CN102206342A - Electric conduction polymer and synthesis method thereof and electroactive electrode with surface covered with electric conduction polymer - Google Patents
Electric conduction polymer and synthesis method thereof and electroactive electrode with surface covered with electric conduction polymer Download PDFInfo
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Abstract
本发明涉及导电聚合物、其合成方法及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。电活性电极表面覆盖上述合成方法所得的导电聚合物。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。所制备的导电聚合物水凝胶具有高离子电导率，具备超亲水性和良好的生物兼容性。
The present invention relates to conducting polymers, methods of their synthesis and electroactive electrodes whose surfaces are covered with said conducting polymers. The synthesis method of the conductive polymer is as follows: polyacid is used as a dopant and a crosslinking agent to polymerize monomers to obtain a conductive polymer hydrogel, and the monomers are pyrrole or its derivatives, thiophene or its derivatives , aniline or its derivatives, the acid group of the polybasic acid contains phosphoric acid group, or the polybasic acid contains at least 2 or more selected from sulfonic acid group, nitric acid group or carboxylic acid group in each molecule A polyacid with a molecular weight of the acid group ≤ 800. The molar ratio of the molar number of acid groups contained in the polybasic acid to the conductive polymer monomer is preferably 1:12˜12:1. The surface of the electroactive electrode is covered with the conductive polymer obtained by the above synthesis method. The preparation method of the conductive polymer described in the invention is simple and does not need to introduce other impurities. The prepared conductive polymer hydrogel has high ionic conductivity, superhydrophilicity and good biocompatibility.
Description
Technical field
The present invention relates to a kind of conductive polymers and synthetic method thereof, surface coverage has the electroactive electrode of described conductive polymers.
Background technology
From MacDiarmid, Hideki Shirakawa, with Heeger invention conductive polymers and to these polymkeric substance mix realize regulating and control to the performance in all directions of metallic state by isolator after, started the frontier that a chemistry and Condensed Matter Physics intersect, at photoelectron, electronics and electrochemical field have produced a large amount of application prospects.Therefore conductive polymers has stable physics and chemical property, and high conductivity, and the dual current carrier conductive mechanism of electron-ion are widely used as the electrode materials of devices such as the relevant transmitter of electrochemistry, energy storage.In addition, the specific conductivity of conductive polymers is relevant with variablees such as redox state, potential of hydrogen, is widely used in intelligent material such as transmitter etc.In recent decades, because underlying cause, conductive polymers hydrogel be at biosensor, chemical sensor, bioelectrode, biofuel cell, microbiological fuel cell, microorganism electrolysis cell, medical-treatment electrode, artificial muscle, artificial organ, fields such as drug release and biofuel cell receive more and more the concern:
1) the conductive polymers hydrogel has nanometer skeleton construction and enough big solid-liquid contacts area, possesses enhanced electron specific conductivity, ion and molecular diffusion effect, helps transporting of electronics in the device;
2) the conductive polymers hydrogel is compared with traditional metal electrode, possesses the feature and advantage of soft material;
3) the conductive polymers hydrogel has biocompatibility, compares with other all materials near biological tissue's environment.
Up to now, have only the limited several method can the compositing conducting polyalcohol hydrogel, be difficult to satisfy because form two prerequisites of hydrogel: the 1) wetting ability of polymkeric substance; 2) polymkeric substance interchain chemistry or physical crosslinking.
At present, the conductive polymers hydrogel can be synthetic by following method:
1) compositing conducting polymkeric substance (promptly having formed the matrix material of non-conductive hydrogel and conductive polymers) in non-conductive polymer based aquagel template;
2) interact by iron or magnesium ion and electronegative polyelectrolyte doping agent and form the water-soluble conducting polymer gel of ionomer;
3) by the amino generation crosslinking reaction of epoxide group and polyaniline, crosslinked polyaniline forms gel.
