CN102443263B - Preparation method for spherical polyelectrolyte brush doped conductive polymer - Google Patents
Preparation method for spherical polyelectrolyte brush doped conductive polymer Download PDFInfo
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Abstract
The invention relates to a preparation method for a spherical polyelectrolyte brush doped conductive polymer nanocomposite material. The method comprises the following steps: preparing a spherical polyelectrolyte brush by surface-initiated polymerization, then introducing to a polymerization system, using an in-situ chemical oxidative polymerization to obtain the spherical polyelectrolyte brush doped nano conductive composite material. The prepared nano conductive composite material has the characteristics of high conductivity, good treatment performance, and simple and convenient operation process.
Description
Technical field
The present invention relates to the preparation method of the conductive doped polymkeric substance of a kind of ball-type polyelectrolyte brush, belong to field of nanometer material technology.
Background technology
Conductive polymers early than 1977 by U.S. scientist Heeger, MacDiarmid and (Shirakawa) cooperation of Japanese scientist Bai Chuanying tree are found.Afterwards, a series of novel conductive superpolymer are come out one after another.Conductive polymers commonly used has polypyrrole (PPy), polyaniline (PANI), Polythiophene and derivative thereof etc.Because the physical and chemical performance of conductive polymers self excellence, it has great using value in fields such as national economy, industrial production.At present, the preparation of conducting polymer materials mainly contains electrochemical synthesis method and chemical oxidization method.The former obtains is generally powdered sample, and the latter can directly obtain conducting polymer thin film.The eigenstate conductive polymers that these two kinds of methods obtain is because the π existence of gripping the structure rigidity molecular chain altogether, and it is relatively poor to make it not be soluble in not high, the mechanical ductility of organic solvent commonly used, specific conductivity.Simultaneously, because the conductive polymers particle is insoluble in reaction system, the mensuration of its chain structure is very difficult, and the very easily crosslinked particulate state that is gathered in the polymerization process, influences performances such as its electroconductibility and stability.Studies show that " doping " can address these problems.Because of the difference of doping ionic species, its specific conductivity often can differ several orders of magnitude.At present, application doping agent more widely is aromatic sulfonic acid derivative and organic sulfonate, as Witco 1298 Soft Acid (DBSA), tosic acid (TsOH), paratoluenesulfonic acid sodium salt (TsONa) etc.
In addition, the mechanical property of conductive polymers and processing characteristics also are important consideration very in actual applications.Discover, in the process of synthetic or post-treatment, with conductive polymers and matrix such as polystyrene (PS), polymethylmethacrylate polymerization, blend such as (PMMA) or carry out " molecule is compound ", can obtain the matrix material that not only has certain electroconductibility but also have excellent mechanical performances.As inorganic nano-particle being carried out after the modification again and the compound better matrix material (PPy/Fe of processing characteristics that obtains of polypyrrole
3O
4, PPy/SiO
2).In recent years, adopt the conductive doped polymkeric substance of polymer dielectric to obtain success.This may be because the polymer dielectric molecular dimension is bigger, is difficult for taking off assorted after dopant ion enters between the macromolecular chain, so the conductivity of gained conductive polymers is comparatively stable.Simultaneously, the entanglement effect that the long flexible chain of polymer dielectric is brought can hinder the growth of polypyrrole chain effectively, makes the polypyrrole that generates can be dissolved in the organic phase because molecular weight is less.
Polymer brush refers to high-density that the end with polymer molecular chain is connected in stromal surface and a kind of special homopolymerization or the Copolymer Systems that form.If the polyelectrolyte chain is connected spherome surface, namely form ball-type polyelectrolyte brush (SPB).Since have ball-type symmetry or accurate symmetrical structure, characteristics such as high grafting density, high charge density, and the ball-type polyelectrolyte brush has been widely used in a plurality of fields, as colloidal stability, composite organic-inorganic material, chemical valve, biocompatibility etc.Given this, can predict, after design is introduced and contained electron-withdrawing group and have the brush shape thing of certain functional group in the conducting polymer objects system, by controlling its structural parameter (grafting density, molecular weight etc.), can improve the specific conductivity of conductive polymers.At present, about the research of the conductive doped polymkeric substance of ball-type polyelectrolyte brush seldom, in view of the dynamic property of conductive polymers itself and the complicacy of the poly-electrolysis brush body of ball-type system, wait further deeply about the research of this aspect.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of novel nano matrix material---the preparation method of the conductive doped polymkeric substance of ball-type polyelectrolyte brush, namely by " doping " the ball-type polyelectrolyte brush is introduced in the polymeric system, obtained electroconductibility favorable conductive polymer nanocomposites by the control to doping agent ball-type polyelectrolyte brush molecular structure.
