所述导电聚合物的电活性电极 Download PDF

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WO2012129805A1
WO2012129805A1 PCT/CN2011/072338 CN2011072338W WO2012129805A1 WO 2012129805 A1 WO2012129805 A1 WO 2012129805A1 CN 2011072338 W CN2011072338 W CN 2011072338W WO 2012129805 A1 WO2012129805 A1 WO 2012129805A1
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conductive polymer
solution
acid
hydrogel
monomer
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French (fr)
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潘力佳
翟东媛
施毅
邱浩
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南京大学
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Publication of WO2012129805A1 publication Critical patent/WO2012129805A1/zh

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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G11/48—Conductive polymers
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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Definitions

  • the present invention relates to a conductive polymer and a method of synthesizing the same, and an electroactive electrode having a surface covered with the conductive polymer.
  • BACKGROUND OF THE INVENTION Since MacDiarmid, Hideki Shirakawa, and Heeger invented conductive polymers and doped these polymers to achieve full-scale performance control from insulator to metal state, a new field of chemical and condensed matter physics was created. The field of optoelectronics, electronics and electrochemistry has generated a lot of application prospects.
  • Conductive polymers have stable physical and chemical properties, high electrical conductivity, and electron-ion double carrier conductivity, and are therefore widely used as electrode materials for electrochemically related sensors, energy storage devices and the like.
  • the conductivity of conductive polymers is related to variables such as redox state and pH, and is widely used in smart materials such as sensors.
  • conductive polymer hydrogels in biosensors, chemical sensors, bioelectrodes, bio-batteries, microbial fuel cells, microbial electrolysis cells, medical electrodes, artificial muscles, artificial organs, drug release and biofuels for the following reasons The battery and other fields are receiving more and more attention:
  • Conductive polymer hydrogels have a nano-frame structure and a large solid-liquid contact area with enhanced electron conductivity, ion and molecular diffusion effects, which facilitate the transport of electrons in the device;
  • Conductive polymer hydrogels have the characteristics and advantages of soft materials compared to conventional metal electrodes
  • Conductive polymer hydrogels are biocompatible and are closest to the biological tissue environment compared to all other materials. To date, there are only a few limited ways to synthesize conductive polymer hydrogels because the two prerequisites for hydrogel formation are difficult to satisfy: 1) the hydrophilicity of the polymer; 2) the chemical or Physical cross-linking.
  • conductive polymer hydrogels can be synthesized by the following methods:
  • the present invention provides a method for synthesizing a conductive polymer, which is simple in preparation and does not require introduction of other impurities.
  • the present invention also provides a conductive polymer obtained by the above synthesis method.
  • the invention also provides an electroactive electrode having a surface covered with the electrically conductive polymer.
  • the conductive polymer is synthesized by using a polybasic acid as a dopant and a crosslinking agent to polymerize a monomer to obtain a conductive polymer hydrogel, the monomer being pyrrole or a derivative thereof, thiophene or a derivative thereof.
  • a polybasic acid as a dopant and a crosslinking agent to polymerize a monomer to obtain a conductive polymer hydrogel, the monomer being pyrrole or a derivative thereof, thiophene or a derivative thereof.
  • the acid group of the polybasic acid contains a phosphate group
  • the polybasic acid contains at least one selected from the group consisting of a sulfonic acid group, a nitrate group or a carboxylic acid group.
  • the acid group has a molecular weight of 800 polybasic acids.
  • the molar ratio of the number of moles of the acid groups contained in the polybasic acid to the conductive polymer monomer is preferably from 1:12 to 12:1, more preferably from 2:1 to 1:2.
  • Preferred polybasic acids are phytic acid, phosphoric acid, polyvinyl phosphate, N-sulfonic acid butyl-3-methylimidazolium hydrogensulfate, N-sulfonic acid butylpyridine hydrogensulfate or 1,2,4,5- At least one of benzenetetracarboxylic acid, wherein the phytic acid structural formula is as shown in formula i, and the structural formula of 1,2,4,5-benzenetetracarboxylic acid is as shown in the formula. More preferably, the polybasic acid is phytic acid.
  • the monomer is subjected to a conventional polymerization method to obtain a conductive polymer hydrogel.
  • the monomer is subjected to chemical oxidative polymerization under the action of an oxidizing agent to obtain a conductive polymer hydrogel.
  • the oxidizing agent is at least one of persulfate, ferric chloride, copper chloride, silver nitrate, hydrogen peroxide, chloroauric acid or ammonium cerium nitrate.
  • the conductive polymer hydrogel has a water content of from 30% to 85%, preferably from 34% to 85%.
  • the method for synthesizing the conductive polymer may specifically include the following steps:
  • the first solution is an aqueous solution
  • the second solution is an aqueous solution or an organic solution
  • the polybasic acid is formulated in the first solution and/or the second solution.
  • the obtained conductive polymer hydrogel is purified and dried to obtain a porous nanostructure conductive polymer.
  • An electroactive electrode having a surface covered with a conductive polymer obtained by the above synthetic method An electroactive electrode having a surface covered with a conductive polymer obtained by the above synthetic method.
  • the method for preparing the electroactive electrode may specifically include the following steps:
  • step (IV) covering the surface of the electrode carrier with the mixed solution obtained in the step (III) by spin coating, smear coating, casting, ink jet printing or screen printing to form a conductive polymer hydrogel electrode structure;
  • the first solution is an aqueous solution
  • the second solution is an aqueous solution or an organic solution
  • the polybasic acid is formulated in the first solution and/or the second solution.
  • monomers such as aniline monomers can be polymerized together to form a long-chain polyaniline structure.
  • the amine group of polyaniline can interact with an acid group (doped acid, DA) to form a doped polyaniline salt, as shown in Fig. 1B.
  • Both the polypyrrole and the polythiophene molecules can undergo a similar acid doping reaction, as shown in Fig. 1C and Fig. 1.
  • the conductive polymer is doped with a polyfunctional doping acid, the conductive polymer forms a network crosslinked structure as shown in FIG. After the conductive polymer hydrogel is lyophilized, its microscopic structure is a monolithic coral-like nanostructure.
  • Fig. 1B 2, 3, high-quality uniform polyaniline hydrogels can be synthesized in large quantities by a simple chemical method using polyfunctional doping acid (management > 3).
  • the preparation method of the conductive polymer of the invention is simple, and no other impurities are introduced, and the hydrogel can be formed in a rapid and high yield in an aqueous solution, which is suitable for mass production.
  • the conductive polymer hydrogel and the monolithic nanostructured conductive polymer material can be prepared as a homogeneous film by dip coating or spin coating the precursor.