Yet above-mentioned all methods have all been introduced impurity or non-functional material without exception, as metal ion or non-functional polymkeric substance.The shortcoming of these methods is, specific conductivity, electrochemical activity or the biocompatibility of conductive polymers have been reduced, detailed analysis is as follows: 1) by conductive polymers and ortho-water gelatinous material such as polyvinyl alcohol, polyoxyethylene glycol, chitosan, polyacrylamide, poly 2-hydroxyethyl methacrylate methyl esters, polyacrylic acid, formation matrix materials such as sodium alginate hydrogel can synthesize the hydrogel of biocompatibility.Reduce conductivity of electrolyte materials and electrochemical activity undoubtedly yet the nand function hydrogel material is compound, thereby reduced the performance of electrode and transmitter; 2) adulterated negative charge polyelectrolyte and metal ion on the conductive polymers are interacted and crosslinked method has been introduced a large amount of impurity metal ions, reduced the activity of biocompatibility and enzyme; 3) for carrying out the electroconductibility that crosslinked method greatly reduces conductive polymers by amino on the polyaniline main chain and epoxide group.In a word, existing synthetic method can not satisfy conductive polymers in biomedical engineering, biofuel cell, the application demand in fields such as microbiological fuel cell.
Summary of the invention
The invention provides a kind of synthetic method of conductive polymers, the preparation method is simple, and need not to introduce other impurity.
The conductive polymers that the present invention also provides above-mentioned synthetic method to obtain.
The present invention also provides surface coverage that the electroactive electrode of described conductive polymers is arranged.
The synthetic method of described conductive polymers is, with polyprotonic acid as doping agent and linking agent, make monomer polymerization obtain the conductive polymers hydrogel, described monomer is at least a in pyrroles's or derivatives thereof, thiophene or derivatives thereof, the aniline or derivatives thereof, and the acid groups of described polyprotonic acid comprises phosphate or polyprotonic acid is the polyprotonic acid that per molecule contains molecular weight≤800 that are selected from acid groups at least a among sulfonic group, nitroxyl or the carboxylic acid group more than 2.
The monomeric mol ratio of the mole number of the acid groups that described polyprotonic acid comprised and conductive polymers is preferably 1: 12～and 12: 1, more preferably 2: 1～1: 2.
Preferred polyprotonic acid is phytic acid, phosphoric acid, polyvinyl phosphoric acid, N-sulfonic acid butyl-3-Methylimidazole hydrosulfate, N-sulfonic acid butyl-pyridinium hydrosulfate or 1,2,4, at least a among the 5-benzene tertacarbonic acid, wherein the phytic acid structural formula is suc as formula shown in the i, and 1,2,4,5-benzene tertacarbonic acid structural formula is suc as formula shown in the ii.More preferably described polyprotonic acid is a phytic acid.
Monomer obtains the conductive polymers hydrogel through conventional polymerization process, under the oxygenant effect, obtains conductive polymers hydrogel through chemical oxidising polymerisation as monomer.Oxygenant is at least a in persulphate, iron(ic) chloride, cupric chloride, Silver Nitrate, hydrogen peroxide, hydrochloro-auric acid or the ceric ammonium nitrate.
The water content of described conductive polymers hydrogel is 30%-85%, is preferably 34%-85%.
The synthetic method of described conductive polymers can may further comprise the steps particularly:
(1) preparation comprises first solution of oxygenant;
(2) preparation comprises monomeric second solution;
(3) first solution is mixed with second solution, make monomer polymerization obtain the conductive polymers hydrogel;
Wherein, in step (1) and (2), first solution is the aqueous solution, and second solution is the aqueous solution or organic solution, and polyprotonic acid is formulated in first solution and/or second solution.
The resulting conductive polymers hydrogel of purifying after drying can obtain the porous nanometer structure conductive polymers.
A kind of electroactive electrode, the conductive polymers of the above-mentioned synthetic method gained of surface coverage.
The preparation method of described electroactive electrode can may further comprise the steps particularly:
(I) preparation comprises first solution of oxygenant;
(II) preparation comprises monomeric second solution;
(III) first solution is mixed with second solution;
The method of (IV) use spin coating, dipping, casting, spray ink Printing or silk screen printing, the mixing solutions that in electrode holder surface coverage step (III), obtains, reaction generates conductive polymers hydrogel electrode structure;
Wherein, step (I) and (II) in, first solution is the aqueous solution, second solution is the aqueous solution or organic solution, polyprotonic acid is formulated in first solution and/or second solution.