Its preparation method is as follows:
At first prepare the controlled nanometer ball-type polyelectrolyte brush of molecular structure with surperficial initiated polymerization, be introduced into then in the polymerization system, use the in-situ chemical oxidative polymerization method, obtain the conductive polymer nanometer composite material that the ball-type polyelectrolyte brush mixes.
The inventive method detailed process is as follows:
1. the preparation of ball-type polyelectrolyte brush
Silane coupling agent γ-methacryloxypropyl trimethoxy silane is joined in the alcohol-water mixture, and with hydrochloric acid regulation system pH=4, wherein the volume ratio of pure water is 3/1～10/1 in the alcohol-water mixture;
50～200nm monodisperse silica microspheres is joined in the reaction system, and the control temperature of reaction is 50 ℃～80 ℃, reacts 4～6 hours;
Isolate the silicon dioxide microsphere of finishing, join in the organic solvent, and introduce anionic monomer and thermal initiator, 10%～50% of monomer consumption improved silica microspheres quality, under the nitrogen protection, polymerization under 30 ℃～40 ℃ temperature, synthesis of nano negatively charged ion ball-type polyelectrolyte brush;
2. the preparation of the conductive doped polymkeric substance of ball-type polyelectrolyte brush
Pyrrole monomer is joined in the alcohol-water mixture, and stirring is fully dissolved it, and wherein the volume ratio of pure water is 1/10～1/3 in the pure water mixed solution;
The ball-type polyelectrolyte brush and the oxygenant that make are joined in the reaction system; the consumption of ball-type polyelectrolyte brush is 5%～17% of pyrrole monomer quality; the oxygenant consumption is 10%～50% of pyrrole monomer molar mass; under the nitrogen protection; polymerization is 2～10 hours under 0 ℃～30 ℃ temperature, the synthetic conductive doped polymkeric substance of ball-type polyelectrolyte brush.
The nuclear of the nanometer ball-type polyelectrolyte brush that is synthesized is nano silica microsphere, and the branch of the nanometer ball-type polyelectrolyte brush that is synthesized is sodium polystyrene sulfonate, and its weight-average molecular weight is 4.64 * 10
2G/mol～5.15 * 10
4G/mol, surface grafting density is 9.7 * 10
-7Mol/g～1.08 * 10
-4Mol/g.
The conductive polymers that is synthesized is polypyrrole.
In the polyelectrolyte brush building-up process, the thermal initiator that adopts is Diisopropyl azodicarboxylate (AIBN), and its consumption is 1%～5% of improved silica microspheres quality.The organic solvent that reaction is used is toluene or ethanol or dimethyl formamide (DMF), preferred toluene.
In the preparation process of the conductive doped polymkeric substance of ball-type polyelectrolyte brush, the oxygenant that adopts is Iron(III) chloride hexahydrate (FeCl
36H
2O); Reaction solvent is alcohol-water mixture, and consumption is 20～90 times of pyrrole monomer quality.
The specific conductivity of the conductive doped polymer nanocomposites of ball-type polyelectrolyte brush that is synthesized is 10～20S/cm.
Outstanding feature of the present invention and beneficial effect are:
1. the conductive doped polymer nanocomposites of ball-type polyelectrolyte brush of the present invention's preparation has the characteristics of high conductivity.By to adding ball-type polyelectrolyte brush molecular structure and polymeric reaction condition parameter control, can obtain the good conductive nano composites of conductivity.
2. preparation method's operating process of the present invention is simple and convenient.
Embodiment
Below by embodiment, further illustrate the present invention, only be the present invention is described and never limit the present invention.
