CN103073888A - Spherical polyelectrolyte brush loaded organic conductive composite micro-nano particle and preparation method thereof - Google Patents
Spherical polyelectrolyte brush loaded organic conductive composite micro-nano particle and preparation method thereof Download PDFInfo
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- CN103073888A CN103073888A CN2013100377319A CN201310037731A CN103073888A CN 103073888 A CN103073888 A CN 103073888A CN 2013100377319 A CN2013100377319 A CN 2013100377319A CN 201310037731 A CN201310037731 A CN 201310037731A CN 103073888 A CN103073888 A CN 103073888A
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Abstract
The invention relates to a spherical polyelectrolyte brush loaded organic conductive composite micro-nano particle and a preparation method thereof. The composite micro-nano particle is composited by a spherical polyelectrolyte brush and an aniline-pyrrole copolymerization conductive polymer. The preparation method comprises the steps of introducing the nano-spherical polyelectrolyte brush into a composite polymeric system, and obtaining the spherical polyelectrolyte brush loaded organic conductive composite micro-nano particle by an in-situ chemical oxidative polymerization method. The preparation method is simple and convenient in operational course; the prepared spherical polyelectrolyte brush loaded organic conductive composite micro-nano particle has the characteristics of high conductivity, controllable particle size and good processing property; the conductive composite micro-nano material with the excellent conductivity can be obtained by controlling a molecular structure of the added spherical polyelectrolyte brush and polymerization reaction condition parameters; and the operational course is simple and convenient.
Description
Technical field
The present invention relates to field of nanocomposite materials, particularly a kind of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle and preparation method thereof.
Background technology
Conductive polymers from 1977 by American scientist Heeger, after MacDiarmid and Japanese scientist's Hideki Shirakawa (Shirakawa) cooperation are found, because the physical and chemical performance of himself excellence has great using value in fields such as national economy, industrial production.Compare to a large amount of reports of conductive polymers polypyrrole, polyaniline, the research of aniline-pyrroles's copolymerization system seems very not enough.Because copolymeric material can overcome the shortcoming of single π-electron in the single homopolymerization system, obtains the more excellent matrix material of performance, therefore, causes gradually people's concern for the aniline-research of pyrroles's copolymerization system.
Similar with single homopolymerization system, the conjugated structure of aniline-pyrroles's copolymerization conductive polymers causes the molecular chain rigidity large, in order to improve this performance, can add oxygenant, doping agent etc. in building-up process.Up to now, mostly concentrate on various templates for this type of research and synthesize the monomer copolymer with nanostructure.As with an one-step electrochemistry method synthesising coated on carbon fiber the PANI-PPy matrix material and use template to prepare pyrroles/aniline compolymer/nano fiber etc. with chemical copolymerization method.
Ball-type polyelectrolyte brush (SPB) refers to high-density an end of charged macromolecular chain is connected in a kind of special homopolymerization or the Copolymer Systems of spherome surface formation.Because it has symmetrical or accurate symmetrical structure, the characteristics such as high grafting density, high charge density have been widely used in a plurality of fields such as stable colloid, chemical valve, biological medicine.The ball-type polyelectrolyte brush is used for single homopolymerization conducting polymer objects system template and mainly is based on kind and the quantity that it could catch and control by electrostatic interaction the ion in the brush layer, and the conductive polymers monomer solid is fixed on the brush layer internal reaction.Obtained at present a small amount of achievement in this respect research, but and its bibliographical information such as Patents as two kinds of monomer copolymerization templates of no-trump.
Summary of the invention
The present invention is directed to the deficiency that exists in the background technology a kind of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle and preparation method thereof is provided.
Concrete technical scheme of the present invention is:
A kind of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle is composited by ball-type polyelectrolyte brush and aniline-pyrroles's copolymerization conductive polymers; In described composite micro-nano particle, the mass percentage content of ball-type polyelectrolyte brush is 5%～15%, and the mass percentage content of aniline-pyrroles's copolymerization conductive polymers is 85%～95%.