As scheme .1A, monomer can form the long-chain polyaniline structure by condensing together as aniline monomer.The amido of polyaniline can (dopant acid, DA) interaction forms the polyaniline salt of doping attitude, shown in figure .1B with acid groups.Polypyrrole and Polythiophene molecule all can carry out similarly acid doping reaction, shown in figure .1C and figure .1.When conductive polymers by mixing with the polyfunctionality dopant acid, conductive polymers forms cross-linked network, as shown in Figure 2.After the freeze-drying of conductive polymers hydrogel, its microtexture is the coralloid nano structure of monoblock.According to figure .1B, 2,3, can synthesize the uniform polyaniline hydrogel of high quality in enormous quantities by a simple chemical process of polyfunctionality dopant acid (functionality＞3) of using.
Conductive polymers preparation method of the present invention is simple, and need not to introduce other impurity, can the high-yield quick rate form hydrogel in the aqueous solution, is suitable for producing in batches.On the other hand, conductive polymers hydrogel and monolithic nano structural conductive polymer materials can be prepared into even matter film by the method for dip-coating, spin coating presoma.This hydrogel can be by the method micrographicsization of spray ink Printing presoma.
The conductive polymers hydrogel can form uniform monolithic coralloid nano structure.In polymerization process, selected polyfunctionality dopant acid has effectively promoted gelation process.Conductive polymers is mixed by the polyfunctionality dopant acid, and same polyfunctionality dopant acid molecule can interact with many polymer chains simultaneously, so conductive polymers is cross-linked to form three-dimensional network-like structure.Multi-element doping acid helps making the surface hydrophilic of conducting polymer, makes the three-dimensional network-like structure of conductive polymers can maintain moisture formation gel.When desiccant gel, volatilized and molecular chain conductive polymers in the space that its moisture occupies is that stiff chain makes its three-dimensional net structure can not cave in, and finally makes conductive polymers form the coralliform porous nanometer structure of mutual commissure.Should point out that prepared hydrogel is that pure doping attitude conductive polymers is formed, but not forms matrix material, so the electroconductibility of conductive polymers and electrochemical activity are retained.In whole synthesizing, do not use metal ion, this makes hydrogel that high biocompatibility be arranged, and is applicable to biosensor, biofuel cell, biofuel cell, microbiological fuel cell, microorganism electrolysis cell, artificial muscle, artificial organ, the application in fields such as drug release.
We find that institute's synthetic hydrogel has the three-dimensional porous nano structure that is made of a shape fibrous texture, and as Fig. 4 A and 4B, the BET surface area of wherein dry back gel is greater than 30m
2G
-1Prepared conductive polymers hydrogel has the about 0.017～0.026Scm of high ionic conductivity
-1The contact angle of conductive polymers hydrogel possesses Superhydrophilic less than 15 °.The conductive polymers hydrogel has good bio-compatibility.
Description of drawings
Figure .1A polyaniline emeraldine schematic arrangement.
The polyaniline emeraldine salt schematic arrangement of figure .1B doping attitude.DA refers to dopant acid (doping acid).
Figure .1C acid doping polypyrrole molecules of salt structural representation.
Figure .1D acid doping Polythiophene (PEDOT) schematic arrangement.
Figure .2 forms schematic diagram of mechanism for the conductive polymers hydrogel.Under the effect of polyfunctionality dopant acid, the conductive polymers chain is crosslinked, and forms the conductive polymers hydrogel.
A kind of synthetic schemes of figure .3 conductive polymers hydrogel.
Polyaniline hydrogel scanning electron microscope image after the figure .4A freeze-drying.
The scanning electron microscope image that polyaniline hydrogel after the figure .4B freeze-drying amplifies.
Polypyrrole hydrogel scanning electron microscope image after the figure .5 freeze-drying.
Polythiophene hydrogel scanning electron microscope image after the figure .6 freeze-drying.
The scanning electron microscope image of the polyaniline hydrogel thin film that figure .7 rotary coating forms.
The scanning electron microscope image of the Medulla Bovis seu Bubali stem cell that grows on the figure .8A phytic acid doped polyaniline hydrogel.
The scanning electron microscope image that the Medulla Bovis seu Bubali stem cell that grows on the figure .8B phytic acid doped polyaniline hydrogel is amplified.
The Medulla Bovis seu Bubali stem cell fluorescence microscopy images of growing on the phosphate-doped polypyrrole hydrogel of figure .9 polyvinyl.
Figure .10 phytic acid doped polyaniline hydrogel glucose oxidase electrode is to the sensing characteristics curve of glucose.
