CN102206342B - 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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- CN102206342B CN102206342B CN201110079884A CN201110079884A CN102206342B CN 102206342 B CN102206342 B CN 102206342B CN 201110079884 A CN201110079884 A CN 201110079884A CN 201110079884 A CN201110079884 A CN 201110079884A CN 102206342 B CN102206342 B CN 102206342B
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Abstract
The invention relates to electric conduction polymer and a synthesis method thereof and an electroactive electrode with a surface covered with the electric conduction polymer. In the synthesis method for the electric conduction polymer, polybasic acid is used as a doping agent and a cross-linking agent, so that a monomer is polymerized to obtain electric conduction polymer hydrogel, wherein the monomer is at least one of pyrrole or a derivative of the pyrrole, thiophene or a derivative of the thiophene, phenylamine or a derivative of the phenylamine; and the acid group of the polybasic acid comprises a phosphate group or polybasic acid of which each molecule comprises more than two acid groups selected from at least one of a sulfonic acid group, nitroxyl or a carboxylic acid group and which has the molecular weight of less than or equal to 800. The molar ratio of the mole number of the acid group contained in the polybasic acid to the mole number of an electric conduction polymer monomer is preferably 1:12-12:1. The electric conduction polymer obtained by the synthesis method is covered by the surface of the electroactive electrode. The electric conduction polymer has a simple preparation method, and other impurities are not required to be led into the electric conduction polymer. The prepared electric conduction polymer hydrogel has high ionic conductivity, super hydrophilicity and high biological compatibility.
Description
Technical field
The present invention relates to a kind of conductive polymers and compound method thereof, surface coverage has the electroactive electrode of said 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 the number of applications prospect.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, the conductive polymers hydrogel is 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 mg ion and electronegative polyelectrolyte doping agent and form the water-soluble conducting polymer gel of ionomer;
3) through the amino generation crosslinking reaction of epoxide group and polyaniline, cross-linked aniline forms gel.
Yet above-mentioned all methods have all been introduced impurity or non-functional material without exception, like metals ion or non-functional polymkeric substance.The shortcoming of these methods is, has reduced specific conductivity, electrochemical activity or the biocompatibility of conductive polymers, and detailed analysis is following: 1) through conductive polymers and ortho-water gelatinous material such as Z 150PH; Polyoxyethylene glycol; Chitosan, SEPIGEL 305, poly 2-hydroxyethyl methacrylate methyl esters; ROHM, 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 property polyelectrolyte and metals 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 compound 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 present invention provides a kind of compound method of conductive polymers, and the preparation method is simple, and need not to introduce other impurity.
The conductive polymers that the present invention also provides above-mentioned compound method to obtain.
The present invention also provides surface coverage that the electroactive electrode of said conductive polymers is arranged.
The compound method of said conductive polymers does; With polyprotonic acid as doping agent and linking agent; Make monomer polymerization obtain the conductive polymers hydrogel; Said 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 said 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 said 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 said polyprotonic acid is a phytic acid.
Monomer obtains the conductive polymers hydrogel through conventional polymerization method, under the oxygenant effect, obtains conductive polymers hydrogel through chemical oxidising polymerisation like 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 cut of said conductive polymers hydrogel is 30%-85%, is preferably 34%-85%.
The compound 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 compound method gained of surface coverage.
The preparation method of said 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 through condensing together like 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, as scheming .1C with shown in the figure .1.When conductive polymers through mixing with the polyfunctionality dopant acid, conductive polymers forms cross-linked network, and is 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 through a simple chemical process of polyfunctionality dopant acid (functionality＞3) of using.
Conductive polymers preparation method according to the invention is simple, and need not to introduce other impurity, can in the aqueous solution, the high-yield quick rate form hydrogel, 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 in the space that its moisture occupies and the molecular chain of conductive polymers 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 metals ion, this makes hydrogel that high biocompatibility 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 up of a shape fibrous texture, and like 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 compound method of conductive polymers is following:
Step 1, the solution that configuration is made up of water and oxygenant.Oxygenant is ammonium persulphate preferably, but other oxygenants also use like iron trichloride, cupric chloride, Silver Nitrate, hydrogen peroxide, hydrochloro-auric acid and other persulphate verivates, like 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, like pyrroles, thiophene and anils such as anisidine, monomethylaniline, MEA, o-alkoxyl aniline and 2; 5-dialkoxy aniline monomer can be respectively applied for synthetic polypyrrole, Polythiophene; Polymethoxy aniline, polyphenylmethyl amine, gathers alkoxyl aniline aniline at polyphenylethyl amine; 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, molecular weight≤800 of polyfunctionality; Said 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, like benzene, and toluene, chloroform, monochloro methane, YLENE, 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 in various difform containers, be cast into difform hydrogel material.