Embodiment 1
(1) the controlled poly-cloudy ionogen brush of nanometer ball-type of surperficial initiated polymerization legal system back-up minor structure:
Reference literature (Kota Sreenivasa Rao, et al. Journal of Colloid and Interface Science 2005 at first; 289:125-131) the synthetic particle diameter of method is the monodisperse silica microspheres of 100nm.Then 40mg γ-methacryloxypropyl trimethoxy silane (KH-570) is joined 100ml alcohol water (10/1, V
/ V) in the mixing solutions, and with hydrochloric acid regulation system pH=4.Hydrolysis is after 1 hour under the room temperature, adds the 20g massfraction in the system and be 4% nano silicon isopropanol suspension, under 70 ℃ of water bath condition, and back flow reaction 5 hours.After being cooled to room temperature, product with centrifugal 30 minutes of supercentrifuge 10000r/min, is discarded supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 3 times again, makes the silicon dioxide microsphere that the surface has reactive group.At last, be that nano silicon isopropanol suspension and the 100ml toluene of 4% above-mentioned modification joins in the there-necked flask magnetic agitation with the 10g massfraction.Under the nitrogen protection, add 12mg thermal initiator AIBN, add 200mg Sodium styrene sulfonate monomer behind the 10min, 40 ℃ were reacted 24 hours down.Then product is used centrifugal 20 minutes of supercentrifuge 8000r/min, discard supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 1 time and 20ml/ distilled water centrifuge washing 2 times successively, and with 60 ℃ of following vacuum-dryings of product 12 hours, namely gets negatively charged ion ball-type polyelectrolyte brush.The weight-average molecular weight of polyelectrolyte brush (
Mw) be 1.79 * 10
3G/mol, surface grafting density (
σ) be 2.01 * 10
-5Mol/g.
(2) the nanometer ball-type gathers the preparation that cloudy ionogen is brushed conductive doped polymer nanocomposites:
Add the pyrrole monomer that 45g water, 11.85g ethanol and 1.34g do not contain stopper in there-necked flask, magnetic agitation makes its dissolving.Under 0 ℃ of condition, add 0.113g negatively charged ion ball-type polyelectrolyte brush (pyrrole monomer quality 17%), logical nitrogen added 2.7g oxygenant FeCl after 15 minutes
36H
2O, polyreaction 8 hours.After reaction finishes the product suction filtration is separated, 20ml/ alcohol-water mixture repetitive scrubbing of filter cake usefulness 3 times is colourless until filtrate.The gained solid obtains the conductive polymers PPy powder that ASPB mixes at 50 ℃ of following vacuum-drying 24h through grinding.Surveying its specific conductivity with four probe method is 20S/cm.
Embodiment 2
According to document (Kota Sreenivasa Rao, et al. Journal of Colloid and Interface Science 2005; 289:125-131) method prepares the silicon dioxide microsphere that particle diameter is about 50nm; Then 40mg γ-methacryloxypropyl trimethoxy silane (KH-570) is joined 100ml alcohol water (3/1, V
/ V) in the mixing solutions, and with hydrochloric acid regulation system pH=4, make its hydrolysis at room temperature after 1 hour, add the 20g massfraction in the system and be 4% nano silicon isopropanol suspension, under 50 ℃ of water bath condition, back flow reaction 6 hours.After being cooled to room temperature, product is used centrifugal 30 minutes of supercentrifuge 10000r/min, discard supernatant liquid, the gained solid is used 10ml dehydrated alcohol centrifuge washing 3 times again, makes the silicon dioxide microsphere that the surface has reactive group; At last the 10g massfraction is joined in the there-necked flask magnetic agitation for nano silicon isopropanol suspension and the 100ml toluene that the 4wt% end group contains reactive group.Under the nitrogen protection, add 4mg thermal initiator AIBN, add 40mg Sodium styrene sulfonate monomer behind the 10min, 40 ℃ were reacted 10 hours down.Then product is used centrifugal 20 minutes of supercentrifuge 8000r/min, discard supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 1 time and 20ml/ distilled water centrifuge washing 2 times successively, and 60 ℃ of following vacuum-dryings of product 12 hours namely get positively charged ion ball-type polyelectrolyte brush.The weight-average molecular weight of polyelectrolyte brush is 4.64 * 10
2G/mol, surface grafting density is 1.08 * 10
-4Mol/g.
Add the pyrrole monomer that 45g water, 11.85g ethanol and 2.68g do not contain stopper in there-necked flask, magnetic agitation makes its dissolving.Reaction system placed under 30 ℃ the environment, add 0.228g negatively charged ion ball-type polyelectrolyte brush (pyrrole monomer quality 8.5%), nitrogen protection added 5.4g oxygenant FeCl after 15 minutes
36H
2O.After the polyreaction 8 hours, the product suction filtration is separated, 20ml/ alcohol-water mixture repetitive scrubbing of filter cake usefulness 3 times is colourless until filtrate.The gained solid obtains the conductive polymers PPy powder that ASPB mixes at 50 ℃ of following vacuum-drying 24h through grinding.Measuring its specific conductivity with four probe method is 10S/cm.