Embodiment
The synthetic method of conductive polymers is as follows:
Step 1, the solution that configuration is made up of water and oxygenant.Oxygenant is ammonium persulphate preferably, but other oxygenants also use as iron trichloride, cupric chloride, Silver Nitrate, hydrogen peroxide, hydrochloro-auric acid and other persulphate derivatives, as Na
2S
2O
8And K
2S
2O
8
Step 2 is dissolved in monomer and acid in water or the organic solvent and constitutes monomer solution.Be monomer aniline in an embodiment, but the organic monomer of other carbon backs also can use, as pyrroles, thiophene and anils such as anisidine, monomethylaniline, ethylaniline, o-alkoxyl aniline and 2,5-dialkoxy aniline monomer can be respectively applied for synthetic polypyrrole, Polythiophene, polymethoxy aniline, polyphenylmethyl amine, polyphenylethyl amine, poly-alkoxyl aniline aniline, gather 2,5-dialkoxy aniline etc.Multi-element doping acid effect is preferably phytic acid, phosphoric acid and the polyvinyl phosphoric acid that contains phosphate group, but other small molecules acid (functionality 〉=2 of polyfunctionality, molecular weight≤800, described functionality is meant the quantity of the contained acid groups of per molecule polyprotonic acid) also can use, as 1,2,4, the 5-benzene tertacarbonic acid, N-sulfonic acid butyl-3-Methylimidazole hydrosulfate, N-sulfonic acid butyl-pyridinium hydrosulfate etc.Reaction can be carried out the synthetic or interfacial polymerization (organic solvent-water two-phase interface is synthetic) of single-phase water solution.In interface polymerization reaction, organic solvent adopts tetracol phenixin (CCl
4), but other can not use with the organic solvent that water dissolves each other yet, as benzene, and toluene, chloroform, monochloro methane, dimethylbenzene, normal hexane, diethyl ether, methylene dichloride and dithiocarbonic anhydride.In embodiments, aniline monomer and phytic acid can be dissolved in water after mixing.
Step 3 is placed on monomer solution in the reaction vessel.The capacity of container can be changeable according to actual needs, adopts tun can realize the production in enormous quantities of polyalcohol hydrogel, also can be cast into difform hydrogel material in various difform containers.
Step 4 is mixed oxidizing agent solution with monomer solution.
Step 5 leaves standstill (from several minutes to a couple of days), forms the hydrogel of polyaniline in several minutes at aqueous phase, can be observed aqueous solution color simultaneously and becomes blackish green.
Step 6, the purifying of hydrogel.Unnecessary ion is removed in hydrogel material dialysis or ion-exchange in deionized water, distilled water.Finally obtain phytic acid doped polyaniline pure water gel.In this step, hydrogel also can go to mix with ammoniacal liquor, removes phytic acid, goes to mix and can not destroy hydrogel structure, because porous polyaniline backbone can keep its shape.Whether form hydrogel, can use counter-rotating to verify (citing document: Metal-and Anion-Binding Supramolecular Gels, Chem.Rev.2010,110,1960-2004.), being about to the container back-off, aqueous solution does not possess flowability and promptly is considered as having formed hydrogel." solution loses flowability " that this patent embodiment reverses in testing refers to the container back-off, do not observe the flow of solution behavior that naked eyes can obviously be differentiated in 30 minutes.
A embodiment: homogeneous reaction
Embodiment 1: phytic acid (functionality 6 contains 6 phosphate radicals) doped polyaniline hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and phytic acid blended monomer solution 25ml, and the ratio of amount of substance is an ammonium persulphate: aniline: phytic acid=3: 6: 1.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and solution loses flowability.At last, dialysis obtains the hydrogel of water content 72% with impurity such as purified water gel deionizing, oligopolymer in deionized water.In this reaction, the blending ratio of reagent can change within the specific limits that (for example: the ratio of the amount of the phosphate group that comprises in aniline and the phytic acid can both form gel at 1: 12～12: 1 in the scope; The ratio of ammonium persulphate and aniline monomer can change in a big way; The concentration that changes reagent within the specific limits can obtain the electrically conductive polyaniline hydrogel of water content 35% to 85%).Resulting hydrogel contact angle in this example＜15 ° is Superhydrophilic.Through the chemical impedance spectrometry, hydrogel has high ionic conductivity 0.025Scm
-1Hydrogel is viewed as the coralliform monoblock porous nanometer material (as shown in Figure 4) that is made of dendritic fiber, specific surface area＞30m through freeze-drying under scanning electronic microscope
2G
-1The phytic acid doped polyaniline hydrogel of being grown has good biocompatibility, as shown in Figure 5 the Medulla Bovis seu Bubali stem cell that grows for hydrogel surface.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 0.02Scm
-1Under the 2000RPM rotating speed, the spin coating precursor solution can form the polyaniline hydrogel thin film that uniform green transparent is conducted electricity.