  • the hydrogel can be micropatterned by the method of ink jet printing of the precursor.
  • Conductive polymer hydrogels form uniform monolithic coral-like nanostructures.
  • the selected polyfunctional doping acid effectively promotes the gelation process.
  • the conductive polymer is doped with a polyfunctional doping acid, and the same polyfunctional doped acid molecule interacts with a plurality of polymer chains, and thus the conductive polymer is crosslinked to form a three-dimensional network structure.
  • the multi-component doping acid is advantageous for making the surface of the conductive polymer hydrophilic, so that the three-dimensional network structure of the conductive polymer can retain moisture to form a gel. When the gel is dried, the space occupied by the moisture is volatilized, and the molecular chain of the conductive polymer is a rigid chain.
  • the prepared hydrogel is a pure doped conductive polymer composition rather than a composite material, and thus the conductivity and electrochemical activity of the conductive polymer are retained. In the whole synthesis, no metal ions are used, which makes the hydrogel highly biocompatible, suitable for biosensors, biofuel cells, bio-batteries, microbial fuel cells, microbial electrolysis cells, artificial muscles, artificial organs, drugs Release applications in areas such as.
  • the synthesized hydrogel has a three-dimensional porous nanostructure composed of a branched fibrous structure, as shown in Figs. 4A and 4B, wherein the dried PEG has a BET surface area of more than 30 m 2 ⁇ g ⁇ o prepared conductive polymer
  • the hydrogel has a high ionic conductivity of about 0.017 to 0.026 S * cm - the conductive polymer hydrogel has a contact angle of less than 15 ° and is super hydrophilic.
  • Conductive polymer hydrogels have good biocompatibility.
  • Fig. 1B is a schematic diagram showing the molecular structure of a polyaniline emeraldine salt in a doped state.
  • DA refers to doping acid.
  • Fig. Schematic diagram of the molecular structure of 1C acid-doped polypyrrole salt.
  • Fig. 1D Schematic diagram of the molecular structure of acid-doped polythiophene (PED0T).
  • Fig. 2 is a schematic diagram showing the formation mechanism of a conductive polymer hydrogel. Under the action of a polyfunctional doping acid, the conductive polymer chains are crosslinked to form a conductive polymer hydrogel.
  • Fig. 3 A synthetic flow chart of a conductive polymer hydrogel.
  • Fig. 4A Scanning electron microscopy image of polyaniline hydrogel after lyophilization.
  • Fig. 4B Scanning electron microscopy image of a magnified polyaniline hydrogel after lyophilization.
  • Fig. 5 Scanning electron microscopy image of polypyrrole hydrogel after lyophilization.
  • Fig. 6 Scanning electron microscopy image of polythiophene hydrogel after lyophilization.
  • Fig. 7 Scanning electron microscopy image of a polyaniline hydrogel film formed by spin coating.
  • Fig. 8A Scanning electron microscopy image of bovine bone marrow stem cells grown on phytic acid doped polyaniline hydrogel.
  • Fig. 8B Scanning electron microscopy image of bovine bone marrow stem cells grown on phytic acid-doped polyaniline hydrogel.
  • Fig. 9 Fluorescence microscopy image of bovine bone marrow stem cells grown on poly(pyrrole) hydrogel doped with polyvinylphosphoric acid.
  • Fig. 10 Sensing curve of phytic acid-doped polyaniline hydrogel glucose oxidase electrode on glucose.
  • the synthesis method of the conductive polymer is as follows: Step 1. Configure a solution consisting of water and oxidant.
  • the oxidizing agent is preferably ammonium persulfate, but other oxidizing agents such as ferric chloride, copper chloride, silver nitrate, hydrogen peroxide, chloroauric acid and other persulfate derivatives such as Na 2 S 2 0 8 and K are also used. 2 S 2 0 8 .
  • the monomer and the acid are dissolved in water or an organic solvent to form a monomer solution.
  • it is a monomeric aniline, but other carbon-based organic monomers such as pyrrole, thiophene and aniline derivatives such as aminoanisole, methylaniline, ethylaniline, o-alkoxyaniline and 2 can also be used.
  • ,5-dialkoxyaniline monomer which can be used for the synthesis of polypyrrole, polythiophene, polymethoxyaniline, polymethylaniline, polyethylaniline, polyalkoxyaniline, poly 2,5- Dialkoxyaniline and the like.
  • the effect of multi-component doping acid is preferably phytic acid containing phosphoric acid groups, phosphoric acid and polyvinyl phosphate, but other small molecular acids of polyfunctionality (functionality 2, molecular weight 800, the functionality refers to polybasic acid per molecule)
  • the number of acid groups contained can also be used, such as 1,2,4,5-benzenetetracarboxylic acid, N-sulfonic acid butyl-3-methylimidazolium hydrogensulfate, N-sulfonic acid butylpyridine sulfuric acid Hydrogen salt, etc.
  • the reaction can be carried out in single-phase aqueous solution synthesis or interfacial polymerization (organic solvent-water two-phase interface synthesis).
  • the organic solvent uses carbon tetrachloride (CC1 4 ), but other organic solvents that are not miscible with water can also be used, such as benzene, toluene, chloroform, methyl chloride, xylene, n-hexane, diethyl ether. , dichloromethane and carbon disulfide.
  • the aniline monomer and the phytic acid are mixed and dissolved in water.
  • Step 3 Place the monomer solution in the reaction vessel.
  • the capacity of the container can be large or small according to actual needs.
  • Large-sized containers can be used for mass production of polymer hydrogels, and can also be cast into hydrogel materials of different shapes in various shapes of containers.
  • Step 4 Mix the oxidizing agent solution with the monomer solution.
  • Step 5 Allow to stand (from a few minutes to several days) to form a polyaniline hydrogel in the aqueous phase within a few minutes, while observing that the color of the aqueous solution turns dark green.
  • Step 6 Purification of the hydrogel.
  • the hydrogel material is dialyzed or deionized in deionized water, distilled water to remove excess ions.
  • a phytic acid doped polyaniline pure hydrogel was obtained.
  • the hydrogel can also be doped with ammonia water.
  • dedoping does not destroy the hydrogel structure because the porous polyaniline backbone can retain its shape.
  • Whether or not a hydrogel is formed can be verified by an inversion experiment (cited by: Metal- and Anion-Binding Supramolecular Gels, Chem. Rev. 2010, 110, 1960-2004.), that is, the container is reversed, and the aqueous solution is not available. Fluidity is considered to form a hydrogel.