Embodiment 3
According to document (Kota Sreenivasa Rao, et al. Journal of Colloid and Interface Science 2005; 289:125-131) method prepares the silicon dioxide microsphere that particle diameter is about 150nm; Then 40mg γ-methacryloxypropyl trimethoxy silane (KH-570) is joined 100ml alcohol water (6/1, V
/ V) in the mixing solutions, and with hydrochloric acid regulation system pH=4, make its hydrolysis at room temperature after 1 hour, add the 20g massfraction in the system and be 4% nano silicon isopropanol suspension, under 80 ℃ of water bath condition, back flow reaction 4 hours.After being cooled to room temperature, product is used centrifugal 30 minutes of supercentrifuge 10000r/min, discard supernatant liquid, the gained solid is used 10ml dehydrated alcohol centrifuge washing 3 times again, makes the silicon dioxide microsphere that the surface has reactive group; At last the 10g massfraction is joined in the there-necked flask magnetic agitation for nano silicon isopropanol suspension and the 100ml toluene that the 4wt% end group contains reactive group.Under the nitrogen protection, add 20mg thermal initiator AIBN, add 120mg Sodium styrene sulfonate monomer behind the 10min, 30 ℃ were reacted 30 hours down.Then product is used centrifugal 20 minutes of supercentrifuge 8000r/min, discard supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 1 time and 20ml/ distilled water centrifuge washing 2 times successively, and 60 ℃ of following vacuum-dryings of product 12 hours namely get negatively charged ion ball-type polyelectrolyte brush.The weight-average molecular weight of polyelectrolyte brush is 5.15 * 10
4G/mol, surface grafting density is 1.455 * 10
-6Mol/g.
Add the pyrrole monomer that 45g water, 11.85g ethanol and 0.67g do not contain stopper in there-necked flask, magnetic agitation makes its dissolving.Reaction system placed under 0 ℃ the environment, add 0.067g negatively charged ion ball-type polyelectrolyte brush (pyrrole monomer quality 10%), nitrogen protection added 1.35g oxygenant FeCl after 15 minutes
36H
2O.After the polyreaction 2 hours, the product suction filtration is separated, 20ml/ alcohol-water mixture repetitive scrubbing of filter cake usefulness 3 times is colourless until filtrate.The gained solid obtains the conductive polymers PPy powder that ASPB mixes at 50 ℃ of following vacuum-drying 24h through grinding.Measuring its specific conductivity with four probe method is 11. 5S/cm.
Embodiment 4
According to document (Kota Sreenivasa Rao, et al. Journal of Colloid and Interface Science 2005; 289:125-131) method prepares the silicon dioxide microsphere that particle diameter is about 200nm; Then 40mg γ-methacryloxypropyl trimethoxy silane (KH-570) is joined 100ml alcohol water (10/1, V
/ V) in the mixing solutions, and with hydrochloric acid regulation system pH=4, make its hydrolysis at room temperature after 1 hour, add the 20g massfraction in the system and be 4% nano silicon isopropanol suspension, under 70 ℃ of water bath condition, back flow reaction 5 hours.After being cooled to room temperature, product is used centrifugal 30 minutes of supercentrifuge 10000r/min, discard supernatant liquid, the gained solid is used 10ml dehydrated alcohol centrifuge washing 3 times again, makes the silicon dioxide microsphere that the surface has reactive group; At last the 10g massfraction is joined in the there-necked flask magnetic agitation for nano silicon isopropanol suspension and the 100ml toluene that the 4wt% end group contains reactive group.Under the nitrogen protection, add 16mg thermal initiator AIBN, add 160mg Sodium styrene sulfonate monomer behind the 10min, 35 ℃ were reacted 24 hours down.Then product is used centrifugal 20 minutes of supercentrifuge 8000r/min, discard supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 1 time and 20ml/ distilled water centrifuge washing 2 times successively, and 60 ℃ of following vacuum-dryings of product 12 hours namely get positively charged ion ball-type polyelectrolyte brush.The weight-average molecular weight of polyelectrolyte brush is 3.23 * 10
4G/mol, surface grafting density is 9.7 * 10
-7Mol/g.