Embodiment 2: phytic acid doped polyaniline hydrogel (water content 34%)
Configuration earlier contains the ammonium persulphate aqueous oxidizing agent solution 1ml of 0.286g, and configuration aniline (0.458ml) and phytic acid (0.921ml) blended monomer solution (concentration can be obtained by counter the pushing away of the water content of hydrogel).Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and solution loses flowability.Obtain the hydrogel of water content 34%.The ionic conductivity of resulting hydrogel is 0.030Scm
-1
Embodiment 3: phytic acid doped polyaniline hydrogel (water content 85%)
Configuration earlier contains the ammonium persulphate aqueous oxidizing agent solution 2.5ml of 0.286g, and configuration aniline (0.458ml) and phytic acid (0.921ml) blended monomer solution 6.5ml.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and solution loses flowability.Obtain the hydrogel of water content 85%.The ionic conductivity of resulting hydrogel is 0.017Scm
-1
Embodiment 4: the phytic acid doped polyaniline hydrogel (phosphate radical in the phytic acid: aniline monomer mol ratio=1: 12)
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and phytic acid blended monomer solution 25ml, and the ratio of amount of substance is an ammonium persulphate: aniline: phytic acid=18: 72: 1.Then two solution are mixed, after 24 hours, slowly form the polyaniline hydrogel.Because the phytic acid content that helps crosslinking structure to form reduces, exceed the critical condition scope that hydrogel forms soon, so required time increases.The color that can be observed this solution become khaki color (reflection that the Polyaniline Doped degree is very little, compare the explanation polyaniline with deep green because very few phytic acid amount but not fully mix), and solution loses flowability.
Embodiment 5: phytic acid doped polyaniline hydrogel (aniline monomer: the phosphate radical mol ratio in the phytic acid=1: 12)
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and phytic acid blended monomer solution 25ml, and the ratio of amount of substance is an ammonium persulphate: aniline: phytic acid=1: 2: 4.Then two solution are mixed, after 12 hours, form the polyaniline hydrogel.Because the amount of phytic acid has surpassed the required amount of Polyaniline Doped, and the unnecessary formation that can not hinder gel with the free phytic acid molecule of aniline reaction in the solution, so required time is longer.The color that can be observed this solution becomes deep green, and solution loses flowability.
Embodiment 6:1,2,4,5-benzene tertacarbonic acid (functionality 4 contains 4 carboxylate radicals) doped polyaniline hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and 1,2,4,5-benzene tertacarbonic acid blended monomer solution 25ml, and the ratio of amount of substance is an ammonium persulphate: aniline: 1,2,4,5-benzene tertacarbonic acid=2: 4: 1.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and solution loses flowability and becomes the jelly shape.At last, dialysis obtains hydrogel with impurity such as purified water gel deionizing, oligopolymer in deionized water.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 0.0026Scm
-1The acidity of carboxylic acid a little less than, therefore the specific conductivity of adulterated polyaniline is lower.