  • the "solution loss of fluidity" in the reverse experiment of the present patent example means that the container is reversed, and no solution flow behavior which is clearly distinguishable by the naked eye is observed within 30 minutes.
  • Example A homogeneous reaction
  • Example 1 Phytic acid (functionality 6, containing 6 phosphates) Doped polyaniline hydrogel
  • the mixing ratio of the reagents can be varied within a certain range (for example, the ratio of the amount of the phosphate groups contained in the aniline to the phytic acid can form a gel in the range of 1:12 to 12:1; persulfuric acid; The ratio of ammonium to aniline monomer can vary over a wide range; the concentration of the reagent can be varied within a range to obtain a conductive polyaniline hydrogel having a water content of 35% to 85%).
  • the hydrogel obtained in this example had a contact angle of ⁇ 15° and was superhydrophilic.
  • the hydrogel has a high ionic conductivity of 0.025 S * cm- ⁇ by chemical impedance spectroscopy.
  • the hydrogel is lyophilized and observed under a scanning electron microscope as a coral-like monolithic porous nanomaterial composed of dendritic fibers.
  • Figure 4 specific surface area >30 !11 2 * ⁇ -
  • the phytic acid-doped polyaniline hydrogel grown has good biocompatibility, as shown in Figure 5 for hydrogel surface growth. Bovine bone marrow stem cells.
  • the powder after lyophilization of the gel is pressed into a block shape, and its conductivity is 0.02 S ⁇ cm by a standard four-probe method.
  • the precursor solution is spin-coated to form a uniform green transparent conductive polyaniline. Hydrogel film.
  • Example 2 Phytic acid doped polyaniline hydrogel (water content 34%)
  • the ionic conductivity of the obtained hydrogel was 0.017 S ⁇ cm -
  • Example 6 1,2,4,5-benzenetetracarboxylic acid (functionality 4, containing 4 carboxylates) doped polyaniline hydrogel
  • dialysis is carried out in deionized water to purify the hydrogel to remove impurities such as ions and oligomers to obtain a hydrogel.
  • the powder after lyophilization of the gel is pressed into a block shape, and its conductivity is tested by a standard four-probe method.
  • the acidity of 0.0026 S - cm 1 carboxylic acid is weak, so the conductivity of doped polyaniline is low.
  • Example 8 N-sulfonic acid butyl-3-methylimidazolium hydrogensulfate (functionality) 2, one sulfonate and one hydrogen sulfate ion at both ends of the molecule) doped polyaniline hydrogel
  • Example 9 Polyvinylphosphoric acid doped polyaniline hydrogel
  • Example 10 Phytic acid (functionality 6, containing 6 phosphates) Doped polypyrrole water Gel
  • ethylene glycol is to increase the solubility of pyrrole.
  • the two solutions are then mixed and polymerization occurs to rapidly produce a polypyrrole hydrogel. It was observed that the color of the solution turned black and the solution lost fluidity.
  • Example 11 Phytic acid-doped poly(2-hydroxyethyl)thiophene water Gel
  • dialysis is carried out in deionized water to purify the hydrogel to remove impurities such as ions and oligomers to obtain a hydrogel of poly-2-(2-hydroxyethyl)thiophene.
  • the powder after lyophilization of the gel was pressed into a block shape and tested to have a conductivity of 6.2 S ⁇ cm- by a standard four-probe method.
  • a hydrogel of polyaniline is formed in the aqueous phase. It was observed that the aqueous phase solution turned dark green and lost fluidity to form a gel. Finally, the organic phase solution is removed and the hydrogel is dialyzed in deionized water to purify the hydrogel to remove impurities such as ions and oligomers. The powder after lyophilization of the gel was pressed into a block shape and tested to have a conductivity of 0.018 S ⁇ cm by a standard four-probe method.
  • Example 2 Interfacial reaction to form a phytic acid-doped polypyrrole hydrogel
  • a hydrogel of polypyrrole is formed in the aqueous phase. It was observed that the aqueous solution turned rapidly to black and lost fluidity to form a gel. Finally, the organic phase solution is removed and the hydrogel is dialyzed in deionized water to purify the hydrogel to remove impurities such as ions and oligomers. The powder after lyophilization of the gel was pressed into a block shape and tested to have a conductivity of 1.8 S ⁇ cm by a standard four probe method.
  • Example 3 Interfacial reaction to form a phosphoric acid doped polypyrrole hydrogel
  • a hydrogel of polypyrrole is formed in the aqueous phase. It was observed that the aqueous phase solution turned rapidly to black and lost fluidity. After the reaction was completed, the organic phase solution was poured off, and the hydrogel was dialyzed in deionized water to purify the hydrogel. The powder after lyophilization of the gel was pressed into a block shape and tested to have a conductivity of 2.1 S ⁇ cm by a standard four-probe method.
  • Example 4 Interfacial reaction to form a polyvinyl phosphate doped polypyrrole hydrogel
  • the polymerization takes place at the interface of the aqueous solution and the organic solution.
  • a hydrogel of polypyrrole is formed in the aqueous phase. It was observed that the aqueous phase solution turned rapidly to black and lost fluidity.
  • the organic phase solution was poured off, and the hydrogel was dialyzed in deionized water and ethanol to purify the hydrogel.
  • the powder after lyophilization of the gel is compressed into a block shape, and the conductivity of the hydrogel obtained by the standard four-probe method is 2.5 S*cm-.
  • the obtained hydrogel has good biocompatibility, as shown in Fig.
  • the present invention provides a method of forming a purely conductive polymer hydrogel (non-composite material), the body of which is a monolithic coral-like conductive polymer nanostructure.
  • the synthesis of conductive polymer hydrogels and monolithic porous nanostructures is easy to mass produce and can be carried out at room temperature without significant contamination of the synthesis process. Since the synthesized conductive polymer hydrogel has the advantages that the pure conductive polymer directly forms the hydrogel host material, has high ion conductivity, super hydrophilicity, and high biocompatibility, the method and material of the present invention can be widely used.
  • conductive polymer hydrogels and their nanostructured devices such as biosensors, chemical sensors, transistors, memories, supercapacitors, lithium batteries, fuel cells, biofuel cells, artificial muscles, artificial organs, drug release, electromagnetic Shielding, anti-corrosion coating, etc.
  • the method crosslinks the conductive polymer in the solution into a whole by doping with a multi-component doping acid and crosslinking the conductive polymer molecular chain to form a monolithic coral-like nanostructure.
  • the reaction can be carried out by an aqueous solution homogeneous reaction or a water-organic solvent two-phase interfacial reaction.