The kernel of described ball-type polyelectrolyte brush is the SiO of particle diameter in 50～200 nm scopes
2,The sodium polystyrene sulfonate of the molecular-weight average of outer brush in 500～2000 g/mol scopes.
The present invention also provides the preparation method of above-mentioned ball-type polyelectrolyte brush load organic conductive composite micro-nano particle,
Comprise the steps:
1) aniline monomer and pyrrole monomer are joined in the acid solution of ball-type polyelectrolyte brush, stirring is fully dissolved it, obtains monomer mixture solution;
2) in atmosphere of inert gases, in mixed monomer solution, add oxygenant, in 0～30 ℃ of lower oxypolymerization 2～8 hours, obtain the black solid particle;
3) gained black particle of upper step is used to wash respectively to supernatant liquor with acid solution identical in the step 1 and alcohol-water mixture be colourless, the centrifugal organic conductive composite micro-nano particle that namely gets ball-type polyelectrolyte brush load.
Preferred version as aforesaid method:
The mol ratio of aniline monomer and pyrrole monomer is aniline monomer/pyrrole monomer=1:2～2:1 in the described step 1;
It is the sulphuric acid soln of 0.5 mol/L～1 mol/L that acid solution in described step 1 and the step 3 is hydrochloric acid soln or the concentration that concentration is 1 mol/L～2 mol/L;
The volume of acid solution is 10～20 times of aniline monomer volume in the described step 1;
The kernel of ball-type polyelectrolyte brush is that particle diameter is the SiO of 50～200 nm in the described step 2
2,The molecular-weight average of outer brush is the sodium polystyrene sulfonate of 500～2000 g/mol;
The quality of ball-type polyelectrolyte brush is 5%～15% of aniline monomer and pyrrole monomer quality sum in the described step 2;
Described oxygenant is ammonium persulphate or ferric chloride hexahydrate or Phenylsulfonic acid iron, and the amount of substance of oxygenant be aniline monomer and pyrrole monomer amount of substance and 10%～50%;
In the described step 3 in the alcohol-water mixture alcohol be V with the volume ratio of water
Alcohol: V
Water=3:1～6:1.
The present invention is incorporated into the ball-type polyelectrolyte brush in the conducting polymer objects system as template, obtains the organic conductive composite micro-nano rice corpuscles that conductivity is good, particle diameter is controlled by the control to ball-type polyelectrolyte brush molecular structure.
The room-temperature conductivity of the ball-type polyelectrolyte brush load organic conductive composite micro-nano rice corpuscles that is synthesized is 1～10 S/cm, and particle diameter is 200～400 nm.
Outstanding feature of the present invention and beneficial effect are:
1. the ball-type polyelectrolyte brush load organic conductive composite micro-nano particle of the present invention's preparation has the advantages that specific conductivity is high, particle diameter is controlled.By to adding the control of ball-type polyelectrolyte brush molecular structure and polymeric reaction condition parameter, can obtain the good conduction composite micro-nano rice material 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.
At first prepare the controlled nanometer ball-type polyelectrolyte brush of molecular structure with surperficial initiated polymerization in the embodiment of the invention, then be introduced in the copolymerization system, use the in situ chemical oxidative polymerization method, obtain the organic conductive composite micro-nano rice corpuscles of ball-type polyelectrolyte brush load.