Embodiment 7: phosphoric acid (comprising 3 H+) doped polyaniline hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and the water-soluble 25ml of phosphoric acid blended monomer, and the ratio of amount of substance is an ammonium persulphate: aniline: phosphoric acid=1: 2: 2.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and solution loses flowability.At last, dialysis obtains hydrogel with impurity such as purified water gel deionizing, oligopolymer in deionized water.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 0.031Scm
-1
Embodiment 8:N-sulfonic acid butyl-3-Methylimidazole hydrosulfate (functionality 2, molecule two ends contain 1 sulfonate radical and 1 hydrogen sulfate ion respectively) doped polyaniline hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and N-sulfonic acid butyl-3-Methylimidazole hydrosulfate blended monomer solution 25ml, the ratio of amount of substance is an ammonium persulphate: aniline: N-sulfonic acid butyl-3-Methylimidazole hydrosulfate=1: 2: 1.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and solution loses flowability and becomes the jelly shape.At last, dialysis obtains hydrogel with impurity such as purified water gel deionizing, oligopolymer in deionized water.Powder after the resultant gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 0.13Scm
-1
Embodiment 9: the phosphate-doped polyaniline hydrogel of polyvinyl
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration aniline and polyvinyl phosphoric acid blended monomer solution 25ml, and the ratio of amount of substance is an ammonium persulphate: aniline: the phosphate group amount in the polyvinyl phosphoric acid=1: 2: 2.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes deep green, and the solution formation gel that loses flowability.At last, dialysis obtains the hydrogel of the phosphate-doped polyaniline of polyvinyl with impurity such as purified water gel deionizing, oligopolymer in deionized water.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 0.018Scm
-1
Embodiment 10: phytic acid (functionality 6 contains 6 phosphate radicals) doping polypyrrole hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and (purpose of additive ethylene glycol is for increasing pyrroles's solubleness to dispose pyrroles, ethylene glycol and phytic acid blended monomer solution 25ml, the ethylene glycol consumption was: with water volume ratio 1: 10), the ratio of amount of substance is an ammonium persulphate: the pyrroles: phytic acid=3: 6: 1.Then two solution are mixed, polyreaction takes place, and produces the polypyrrole hydrogel rapidly.The color that can be observed this solution becomes black, and solution loses flowability.At last, dialysis obtains the polypyrrole hydrogel with impurity such as purified water gel deionizing, oligopolymer, ethylene glycol in deionized water.Powder after the resultant gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 4.3Scm
-1
Embodiment 11: phytic acid mixes and gathers 2-(2-hydroxyethyl) thiophene hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration 2-(2-hydroxyethyl) thiophene and phytic acid blended monomer solution, and the ratio of amount of substance is ammonium persulphate: 2-(2-hydroxyethyl) thiophene: phytic acid=3: 6: 1.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes mazarine, and the solution formation gel that loses flowability.At last, dialysis obtains the hydrogel of poly-2-(2-hydroxyethyl) thiophene with impurity such as purified water gel deionizing, oligopolymer in deionized water.Powder after the resultant gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 5.6Scm
-1
Embodiment 12: phosphate-doped poly-2-(2-hydroxyethyl) thiophene hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, and configuration 2-(2-hydroxyethyl) thiophene and phytic acid blended monomer solution, and the ratio of amount of substance is ammonium persulphate: 2-(2-hydroxyethyl) thiophene: phosphoric acid=1: 2: 2.Then two solution are mixed, in several minutes, polyreaction takes place, and produces the polyaniline hydrogel.The color that can be observed this solution becomes mazarine, and the solution formation gel that loses flowability.At last, dialysis obtains the hydrogel of poly-2-(2-hydroxyethyl) thiophene with impurity such as purified water gel deionizing, oligopolymer in deionized water.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 6.2Scm
-1
B embodiment: surface reaction
Embodiment 1: surface reaction generates phytic acid doped polyaniline hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, adds phytic acid.And configuration aniline and tetracol phenixin blended monomer organic solution 25ml.The ratio of amount of substance is an ammonium persulphate: aniline: phytic acid=3: 6: 1.Monomer organic solution is placed in the container, slowly pour aqueous oxidizing agent solution again into and form isolating water-tetracol phenixin two phase liquid.In several minutes, polyreaction is in the generation at the interface of the aqueous solution and organic solution.Form the hydrogel of polyaniline at aqueous phase.Can be observed aqueous phase solution and transfer sap green to, and the formation gel that loses flowability.At last, remove organic phase solution, with hydrogel in deionized water dialysis with impurity such as purified water gel deionizing, oligopolymer.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 0.018Scm
-1