  • Different conductive polymer hydrogels can be obtained by selecting various monomers, solvents, oxidizing agents and polybasic acid.
  • the precursor solution is mixed and dropped on the surface of the platinum electrode to form a hydrogel, and then exchanged with deionized water to remove impurity ions.
  • glucose oxidase is added dropwise, and the electrode and the calomel electrode are added.
  • Etc. constitutes a 3-electrode system.
  • An aqueous glucose solution was added to the solution, and each drop was added to form a 1 mmol/L glucose increment.
  • the hydrogel enzyme electrode is very sensitive to glucose sensing with a response time of 6 s, whereas conventional polyaniline-prepared enzyme electrodes are typically on the order of several minutes.

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导电聚合物及其合成方法、 表面覆盖有所述导电聚合物的电活性电极 技术领域 本发明涉及一种导电聚合物及其合成方法、 表面覆盖有所述导电聚合物的电活性电极。 背景技术 自 MacDiarmid, Hideki Shirakawa, 和 Heeger发明导电聚合物及对这些聚合物进行掺杂实 现由绝缘体到金属态的全方面性能调控后， 开创了一个化学与凝聚态物理相交叉的新领域， 在光电子， 电子和电化学领域产生了大量的应用前景。 导电聚合物具有稳定的物理和化学性 质，高电导率， 以及电子-离子双重载流子导电机制， 因此被广泛应用为电化学相关的传感器、 能源存储等器件的电极材料。 此外， 导电聚合物的电导率与氧化还原状态、 酸碱度等变量相 关， 被广泛用于智能材料如传感器等。 近几十年来， 因为下列原因， 导电聚合物水凝胶在生 物传感器， 化学传感器， 生物电极， 生物电池， 微生物燃料电池， 微生物电解池， 医疗电极， 人造肌肉， 人造器官， 药物释放和生物燃料电池等领域受到越来越多关注：
1 ) 导电聚合物水凝胶具有纳米框架结构和足够大的固体-液体接触面积， 具备增强的电 子电导率、 离子和分子扩散效应， 有利于器件中电子的输运；
2) 导电聚合物水凝胶与传统的金属电极相比， 具备软材料的特征和优点；
3 ) 导电聚合物水凝胶具有生物相容性， 与其他所有材料相比最接近生物组织环境。 截至目前为止， 只有有限的几种方法可以合成导电聚合物水凝胶， 因为形成水凝胶的两 个先决条件难以满足： 1 ) 聚合物的亲水性； 2) 聚合物链间的化学或物理交联。
目前， 导电聚合物水凝胶可由以下方法合成：
1 )在非导电聚合物基水凝胶模板中合成导电聚合物（即形成了不导电水凝胶与导电聚合 物的复合材料)；
2)由铁或镁离子和带负电荷的聚电解质掺杂剂相互作用形成离子交联的水溶性导电聚合 物凝胶；
3 ) 通过环氧基团与聚苯胺的氨基发生交联反应， 交联聚苯胺形成凝胶。
然而， 上述所有方法都无一例外引入了杂质或非功能性材料， 如金属离子或无功能的聚 合物。 这些方法的缺点在于， 降低了导电聚合物的电导率、 电化学活性或生物相容性， 详细 分析如下： 1 ) 通过导电聚合物与普通水凝胶材料如聚乙烯醇， 聚乙二醇， 壳聚糖， 聚丙烯 酰胺， 聚 2-羟乙基甲基丙烯酸甲酯， 聚丙烯酸， 海藻酸钠水凝胶等形成复合材料可以合成出 生物相容性的水凝胶。然而与非功能水凝胶材料复合无疑降低了材料的电导率和电化学活性， 从而降低了电极和传感器的性能； 2)将导电聚合物上掺杂的负电荷性聚电解质与金属离子相 互作用而交联的方法， 引入了大量的金属离子杂质， 降低了生物相容性和酶的活性； 3)对于 由聚苯胺主链上的氨基与环氧基团进行交联的方法大大降低了导电聚合物的导电性。 总之， 现有的合成方法不能满足导电聚合物在生物医学工程， 生物电池， 微生物燃料电池等领域的 应用需求。 发明内容 本发明提供一种导电聚合物的合成方法， 制备方法简单， 且无需引入其他杂质。
本发明还提供上述合成方法得到的导电聚合物。
本发明还提供表面覆盖有所述导电聚合物的电活性电极。
所述导电聚合物的合成方法为， 以多元酸作为掺杂剂和交联剂， 使单体聚合得到导电聚 合物水凝胶， 所述单体为吡咯或其衍生物、 噻吩或其衍生物、 苯胺或其衍生物中的至少一种， 所述多元酸的酸基团包含磷酸基、 或者多元酸为每分子含 2个以上选自磺酸基、 硝酸基或羧 酸基中至少一种的酸基团的分子量 800的多元酸。
所述多元酸所包含的酸基团的摩尔数与导电聚合物单体的摩尔比优选为 1 : 12-12： 1， 更优选为 2:1~1:2。
优选的多元酸为植酸、 磷酸、 聚乙烯基磷酸、 N-磺酸丁基 -3-甲基咪唑硫酸氢盐、 N-磺酸 丁基吡啶硫酸氢盐或 1,2,4,5-苯四羧酸中的至少一种， 其中植酸结构式如式 i所示， 1,2,4,5- 苯四羧酸结构式如式 ϋ所示。 更优选所述多元酸为植酸。
Figure imgf000004_0001