Add the pyrrole monomer that 60g water, 15.78g ethanol and 1.34g do not contain stopper in there-necked flask, magnetic agitation makes its dissolving.Reaction system placed under 0 ℃ the environment, add 0.067g negatively charged ion ball-type polyelectrolyte brush (pyrrole monomer quality 5%), nitrogen protection added 2.7g oxygenant FeCl after 15 minutes
36H
2O.After the polyreaction 6 hours, the product suction filtration is separated, 20ml/ alcohol-water mixture repetitive scrubbing of filter cake usefulness 3 times is colourless until filtrate.The gained solid obtains the conductive polymers PPy powder that ASPB mixes at 50 ℃ of following vacuum-drying 24h through grinding.Measuring its specific conductivity with four probe method is 16.8S/cm.
Embodiment 5
According to document (Kota Sreenivasa Rao, et al. Journal of Colloid and Interface Science 2005; 289:125-131) method prepares the silicon dioxide microsphere that particle diameter is about 100nm; Then 40mg γ-methacryloxypropyl trimethoxy silane (KH-570) is joined 100ml alcohol water (10/1, V
/ V) in the mixing solutions, and with hydrochloric acid regulation system pH=4, make its hydrolysis at room temperature after 1 hour, add the 20g massfraction in the system and be 4% nano silicon isopropanol suspension, under 70 ℃ of water bath condition, back flow reaction 5 hours.After being cooled to room temperature, product is used centrifugal 30 minutes of supercentrifuge 10000r/min, discard supernatant liquid, the gained solid is used 10ml dehydrated alcohol centrifuge washing 3 times again, makes the silicon dioxide microsphere that the surface has reactive group; At last the 10g massfraction is joined in the there-necked flask magnetic agitation for nano silicon isopropanol suspension and the 100ml ethanol that the 4wt% end group contains reactive group.Under the nitrogen protection, add 12mg thermal initiator AIBN, add 200mg Sodium styrene sulfonate monomer behind the 10min, 40 ℃ were reacted 24 hours down.Then product is used centrifugal 20 minutes of supercentrifuge 8000r/min, discard supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 1 time and 20ml/ distilled water centrifuge washing 2 times successively, and 60 ℃ of following vacuum-dryings of product 12 hours namely get positively charged ion ball-type polyelectrolyte brush.The weight-average molecular weight of polyelectrolyte brush is 1.79 * 10
3G/mol, surface grafting density is 2.01 * 10
-5Mol/g.
Add the pyrrole monomer that 50g water, 7.89g ethanol and 2.68g do not contain stopper in there-necked flask, magnetic agitation makes its dissolving.Reaction system placed under 10 ℃ the environment, add 0.268g negatively charged ion ball-type polyelectrolyte brush (pyrrole monomer quality 10%), nitrogen protection added 3.24g oxygenant FeCl after 15 minutes
36H
2O.After the polyreaction 10 hours, the product suction filtration is separated, 20ml/ alcohol-water mixture repetitive scrubbing of filter cake usefulness 3 times is colourless until filtrate.The gained solid obtains the conductive polymers PPy powder that ASPB mixes at 50 ℃ of following vacuum-drying 24h through grinding.Measuring its specific conductivity with four probe method is 15.6S/cm.
Embodiment 6
According to document (Kota Sreenivasa Rao, et al. Journal of Colloid and Interface Science 2005; 289:125-131) method prepares the silicon dioxide microsphere that particle diameter is about 100nm; Then 40mg γ-methacryloxypropyl trimethoxy silane (KH-570) is joined 100ml alcohol water (10/1, V
/ V) in the mixing solutions, and with hydrochloric acid regulation system pH=4, make its hydrolysis at room temperature after 1 hour, add the 20g massfraction in the system and be 4% nano silicon isopropanol suspension, under 70 ℃ of water bath condition, back flow reaction 5 hours.After being cooled to room temperature, product is used centrifugal 30 minutes of supercentrifuge 10000r/min, discard supernatant liquid, the gained solid is used 10ml dehydrated alcohol centrifuge washing 3 times again, makes the silicon dioxide microsphere that the surface has reactive group; At last the 10g massfraction is joined in the there-necked flask magnetic agitation for nano silicon isopropanol suspension and the 100ml dimethyl formamide that the 4wt% end group contains reactive group.Under the nitrogen protection, add 12mg thermal initiator AIBN, add 200mg Sodium styrene sulfonate monomer behind the 10min, 40 ℃ were reacted 24 hours down.Then product is used centrifugal 20 minutes of supercentrifuge 8000r/min, discard supernatant liquid, the gained solid is used 10ml/ dehydrated alcohol centrifuge washing 1 time and 20ml/ distilled water centrifuge washing 2 times successively, and 60 ℃ of following vacuum-dryings of product 12 hours namely get positively charged ion ball-type polyelectrolyte brush.The weight-average molecular weight of polyelectrolyte brush is 1.79 * 10
3G/mol, surface grafting density is 2.01 * 10
-5Mol/g.