Step 4 is mixed oxidizing agent solution with monomer solution.
Step 5 leaves standstill (from several minutes to a couple of days), in several minutes, forms the hydrogel of polyaniline 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 IX in deionized water, zero(ppm) 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 regarded 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 cut 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 cut 35% to 85%).Resulting hydrogel contact angle in this instance＜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 (shown in accompanying drawing 4) that is made up of dendritic fiber, specific surface area＞30m through freeze-drying under sem
2G
-1The phytic acid doped polyaniline hydrogel of being grown has good biocompatibility, is depicted as the Medulla Bovis seu Bubali stem cell of hydrogel surface growth like accompanying drawing 5.Powder after the gel freeze-drying is pressed into bulk, is 0.02Scm through its specific conductivity of standard four point probe method test
-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 cut 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 cut 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 cut 34%.The ionic conductivity of resulting hydrogel is 0.030Scm
-1
Embodiment 3: phytic acid doped polyaniline hydrogel (water cut 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 cut 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, is 0.0026Scm through its specific conductivity of standard four point probe method test
-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, is 0.031Scm through its specific conductivity of standard four point probe method test
-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, is 0.13Scm through its specific conductivity of standard four point probe method test
-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, is 0.018Scm through its specific conductivity of standard four point probe method test
-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 terepthaloyl moietie is for increasing pyrroles's solubleness to dispose pyrroles, terepthaloyl moietie and phytic acid blended monomer solution 25ml; The terepthaloyl moietie 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, terepthaloyl moietie in deionized water.Powder after the resultant gel freeze-drying is pressed into bulk, is 4.3Scm through its specific conductivity of standard four point probe method test
-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 gathering the hydrogel of 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, is 5.6Scm through its specific conductivity of standard four point probe method test
-1
Embodiment 12: phosphate-doped 2-(2-hydroxyethyl) the thiophene hydrogel that gathers
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 gathering the hydrogel of 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, is 6.2Scm through its specific conductivity of standard four point probe method test
-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, is 0.018Scm through its specific conductivity of standard four point probe method test
-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 the aqueous solution and organic solution at the interface.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, is 1.8Scm through its specific conductivity of standard four point probe method test
-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 the aqueous solution and organic solution at the interface.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, is 2.1Scm through its specific conductivity of standard four point probe method test
-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, is 2.5Scm through its specific conductivity of standard four point probe method test
-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 and the material of this patent invention can be widely used in the device based on conductive polymers hydrogel and nanostructure thereof, like 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 through 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 P-FAD 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.
Claims (12)
1. the compound method of a conductive polymers; It is characterized in that; As doping agent and linking agent, make monomer with polyprotonic acid under the oxygenant effect, obtain the conductive polymers hydrogel through chemical oxidising polymerisation; Said monomer is at least a in pyrroles's or derivatives thereof, thiophene or derivatives thereof, the aniline or derivatives thereof; The acid groups of said 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, and aforementioned polyprotonic acid is phytic 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.
2. the compound method of conductive polymers as claimed in claim 1 is characterized in that the mole number of the acid groups that polyprotonic acid comprises and the monomeric mol ratio of conductive polymers are 1:12 ~ 12:1.
3. the compound method of conductive polymers as claimed in claim 1 is characterized in that the mole number of the acid groups that polyprotonic acid comprises and the monomeric mol ratio of conductive polymers are 2:1 ~ 1:2.
4. the compound method of conductive polymers as claimed in claim 1 is characterized in that said polyprotonic acid is a phytic acid.
5. like the compound method of claim 1 or 2 each described conductive polymerss, the water cut that it is characterized in that said conductive polymers hydrogel is 30%-85%.
6. the compound method of conductive polymers as claimed in claim 5, the water cut that it is characterized in that said conductive polymers hydrogel is 34%-85%.
7. according to claim 1 or claim 2 the compound method of conductive polymers is characterized in that oxygenant is at least a in persulphate, iron(ic)chloride, cupric chloride, Silver Nitrate, hydrogen peroxide, hydrochloro-auric acid or the ceric ammonium nitrate.
8. according to claim 1 or claim 2 the compound method of conductive polymers is characterized in that may further comprise the steps:
(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.
9. according to claim 1 or claim 2 the compound method of conductive polymers, it is characterized in that further comprising the steps of: the resulting conductive polymers hydrogel of purifying after drying obtains the porous nanometer structure conductive polymers.
10. the conductive polymers of each said compound method gained among the claim 1-9.
11. an electroactive electrode, the conductive polymers of each said compound method gained among the surface coverage claim 1-9.
12. the preparation method of the described electroactive electrode of claim 11 may further comprise the steps:
(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, in step (I) and (II), 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.
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