单体经常规聚合方法得到导电聚合物水凝胶， 如单体在氧化剂作用下， 经化学氧化聚合 得到导电聚合物水凝胶。 氧化剂为过硫酸盐、 氯化铁、 氯化铜、 硝酸银、 过氧化氢、 氯金酸 或硝酸铈铵中的至少一种。 所述导电聚合物水凝胶的含水量为 30%-85%， 优选为 34%-85%。 所述的导电聚合物的合成方法具体地可以包括以下步骤：
( 1 ) 配制包含氧化剂的第一溶液；
(2) 配制包含单体的第二溶液；
(3) 将第一溶液与第二溶液混合， 使单体聚合得到导电聚合物水凝胶；
其中， 步骤 （1 ) 和 （2) 中， 第一溶液为水溶液， 第二溶液为水溶液或有机溶液， 多元 酸配制在第一溶液和 /或第二溶液中。
纯化所得到的导电聚合物水凝胶后干燥可以得到多孔纳米结构导电聚合物。
一种电活性电极， 表面覆盖上述合成方法所得的导电聚合物。
所述电活性电极的制备方法具体地可以包括以下步骤：
(I) 配制包含氧化剂的第一溶液；
(II) 配制包含单体的第二溶液；
(III) 将第一溶液与第二溶液混合；
(IV) 使用旋涂、 蘸涂、 浇铸、 喷墨打印或丝网印刷的方法， 在电极载体表面覆盖步骤 (III) 中得到的混合溶液， 反应生成导电聚合物水凝胶电极结构；
其中， 步骤 （ I ) 和 （Π ) 中， 第一溶液为水溶液， 第二溶液为水溶液或有机溶液， 多 元酸配制在第一溶液和 /或第二溶液中。
如图 . 1A， 单体， 如苯胺单体可以通过聚合在一起， 形成长链聚苯胺结构。 聚苯胺的胺 基可与酸基团 （掺杂酸， DA)相互作用形成掺杂态的聚苯胺盐， 如图. 1B所示。 聚吡咯和聚 噻吩分子均可进行类似的酸掺杂反应， 如图. 1C和图. 1所示。 当导电聚合物通过与多官能度 掺杂酸掺杂， 导电聚合物形成网状交联结构， 如图 2所示。 导电聚合物水凝胶冻干后， 其微 观结构为整块的珊瑚状纳米结构。根据图 .1B， 2, 3，通过一个简单的使用多官能度掺杂酸（官 能度 >3) 的化学方法可以大批量合成高质量均匀的聚苯胺水凝胶。
本发明所述导电聚合物制备方法简单， 且无需引入其他杂质， 可以在水溶液中快速高产 率形成水凝胶， 适合于批量生产。 另一方面， 导电聚合物水凝胶和单块纳米结构导电聚合物 材料可由浸涂、 旋涂前驱体的方法制备成匀质薄膜。 该水凝胶可以由喷墨打印前驱体的方法 微图形化。
导电聚合物水凝胶能形成均匀的单块珊瑚状纳米结构。 在聚合过程中， 所选择的多官能 度掺杂酸有效促进了凝胶化过程。 导电聚合物被多官能度掺杂酸掺杂， 同时同一多官能度掺 杂酸分子会与多条聚合物链发生相互作用， 因此导电聚合物被交联形成三维网络状结构。 多 元掺杂酸有利于使导电高分子的表面亲水， 使导电聚合物的三维网络状结构能保持住水分形 成凝胶。 当干燥凝胶时， 其水分占据的空间被挥发、 并且导电聚合物的分子链为刚性链使得 其三维网络结构不会坍塌， 最终使导电聚合物形成互相交连的珊瑚状多孔纳米结构。应指出， 所制备的水凝胶是纯的掺杂态导电聚合物组成， 而非形成复合材料， 因此导电聚合物的导电 性和电化学活性被保留。 在整个合成中， 没有使用金属离子， 这使得水凝胶有高的生物相容 性， 适用于生物传感器， 生物燃料电池， 生物电池， 微生物燃料电池， 微生物电解池， 人造 肌肉， 人造器官， 药物释放等领域的应用。
我们发现所合成的水凝胶具有由支状纤维结构构成的三维多孔纳米结构，如图 4A和 4B， 其中干燥后凝胶的 BET表面面积大于 30 m2 · g^ o 所制备的导电聚合物水凝胶具有高离子电 导率约 0.017~0.026 S * cm- 导电聚合物水凝胶的接触角小于 15°， 具备超亲水性。 导电聚合 物水凝胶具有良好的生物兼容性。 附图说明 图. 1A聚苯胺翠绿亚胺分子结构示意图。
图. 1B掺杂态的聚苯胺翠绿亚胺盐分子结构示意图。 DA指掺杂酸 （doping acid) 。 图. 1C酸掺杂聚吡咯盐分子结构示意图。
图. 1D 酸掺杂聚噻吩 （PED0T) 分子结构示意图。
图. 2为导电聚合物水凝胶形成机制示意图。 在多官能度掺杂酸的作用下， 导电聚合物链 被交联， 形成导电聚合物水凝胶。
图. 3导电聚合物水凝胶的一种合成流程图。
图. 4A冻干后的聚苯胺水凝胶扫描电镜图像。
图. 4B 冻干后的聚苯胺水凝胶放大的扫描电镜图像。
图. 5冻干后的聚吡咯水凝胶扫描电镜图像。
图. 6冻干后的聚噻吩水凝胶扫描电镜图像。
图. 7旋转涂布形成的聚苯胺水凝胶薄膜的扫描电镜图像。
图.8A植酸掺杂聚苯胺水凝胶上生长的牛骨髓干细胞的扫描电镜图像。
图.8B植酸掺杂聚苯胺水凝胶上生长的牛骨髓干细胞放大的扫描电镜图像。
图.9聚乙烯基磷酸掺杂聚吡咯水凝胶上生长的牛骨髓干细胞荧光显微镜图像。
图.10 植酸掺杂聚苯胺水凝胶葡萄糖氧化酶电极对葡萄糖的传感特性曲线。
具体实施方式 导电聚合物的合成方法如下: 步骤 1， 配置由水和氧化剂组成的溶液。 氧化剂最好是过硫酸铵， 但其他氧化剂也使用 如三氯化铁、氯化铜、硝酸银、过氧化氢、氯金酸和其他过硫酸盐衍生物，如 Na2S208和 K2S208。
步骤 2， 将单体和酸溶解在水或有机溶剂中构成单体溶液。 在实施例中为单体苯胺， 但 其他碳基的有机单体也可使用， 如吡咯、 噻吩和苯胺衍生物如氨基苯甲醚、 甲基苯胺、 乙基 苯胺、 邻烷氧基苯胺和 2,5-二烷氧基苯胺单体， 可分别用于合成聚吡咯， 聚噻吩， 聚甲氧基 苯胺， 聚甲基苯胺， 聚乙基苯胺、 聚烷氧基苯胺苯胺， 聚 2,5-二烷氧基苯胺等。 多元掺杂酸 效果最好为含有磷酸基团的植酸、 磷酸和聚乙烯基磷酸， 但多官能度的其他小分子酸 （官能 度 2，分子量 800，所述官能度是指每分子多元酸所含酸基团的数量)也可以使用，如 1,2,4,5- 苯四羧酸， N-磺酸丁基 -3-甲基咪唑硫酸氢盐、 N-磺酸丁基吡啶硫酸氢盐等。 反应可以进行单 相水溶液合成或界面聚合 （有机溶剂-水两相界面合成）。 在界面聚合反应中， 有机溶剂采用 四氯化碳 （CC14)， 但其他不与水互溶的有机溶剂也可使用， 如苯， 甲苯， 氯仿， 一氯甲烷， 二甲苯， 正己烷， 二***， 二氯甲烷和二硫化碳。 在实施方案中， 苯胺单体和植酸混合后能 溶解于水。