Add the pyrrole monomer that 200g water, 15.78g ethanol and 2.68g do not contain stopper in there-necked flask, magnetic agitation makes its dissolving.Reaction system placed under 0 ℃ the environment, add 0.268g negatively charged ion ball-type polyelectrolyte brush (pyrrole monomer quality 10%), nitrogen protection added 1.08g oxygenant FeCl after 15 minutes
36H
2O.After the polyreaction 6 hours, the product suction filtration is separated, 20ml/ alcohol-water mixture repetitive scrubbing of filter cake usefulness 3 times is colourless until filtrate.The gained solid obtains the conductive polymers PPy powder that ASPB mixes at 50 ℃ of following vacuum-drying 24h through grinding.Measuring its specific conductivity with four probe method is 14.3S/cm.
Claims (6)
1. the preparation method of the conductive doped polymkeric substance of ball-type polyelectrolyte brush is characterized in that, comprises the steps:
The preparation of ball-type polyelectrolyte brush
Silane coupling agent γ-methacryloxypropyl trimethoxy silane is joined in the alcohol-water mixture, and with hydrochloric acid regulation system pH=4, wherein the volume ratio of pure water is 3/1～10/1 in the alcohol-water mixture;
50～200nm monodisperse silica microspheres is joined in the reaction system, and the control temperature of reaction is 50 ℃～80 ℃, reacts 4～6 hours;
Isolate the silicon dioxide microsphere of finishing, join in the organic solvent, and introduce anionic monomer and thermal initiator, the monomer consumption is 10%～50% of improved silica microspheres quality, under the nitrogen protection, polymerization under 30 ℃～40 ℃ temperature, synthesis of nano negatively charged ion ball-type polyelectrolyte brush; Described anionic monomer is Sodium styrene sulfonate, and described thermal initiator is Diisopropyl azodicarboxylate;
2) preparation of the conductive doped polymkeric substance of ball-type polyelectrolyte brush
Pyrrole monomer is joined in the alcohol-water mixture, and stirring is fully dissolved it, and wherein the volume ratio of pure water is 1/10～1/3 in the pure water mixed solution;
The ball-type polyelectrolyte brush and the oxygenant that make are joined in the reaction system, the consumption of ball-type polyelectrolyte brush is 5%～17% of pyrrole monomer quality, the oxygenant consumption is 10%～50% of pyrrole monomer molar mass, under the nitrogen protection, polymerization is 2～10 hours under 0 ℃～30 ℃ temperature, the synthetic conductive doped polymkeric substance of ball-type polyelectrolyte brush; Described oxygenant is Iron(III) chloride hexahydrate.
2. preparation method according to claim 1 is characterized in that, the nanometer ball-type polyelectrolyte brush that is synthesized, and its weight-average molecular weight is 4.64 * 10
2G/mol～5.15 * 10
4G/mol, surface grafting density is 9.7 * 10
-7Mol/g～1.08 * 10
-4Mol/g.
3. preparation method according to claim 1 and 2 is characterized in that, in the polyelectrolyte brush building-up process, the thermal initiator that adopts is Diisopropyl azodicarboxylate, and its consumption is 1%～5% of improved silica microspheres quality.
4. preparation method according to claim 1 and 2 is characterized in that, in the polyelectrolyte brush building-up process, the organic solvent that reaction is used is toluene or ethanol or dimethyl formamide.
5. preparation method according to claim 1 and 2 is characterized in that, in the preparation process of the conductive doped polymkeric substance of ball-type polyelectrolyte brush, the consumption of reaction solvent alcohol-water mixture is 20～90 times of pyrrole monomer quality.
6. preparation method according to claim 1 and 2 is characterized in that, the specific conductivity of the conductive doped polymer nanocomposites of ball-type polyelectrolyte brush that is synthesized is 10～20S/cm.
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