Embodiment 2: surface reaction generates phytic acid doping polypyrrole hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, adds phytic acid.And configuration pyrroles and tetracol phenixin blended monomer organic solution 25ml.The ratio of amount of substance is an ammonium persulphate: the pyrroles: phytic acid=3: 6: 1.Monomer organic solution is placed in the container, slowly pour aqueous oxidizing agent solution again into and form isolating water-tetracol phenixin two phase liquid.Pouring into simultaneously, polyreaction takes place rapidly at the interface the aqueous solution and organic solution.Form the hydrogel of polypyrrole at aqueous phase.Can be observed aqueous phase solution and transfer black rapidly to, and the formation gel that loses flowability.At last, remove organic phase solution, with hydrogel in deionized water dialysis with impurity such as purified water gel deionizing, oligopolymer.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 1.8Scm
-1
Embodiment 3: surface reaction generates phosphate-doped polypyrrole hydrogel
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, adds phosphoric acid.And configuration pyrroles and tetracol phenixin blended monomer organic solution 25ml.The ratio of amount of substance is an ammonium persulphate: the pyrroles: phosphoric acid=1: 2: 2.Monomer organic solution is placed in the container, slowly pour aqueous oxidizing agent solution again into and form isolating water-tetracol phenixin two phase liquid.Pouring into simultaneously, polyreaction takes place rapidly at the interface the aqueous solution and organic solution.Form the hydrogel of polypyrrole at aqueous phase.Can be observed aqueous phase solution and transfer black rapidly to, and lose flowability.After reaction finishes, outwell organic phase solution, with hydrogel in deionized water dialysis with the purified water gel.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 2.1Scm
-1
Embodiment 4: surface reaction generates the phosphate-doped polypyrrole hydrogel of polyvinyl
Elder generation's configuration concentration is the ammonium persulphate aqueous oxidizing agent solution 20ml of 2M, adds polyvinyl phosphoric acid.And configuration pyrroles and tetracol phenixin blended monomer organic solution 25ml.The ratio of amount of substance is an ammonium persulphate: aniline: the phosphate group amount in the polyvinyl phosphoric acid=1: 2: 2.Monomer organic solution is placed in the container, slowly pour aqueous oxidizing agent solution again into and form isolating water-tetracol phenixin two phase liquid.In some seconds, polyreaction is in the generation at the interface of the aqueous solution and organic solution.Form the hydrogel of polypyrrole at aqueous phase.Can be observed aqueous phase solution and transfer black rapidly to, and lose flowability.After reaction finishes, outwell organic phase solution, with hydrogel in deionized water and ethanol dialysis with the purified water gel.Powder after the gel freeze-drying is pressed into bulk, and testing its specific conductivity through standard four point probe method is 2.5Scm
-1The hydrogel that is obtained has good biocompatibility, sees that Fig. 7 is the fluorescence microscopy images of the Medulla Bovis seu Bubali stem cell that grows on the phosphate-doped polypyrrole hydrogel of polyvinyl.
In a word, the invention provides a method (non-matrix material) that forms pure conductive polymers hydrogel, the main body of hydrogel is the coralliform conductive polymer nanometer structure of monoblock.The synthetic volume production that is easy to of conductive polymers hydrogel and monoblock porous nanometer structure can at room temperature be carried out, and it is very green that building-up process does not produce pollution.Because having pure conductive polymers, institute's synthetic conductive polymers hydrogel directly forms hydrogel material of main part, macroion electroconductibility, Superhydrophilic, advantage that biocompatibility is high, the method of this patent invention and material can be widely used in the device based on conductive polymers hydrogel and nanostructure thereof, as biosensor, chemical sensor, transistor, storer, ultracapacitor, lithium cell, fuel cell, biofuel cell, artificial muscle, artificial organ, drug release, electromagnetic shielding, anticorrosion decorations coating etc.This method is mixed and the crosslinked conducting polymer molecular chain by using multi-element doping acid, and the conductive polymers in the solution is cross-linked into an integral body, forms the coralloid nano structure of monoblock.This reaction can adopt aqueous solution homogeneous reaction or water-two kinds of schemes of organic solvent two-phase interface reaction to carry out.Select various monomers, solvent, oxygenant can obtain different conductive polymers hydrogels with multi-element doping acid.
C embodiment: phytic acid doped polyaniline hydrogel glucose oxidase electrode
Press the prescription among the A embodiment 1, mixing obtains precursor solution and drops in platinum electrode surface, removes foreign ion with the deionized water exchange behind the formation hydrogel, and the dropping glucose oxidase constitutes 3 electrode systems with this electrode and mercurous chloride electrode etc. after the oven dry.The D/W that progressively increases in the solution, every dropping once forms the glucose increment of 1mmol/L.Can be by finding out among Figure 10, the hydrogel enzyme electrodes is very responsive to the sensing of glucose, and the time of response is 6s, and the enzyme electrodes of common polyaniline preparation is usually in the some minutes magnitude.
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