步骤 3， 将单体溶液放置在反应容器中。 容器的容量可根据实际需要可大可小， 采用大 型容器可实现聚合物水凝胶的大批量生产， 亦可在各种不同形状的容器中浇铸成不同形状的 水凝胶材料。
步骤 4， 将氧化剂溶液与单体溶液混合。
步骤 5， 静置 （从数分钟到数天）， 在几分钟内在水相中形成聚苯胺的水凝胶， 同时可观 察到水溶液颜色变成墨绿色。
步骤 6， 水凝胶的纯化。 将水凝胶材料在去离子水、 蒸馏水中渗析或离子交换除去多余 的离子。 最终得到植酸掺杂聚苯胺纯水凝胶。 在这一步中， 水凝胶也可以用氨水去掺杂， 除 去植酸， 去掺杂不会破坏水凝胶结构， 因为多孔聚苯胺骨干已经可以保留其形状。 是否形成 水凝胶，可以使用反转实验进行验证（引用文献： Metal- and Anion-Binding Supramolecular Gels, Chem. Rev. 2010, 110, 1960-2004。）， 即将容器倒扣， 含水的溶液不具备流动性即视为形成了 水凝胶。 本专利实施例反转实验中的 "溶液失去流动性"指将容器倒扣， 30分钟内未观察到 肉眼可明显分辨的溶液流动行为。
A实施例： 均相反应 实施例 1 : 植酸 （官能度 6， 含 6个磷酸根） 掺杂聚苯胺水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和植酸混合的单体水溶 液 25ml， 物质的量之比为过硫酸铵： 苯胺： 植酸 =3 : 6： 1。 然后将两溶液混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深绿色， 并且溶液失去流动 性。 最后， 在去离子水中渗析以纯化水凝胶除去离子、 低聚物等杂质得到含水量 72%的水凝 胶。 在这个反应中， 试剂的混合比例可以在一定范围内变化 （例如： 苯胺与植酸中包含的磷 酸基团的量的比在 1 : 12〜12： 1范围内都能形成凝胶； 过硫酸铵与苯胺单体的比例可在较大 范围内变化；在一定范围内变化试剂的浓度可获得含水量 35 %至 85 %的导电聚苯胺水凝胶）。 本实例中所得到的水凝胶接触角 <15°， 为超亲水性。 经化学阻抗谱测量， 水凝胶具有高的离 子电导率 0.025 S * cm- ^ 水凝胶经过冻干， 在扫描电子显微镜下观察为由枝状纤维构成的珊 瑚状整块多孔纳米材料（如附图 4所示）， 比表面积>30 !112 * §- 所生长的植酸掺杂聚苯胺水 凝胶具有很好的生物相容性， 如附图 5所示为水凝胶表面生长的牛骨髓干细胞。 凝胶冻干后 的粉末压成块状， 经标准四探针方法测试其电导率为 0.02 S · cm- 在 2000 RPM转速下， 旋 涂前驱体溶液， 可形成均匀的绿色透明导电的聚苯胺水凝胶薄膜。
实施例 2: 植酸掺杂聚苯胺水凝胶 （含水量 34% )
先配置含 0.286g的过硫酸铵氧化剂水溶液 1 ml，并配置苯胺（0.458 ml)和植酸 (0.921 ml) 混合的单体水溶液 （浓度可以由水凝胶的含水量反推得到）。 然后将两溶液混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深绿色， 并且溶液失去流动 性。 得到含水量 34%的水凝胶。 所得到的水凝胶的离子电导率为 0.030 S * cm- 实施例 3: 植酸掺杂聚苯胺水凝胶 （含水量 85% )
先配置含 0.286g的过硫酸铵氧化剂水溶液 2.5 ml， 并配置苯胺 （0.458 ml) 和植酸 (0.921 ml)混合的单体水溶液 6.5 ml。 然后将两溶液混合， 数分钟内， 聚合反应发生， 产生聚苯胺水 凝胶。可观察到该溶液的颜色变为深绿色， 并且溶液失去流动性。得到含水量 85%的水凝胶。 所得到的水凝胶的离子电导率为 0.017 S · cm- 实施例 4: 植酸掺杂聚苯胺水凝胶 （植酸中的磷酸根： 苯胺单体摩尔比 =1:12) 先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和植酸混合的单体水溶 液 25ml， 物质的量之比为过硫酸铵： 苯胺： 植酸 =18: 72： 1。 然后将两溶液混合， 24小时之 后， 缓慢形成聚苯胺水凝胶。 因为有助于交联结构形成的植酸含量减少， 快超出水凝胶形成 的临界条件范围， 所以所需时间增加。 可观察到该溶液的颜色变为土黄色 （聚苯胺掺杂度很 小的反映，与深绿色相比说明聚苯胺由于过少的植酸量而非充分掺杂），并且溶液失去流动性。
实施例 5: 植酸掺杂聚苯胺水凝胶 （苯胺单体： 植酸中的磷酸根摩尔比 =1:12) 先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和植酸混合的单体水溶 液 25ml， 物质的量之比为过硫酸铵： 苯胺： 植酸 =1 : 2： 4。 然后将两溶液混合， 12小时之 后， 形成聚苯胺水凝胶。 由于植酸的量超过了聚苯胺掺杂所需的量， 并且溶液中多余的未与 苯胺反应的自由植酸分子会阻碍凝胶的形成， 因此所需时间较长。 可观察到该溶液的颜色变 为深绿色， 并且溶液失去流动性。
实施例 6: 1,2,4,5-苯四羧酸 （官能度 4， 含 4个羧酸根） 掺杂聚苯胺水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和 1,2,4,5-苯四羧酸混合 的单体水溶液 25ml， 物质的量之比为过硫酸铵： 苯胺： 1,2,4,5-苯四羧酸 =2: 4： 1。 然后将两 溶液混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深绿 色， 并且溶液失去流动性成为果冻状。 最后， 在去离子水中渗析以纯化水凝胶除去离子、 低 聚物等杂质得到水凝胶。 凝胶冻干后的粉末压成块状， 经标准四探针方法测试其电导率为 0.0026 S - cm 1 羧酸的酸性较弱， 因此掺杂的聚苯胺的电导率较低。