Embodiment 1
With two kinds of monomer mass sums of 80 mg(5%) ball-type polyelectrolyte brush (ASPB, karyosome footpath: 100 nm, brush weight-average molecular weight: 2000 g/mol, synthetic method is seen Express Polymer Letters Vol. 6 (2012) pp 680-686) ultra-sonic dispersion is at 18.9 mL, concentration is in the aqueous hydrochloric acid of 2 mol/L, the aniline (0.9 mL) and pyrroles (0.7 mL) monomer that add Isoequivalent weight after 20 minutes, magnetic agitation.Reaction system placed under 0 ℃ the environment, nitrogen protection is after 20 minutes, adds 2.28 g ammonium persulphates (amount of two kinds of monomeric substances and 50%), and system gradually becomes black.Reaction continued after 6 hours, and the product suction filtration is separated, and filter cake is with aqueous hydrochloric acid and the alcohol-water mixture (V of 2 mol/L
Alcohol/ V
Water=3) washing is 3 times, until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 5.6%, and the massfraction of organic conductive multipolymer is 94.4%.Measuring its specific conductivity with four probe method is 1.6 S/cm, and particle diameter is about 300 nm.
Embodiment 2
With two kinds of monomer mass sums of 160 mg(10%) ASPB(karyosome footpath: 50 nm, the brush weight-average molecular weight: 500 g/mol) ultra-sonic dispersion is at 18.9 mL, in the aqueous hydrochloric acid of 2 mol/L, the aniline (0.9 mL) and pyrroles (0.7 mL) monomer that add Isoequivalent weight after 20 minutes, magnetic agitation.Reaction system placed under 30 ℃ the environment, nitrogen protection is after 20 minutes, adds 1.82 g ammonium persulphates (amount of two kinds of monomeric substances and 40%), and system gradually becomes black.Reaction continued after 2 hours, and the product suction filtration is separated, and filter cake is with aqueous hydrochloric acid and the alcohol-water mixture (V of 2 mol/L
Alcohol/ V
Water=4) washing is until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 9.9%, and the massfraction of organic conductive multipolymer is 90.1%.Measuring its specific conductivity with four probe method is 2.2 S/cm, and particle diameter is about 200 nm.
Embodiment 3
With two kinds of monomer mass sums of 240 mg(15%) ASPB(karyosome footpath: 150 nm, the brush weight-average molecular weight: 1000 g/mol) ultra-sonic dispersion is at 18.9 mL, in the aqueous hydrochloric acid of 2 mol/L, the aniline (0.9 mL) and pyrroles (0.7 mL) monomer that add Isoequivalent weight after 20 minutes, magnetic agitation.Reaction system placed under 5 ℃ the environment, argon shield is after 20 minutes, adds 1.37 g ammonium persulphates (amount of two kinds of monomeric substances and 30%), and system gradually becomes black.Reaction continued after 8 hours, and the product suction filtration is separated, and filter cake is with aqueous hydrochloric acid and the alcohol-water mixture (V of 2 mol/L
Alcohol/ V
Water=5) repetitive scrubbing is until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 15%, and the massfraction of organic conductive multipolymer is 85%.Measuring its specific conductivity with four probe method is 4.6 S/cm, and particle diameter is about 320 nm.
Embodiment 4
With two kinds of monomer mass sums of 120 mg(7.5%) ASPB(karyosome footpath: 200 nm, the brush weight-average molecular weight: 1500 g/mol) ultra-sonic dispersion is at 18.9 mL, in the aqueous hydrochloric acid of 2 mol/L, the aniline (0.9 mL) and pyrroles (0.7 mL) monomer that add Isoequivalent weight after 20 minutes, magnetic agitation.Reaction system placed under 5 ℃ the environment, nitrogen protection is after 20 minutes, adds 0.91 g ammonium persulphate (amount of two kinds of monomeric substances and 20%), and system gradually becomes black.Reaction continued after 6 hours, and the product suction filtration is separated, and filter cake is with aqueous hydrochloric acid and the alcohol-water mixture (V of 2 mol/L
Alcohol/ V
Water=6) repetitive scrubbing is until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 7.8%, and the massfraction of organic conductive multipolymer is 92.2%.Measuring its specific conductivity with four probe method is 5.2 S/cm, and particle diameter is about 400 nm.