实施例 7: 磷酸 （包含 3个 H+) 掺杂聚苯胺水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和磷酸混合的单体水溶 25ml, 物质的量之比为过硫酸铵： 苯胺： 磷酸 =1 : 2： 2。 然后将两溶液混合， 数分钟内， 聚 合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深绿色， 并且溶液失去流动性。 最后， 在去离子水中渗析以纯化水凝胶除去离子、 低聚物等杂质得到水凝胶。 凝胶冻干后的 粉末压成块状， 经标准四探针方法测试其电导率为 0.031 S · cm- 实施例 8: N-磺酸丁基 -3-甲基咪唑硫酸氢盐 （官能度 2， 分子两端分别含 1个磺酸根和 1个硫酸氢离子） 掺杂聚苯胺水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和 N-磺酸丁基 -3-甲基咪 唑硫酸氢盐混合的单体水溶液 25ml， 物质的量之比为过硫酸铵： 苯胺： N-磺酸丁基 -3-甲基咪 唑硫酸氢盐 =1 : 2： 1。 然后将两溶液混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深绿色， 并且溶液失去流动性成为果冻状。 最后， 在去离子水中 渗析以纯化水凝胶除去离子、低聚物等杂质得到水凝胶。所得到凝胶冻干后的粉末压成块状， 经标准四探针方法测试其电导率为 0.13 S · cm- 实施例 9: 聚乙烯基磷酸掺杂聚苯胺水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置苯胺和聚乙烯基磷酸混合的 单体水溶液 25ml， 物质的量之比为过硫酸铵： 苯胺： 聚乙烯基磷酸中的磷酸基团量 =1 : 2： 2。 然后将两溶液混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色 变为深绿色， 并且溶液失去流动性形成凝胶。 最后， 在去离子水中渗析以纯化水凝胶除去离 子、 低聚物等杂质得到聚乙烯基磷酸掺杂聚苯胺的水凝胶。 凝胶冻干后的粉末压成块状， 经 标准四探针方法测试其电导率为 0.018 S · cm- 实施例 10: 植酸 （官能度 6， 含 6个磷酸根） 掺杂聚吡咯水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml， 并配置吡咯、 乙二醇和植酸混合的 单体水溶液 25ml (添加剂乙二醇的目的为增加吡咯溶解度， 乙二醇用量为： 与水体积比 1 : 10)， 物质的量之比为过硫酸铵： 吡咯： 植酸 =3: 6： 1。 然后将两溶液混合， 聚合反应发生， 迅速产生聚吡咯水凝胶。 可观察到该溶液的颜色变为黑色， 并且溶液失去流动性。 最后， 在 去离子水中渗析以纯化水凝胶除去离子、 低聚物、 乙二醇等杂质得到聚吡咯水凝胶。 所得到 凝胶冻干后的粉末压成块状， 经标准四探针方法测试其电导率为 4.3 S · cm- 实施例 11 : 植酸掺杂聚 2-(2-羟乙基)噻吩水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置 2-(2-羟乙基)噻吩和植酸混合 的单体水溶液， 物质的量之比为过硫酸铵： 2-(2-羟乙基)噻吩： 植酸 =3 : 6： 1。 然后将两溶液 混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深蓝色， 并且溶液失去流动性形成凝胶。 最后， 在去离子水中渗析以纯化水凝胶除去离子、 低聚物等 杂质得到聚 2-(2-羟乙基)噻吩的水凝胶。所得到凝胶冻干后的粉末压成块状，经标准四探针方 法测试其电导率为 5.6 S · cm- 实施例 12: 磷酸掺杂聚 2-(2-羟乙基)噻吩水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 并配置 2-(2-羟乙基)噻吩和植酸混合 的单体水溶液， 物质的量之比为过硫酸铵： 2-(2-羟乙基)噻吩： 磷酸 =1 : 2： 2。 然后将两溶液 混合， 数分钟内， 聚合反应发生， 产生聚苯胺水凝胶。 可观察到该溶液的颜色变为深蓝色， 并且溶液失去流动性形成凝胶。 最后， 在去离子水中渗析以纯化水凝胶除去离子、 低聚物等 杂质得到聚 2-(2-羟乙基)噻吩的水凝胶。凝胶冻干后的粉末压成块状，经标准四探针方法测试 其电导率为 6.2 S · cm-
B实施例： 界面反应 实施例 1 : 界面反应生成植酸掺杂聚苯胺水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 添加植酸。 并配置苯胺和四氯化碳 混合的单体有机溶液 25 ml。 物质的量之比为过硫酸铵： 苯胺： 植酸 =3: 6： 1。 将单体有机溶 液放置容器中， 再缓慢倒入氧化剂水溶液形成分离的水-四氯化碳两相溶液。 在数分钟内， 聚 合反应在水溶液和有机溶液的界面处发生。 在水相中形成聚苯胺的水凝胶。 可观察到水相溶 液转为暗绿色， 并失去流动性形成凝胶。 最后， 去除有机相溶液， 将水凝胶在去离子水中渗 析以纯化水凝胶除去离子、 低聚物等杂质。 凝胶冻干后的粉末压成块状， 经标准四探针方法 测试其电导率为 0.018 S · cm- 实施例 2: 界面反应生成植酸掺杂聚吡咯水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 添加植酸。 并配置吡咯和四氯化碳 混合的单体有机溶液 25 ml。 物质的量之比为过硫酸铵： 吡咯： 植酸 =3: 6： 1。 将单体有机溶 液放置容器中， 再缓慢倒入氧化剂水溶液形成分离的水-四氯化碳两相溶液。 在倒入同时， 聚 合反应在水溶液和有机溶液的界面处迅速发生。 在水相中形成聚吡咯的水凝胶。 可观察到水 相溶液迅速转为黑色， 并失去流动性形成凝胶。 最后， 去除有机相溶液， 将水凝胶在去离子 水中渗析以纯化水凝胶除去离子、 低聚物等杂质。 凝胶冻干后的粉末压成块状， 经标准四探 针方法测试其电导率为 1.8 S · cm- 实施例 3: 界面反应生成磷酸掺杂聚吡咯水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 添加磷酸。 并配置吡咯和四氯化碳 混合的单体有机溶液 25 ml。 物质的量之比为过硫酸铵： 吡咯： 磷酸 =1 : 2： 2。 将单体有机溶 液放置容器中， 再缓慢倒入氧化剂水溶液形成分离的水-四氯化碳两相溶液。 在倒入同时， 聚 合反应在水溶液和有机溶液的界面处迅速发生。 在水相中形成聚吡咯的水凝胶。 可观察到水 相溶液迅速转为黑色， 并失去流动性。 反应结束后， 倒掉有机相溶液， 将水凝胶在去离子水 中渗析以纯化水凝胶。 凝胶冻干后的粉末压成块状， 经标准四探针方法测试其电导率为 2.1 S · cm— 实施例 4: 界面反应生成聚乙烯基磷酸掺杂聚吡咯水凝胶
先配置浓度为 2 M的过硫酸铵氧化剂水溶液 20 ml, 添加聚乙烯基磷酸。 并配置吡咯和 四氯化碳混合的单体有机溶液 25 ml。物质的量之比为过硫酸铵： 苯胺： 聚乙烯基磷酸中的磷 酸基团量 =1 : 2： 2。 将单体有机溶液放置容器中， 再缓慢倒入氧化剂水溶液形成分离的水- 四氯化碳两相溶液。 在若干秒内， 聚合反应在水溶液和有机溶液的界面处发生。 在水相中形 成聚吡咯的水凝胶。 可观察到水相溶液迅速转为黑色， 并失去流动性。 反应结束后， 倒掉有 机相溶液， 将水凝胶在去离子水和乙醇中渗析以纯化水凝胶。 凝胶冻干后的粉末压成块状， 经标准四探针方法测试其电导率为 2.5 S * cm- 所获得的水凝胶有很好的生物相容性， 见图 7为聚乙烯基磷酸掺杂聚吡咯水凝胶上生长的牛骨髓干细胞的荧光显微镜图像。 总之， 本发明提供了一个形成纯导电聚合物水凝胶的方法（非复合材料）， 水凝胶的主体 为整块的珊瑚状导电聚合物纳米结构。 导电聚合物水凝胶和整块多孔纳米结构的合成易于量 产， 可在室温下进行， 合成过程不产生污染非常绿色。 由于所合成的导电聚合物水凝胶具有 纯导电聚合物直接形成水凝胶主体材料、 高离子导电性、 超亲水性、 生物相容性高的优点， 本专利发明的方法和材料可广泛应用于基于导电聚合物水凝胶及其纳米结构的器件， 如生物 传感器、 化学传感器、 晶体管、 存储器、 超级电容器、 锂电池、 燃料电池、 生物燃料电池、 人造肌肉、 人造器官、 药物释放、 电磁屏蔽、 防腐饰涂层等。 该方法通过使用多元掺杂酸掺 杂并交联导电聚合物分子链， 将溶液中的导电聚合物交联成一个整体， 形成整块的珊瑚状纳 米结构。该反应可采用水溶液均相反应或水 -有机溶剂两相界面反应两种方案进行。选择各种 单体， 溶剂， 氧化剂和多元掺杂酸可以获得不同的导电聚合物水凝胶。
C实施例： 植酸掺杂聚苯胺水凝胶葡萄糖氧化酶电极
按 A实施例 1中的配方， 混合得到前驱体溶液滴在铂电极表面， 形成水凝胶后与去离子 水交换去除杂质离子， 烘干后滴加葡萄糖氧化酶， 将该电极与甘汞电极等构成 3电极体系。 往溶液中递加葡萄糖水溶液， 每滴加一次形成 1 mmol/L的葡萄糖增量。可以由图 10中看出， 水凝胶酶电极对葡萄糖的传感非常敏感， 响应时间为 6s， 而通常的聚苯胺制备的酶电极通常 在若干分钟量级。

Claims

权利要求书
1. 一种导电聚合物的合成方法， 其特征在于， 以多元酸作为掺杂剂和交联剂， 使单体 聚合得到导电聚合物水凝胶， 所述单体为吡咯或其衍生物、 噻吩或其衍生物、 苯胺或其衍生 物中的至少一种， 所述多元酸的酸基团包含磷酸基、 或者多元酸为每分子含 2个以上选自磺 酸基、 硝酸基或羧酸基中至少一种的酸基团的分子量 800的多元酸。
2. 如权利要求 1 所述的导电聚合物的合成方法， 其特征在于多元酸所包含的酸基团的 摩尔数与导电聚合物单体的摩尔比为 1 : 12-12： 1， 优选为 2:1~1:2。
3. 如权利要求 1或 2所述的导电聚合物的合成方法， 其特征在于所述多元酸为植酸、 磷酸、聚乙烯基磷酸、 N-磺酸丁基 -3-甲基咪唑硫酸氢盐、 N-磺酸丁基吡啶硫酸氢盐或 1,2,4,5- 苯四羧酸中的至少一种。
4. 如权利要求 3所述的导电聚合物的合成方法， 其特征在于所述多元酸为植酸。
5. 如权利要求 1-4中任一项所述的导电聚合物的合成方法，其特征在于所述导电聚合物 水凝胶的含水量为 30%-85%， 优选为 34%-85%。
6. 如权利要求 1-4中任一项所述的导电聚合物的合成方法，其特征在于单体在氧化剂作 用下， 经化学氧化聚合得到导电聚合物水凝胶。
7. 如权利要求 6所述的导电聚合物的合成方法， 其特征在于氧化剂为过硫酸盐、 氯化 铁、 氯化铜、 硝酸银、 过氧化氢、 氯金酸或硝酸铈铵中的至少一种。
8. 如权利要求 6或 7所述的导电聚合物的合成方法， 其特征在于包括以下步骤：
( 1 ) 配制包含氧化剂的第一溶液；
(2) 配制包含单体的第二溶液；
(3) 将第一溶液与第二溶液混合， 使单体聚合得到导电聚合物水凝胶；
其中， 步骤 （1 ) 和 （2) 中， 第一溶液为水溶液， 第二溶液为水溶液或有机溶液， 多元 酸配制在第一溶液和 /或第二溶液中。
9. 如权利要求 1-8 中任一项所述的导电聚合物的合成方法， 其特征在于还包括以下步 骤： 纯化所得到的导电聚合物水凝胶后干燥得到多孔纳米结构导电聚合物。
10. 权利要求 1-9中任一项所述合成方法所得的导电聚合物。
11. 一种电活性电极， 表面覆盖权利要求 1-9中任一项所述合成方法所得的导电聚合物。
12. 权利要求 11所述的电活性电极的制备方法， 包括以下步骤：
(I) 配制包含氧化剂的第一溶液；
(II) 配制包含单体的第二溶液； (in) 将第一溶液与第二溶液混合；
(IV) 使用旋涂、 蘸涂、 浇铸、 喷墨打印或丝网印刷的方法， 在电极载体表面覆盖步 骤 （III) 中得到的混合溶液， 反应生成导电聚合物水凝胶电极结构；
其中， 步骤 （ I ) 和 （Π ) 中， 第一溶液为水溶液， 第二溶液为水溶液或有机溶液， 多 元酸配制在第一溶液和 /或第二溶液中。
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