Embodiment 5
With two kinds of monomer mass sums of 126.5 mg(5%) ASPB(karyosome footpath: 100 nm, the brush weight-average molecular weight: 1000 g/mol) ultra-sonic dispersion is at 18.9 mL, in the aqueous hydrochloric acid of 1 mol/L, the ratio that adds amount of substance after 20 minutes is aniline (1.8 mL) and pyrroles (0.7 mL) monomer of 2:1, magnetic agitation.Reaction system placed under 5 ℃ the environment, argon shield is after 20 minutes, adds 0.684 g ammonium persulphate (amount of two kinds of monomeric substances and 10%), and system gradually becomes black.Reaction continued after 2 hours, and the product suction filtration is separated, and filter cake is with aqueous hydrochloric acid and the alcohol-water mixture (V of 1 mol/L
Alcohol/ V
Water=3) repetitive scrubbing is until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 5.3%, and the massfraction of organic conductive multipolymer is 94.7%.Measuring its specific conductivity with four probe method is 1.1 S/cm, and particle diameter is about 250 nm.
Embodiment 6
With two kinds of monomer mass sums of 284 mg(12.5%) ASPB(karyosome footpath: 100 nm, the brush weight-average molecular weight: 2000 g/mol) ultra-sonic dispersion is at 18.9 mL, in the aqueous sulfuric acid of 1 mol/L, the ratio that adds amount of substance after 20 minutes is aniline (0.9 mL) and pyrroles (1.4 mL) monomer of 1:2, magnetic agitation.Reaction system placed under 5 ℃ the environment, nitrogen protection is after 20 minutes, adds 2 g Phenylsulfonic acid iron (amount of two kinds of monomeric substances and 10%), and system gradually becomes black.Reaction continued after 5 hours, and the product suction filtration is separated, and filter cake is with aqueous sulfuric acid and the alcohol-water mixture (V of 1 mol/L
Alcohol/ V
Water=3) repetitive scrubbing is until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 12.2%, and the massfraction of organic conductive multipolymer is 87.8%.Measuring its specific conductivity with four probe method is 5.1 S/cm, and particle diameter is about 300 nm.
Embodiment 7
With two kinds of monomer mass sums of 80 mg(5%) ASPB(karyosome footpath: 100 nm, the brush weight-average molecular weight: 2000 g/mol) ultra-sonic dispersion is at 18.9 mL, 0.5 in the aqueous sulfuric acid of mol/L, the aniline (0.9 mL) and pyrroles (0.7 mL) monomer that add Isoequivalent weight after 20 minutes, magnetic agitation.Reaction system placed under 0 ℃ the environment, nitrogen protection added 4 g FeCl after 20 minutes
36H
2The amount of two kinds of monomeric substances of O(and 50%), system gradually becomes black.Reaction continued after 5 hours, and the product suction filtration is separated, and filter cake is with aqueous sulfuric acid and the alcohol-water mixture (V of 0.5 mol/L
Alcohol/ V
Water=3) repetitive scrubbing is until filtrate is colourless.The gained filter cake is 50 ℃ of lower vacuum-dryings 24 hours, then obtains the aniline of ball-type polyelectrolyte brush load-pyrroles's copolymerization conductive polymers powder through grinding.Wherein the massfraction of ball-type polyelectrolyte brush is 5%, and the massfraction of organic conductive multipolymer is 95%.Measuring its specific conductivity with four probe method is 1.3 S/cm, and particle diameter is about 300 nm.
Claims (10)
1. a ball-type polyelectrolyte brush load organic conductive composite micro-nano particle is characterized in that: be composited by ball-type polyelectrolyte brush and aniline-pyrroles's copolymerization conductive polymers; In described composite micro-nano particle, the mass percentage content of ball-type polyelectrolyte brush is 5%～15%, and the mass percentage content of aniline-pyrroles's copolymerization conductive polymers is 85%～95%.
2. ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 1, it is characterized in that: the kernel of described ball-type polyelectrolyte brush is the SiO of particle diameter in 50～200 nm scopes
2,The sodium polystyrene sulfonate of the molecular-weight average of outer brush in 500～2000 g/mol scopes.
3. the preparation method such as the described ball-type polyelectrolyte brush of right 1-2 load organic conductive composite micro-nano particle is characterized in that: comprise the steps:
1) aniline monomer and pyrrole monomer are joined in the acid solution of ball-type polyelectrolyte brush, stirring is fully dissolved it, obtains monomer mixture solution;
2) in atmosphere of inert gases, in mixed monomer solution, add oxygenant, in 0～30 ℃ of lower oxypolymerization 2～8 hours, obtain the black solid particle;
Gained black particle of upper step used to wash respectively to supernatant liquor with acid solution identical in the step 1 and alcohol-water mixture be colourless, the centrifugal organic conductive composite micro-nano particle that namely gets ball-type polyelectrolyte brush load.
4. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3, it is characterized in that: the mol ratio of aniline monomer and pyrrole monomer is aniline monomer/pyrrole monomer=1:2～2:1 in the described step 1.
5. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3 is characterized in that: the acid solution in described step 1 and the step 3 is that concentration is that hydrochloric acid soln or the concentration of 1 mol/L～2 mol/L is the sulphuric acid soln of 0.5 mol/L～1 mol/L.
6. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3 is characterized in that: the volume of acid solution is 10～20 times of aniline monomer volume in the described step 1.
7. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3, it is characterized in that: the kernel of ball-type polyelectrolyte brush is that particle diameter is the SiO of 50～200 nm in the described step 1
2,The molecular-weight average of outer brush is the sodium polystyrene sulfonate of 500～2000 g/mol.
8. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3, it is characterized in that: the quality of ball-type polyelectrolyte brush is 5%～15% of aniline monomer and pyrrole monomer quality sum in the described step 1.
9. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3, it is characterized in that: described oxygenant is ammonium persulphate or ferric chloride hexahydrate or Phenylsulfonic acid iron, and the amount of substance of oxygenant be aniline monomer and pyrrole monomer amount of substance and 10%～50%.
10. the preparation method of ball-type polyelectrolyte brush load organic conductive composite micro-nano particle as claimed in claim 3 is characterized in that: in the described step 3 in the alcohol-water mixture volume ratio of alcohol and water be V
Alcohol: V
Water=3:1～6:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010734A (en) * | 2016-05-30 | 2016-10-12 | 青岛科技大学 | Rough-surface polyaniline/polypyrrole copolymer nano-fiber electrorheological fluid and preparation method thereof |
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|---|---|---|---|---|
| CN101104687A (en) * | 2007-07-09 | 2008-01-16 | 同济大学 | Conductive pyrrylethylaniline polymer and preparation method thereof |
| US20100116691A1 (en) * | 2008-11-07 | 2010-05-13 | University Of Connecticut | Biosensor for continuous monitoring of metabolites and proteins and methods of manufacture thereof |
| CN102443263A (en) * | 2011-10-31 | 2012-05-09 | 武汉大学 | Preparation method for spherical polyelectrolyte brush doped conductive polymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104687A (en) * | 2007-07-09 | 2008-01-16 | 同济大学 | Conductive pyrrylethylaniline polymer and preparation method thereof |
| US20100116691A1 (en) * | 2008-11-07 | 2010-05-13 | University Of Connecticut | Biosensor for continuous monitoring of metabolites and proteins and methods of manufacture thereof |
| CN102443263A (en) * | 2011-10-31 | 2012-05-09 | 武汉大学 | Preparation method for spherical polyelectrolyte brush doped conductive polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010734A (en) * | 2016-05-30 | 2016-10-12 | 青岛科技大学 | Rough-surface polyaniline/polypyrrole copolymer nano-fiber electrorheological fluid and preparation method thereof |
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