CN100478388C - Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline - Google Patents
Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline Download PDFInfo
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- CN100478388C CN100478388C CNB2006100979031A CN200610097903A CN100478388C CN 100478388 C CN100478388 C CN 100478388C CN B2006100979031 A CNB2006100979031 A CN B2006100979031A CN 200610097903 A CN200610097903 A CN 200610097903A CN 100478388 C CN100478388 C CN 100478388C
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Abstract
This invention discloses a method for preparing polystyrene/polyaniline conductive polymer composite particles. The method comprises: adding polystyrene emulsion into a mixture of aniline and water, ultrasonicating and stirring so that aniline swells in polystyrene particles, adding oxidant aqueous solution, and dropping acid aqueous solution so that aniline polymerizes at the surface of polystyrene particles to form polystyrene/polyaniline conductive polymer composite particles.
Description
(1) technical field:
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method with conductive, high molecular compound particles of polystyrene/polyaniline of nucleocapsid structure.
(2) technical background:
Conductive polymers latex nano-complex particle material integrates the functional of the electroconductibility of polymer self and nano particle, having molecular structure can design, specific conductivity can be regulated and advantage such as morphological specificity may command, and its colloid dispersive characteristic is expected to improve the shortcoming of the ubiquitous processing difficulties of conducting polymer, thereby at electric driven color-changing part, electroluminescent cell, the bio-medical transmitter, anticorrosive and the antistatic coating in metallic surface, novel wave-absorbing and camouflage coating, rechargeable battery, the petroleum cracking catalyzer, aspects such as supramolecule self-assembly have the potential application prospect.
The monomer aniline cost of polyaniline is lower, and polyaniline is easy to synthetic and specific conductivity is higher, environmental stability is good, and being considered to has one of conductive polymers of actual application prospect most; Polystyrene particle mature preparation process and have relative high glass transition, therefore, synthesize with polystyrene particle as the model polymkeric substance, polyaniline is as the conducting function component, and the polystyrene/polyaniline particle with core-shell type structure has important theory and is worth and Practical significance.
See with regard to present research situation, the exemplary steps of synthetic polystyrene/polyaniline core-shell particles is: at first adopt the heterogeneous polymerization method to prepare polystyrene particle, regulate polystyrene emulsion with hydrochloric acid and become strongly-acid, add monomer aniline (perhaps in the neutral polystyrene emulsion, directly dissolving the anilinechloride monomer) again, cause aniline monomer by adding oxygenant then, make it carry out chemical oxidising polymerisation.In order to impel the polymerization that is in the aniline in the solution to occur in the surface of polystyrene particle as much as possible, thereby more effectively obtain polystyrene/polyaniline nuclear-shell composite particles, existing research all is conceived to the surface modification or the finishing of polystyrene particle, to strengthen the interaction between itself and the polyaniline.Wang etc. are the polystyrene particle of anamorphic zone positive charge in advance, then at its surface adsorption anionic emulsifier sodium lauryl sulphate molecule, to strengthen electrostatic attraction effect (the reference 1:Synthetic Metals of cationic intermediates in itself and the polyaniline polymerization process, 2001,119,155-156).People such as Barthet are stablizer with the Polyvinylpyrolidone (PVP), carry out vinylbenzene and the dispersion copolymerization of vinylbenzenesulfonic acid sodium is closed, thereby introduce sulfonic acid group to strengthen its electronegativity (reference 2:Langmuir, 1998 on the polystyrene particle surface, 14,2032-2041).Nicolas etc. adopt in cinnamic dispersion polymerization and contain amino tensio-active agent, gained polystyrene particle surface is rich amino, make the ligation that has hydrogen bond between itself and the polyaniline chain, thereby formation (the reference 3:Langmuir that helps the polyaniline shell, 2005,21,1575-1583).Above-mentioned preparation method's something in common is, one, the aniline monomer in the polymerization all are dissolved in the external phase of polystyrene emulsion with the form of anilinechloride; Its two, polystyrene particle is surface-functionalized, strengthening the interaction between itself and aniline polymerization cationic intermediates and the polyaniline chain, thereby promote the formation of nuclear-shell composite particles.
(3) summary of the invention:
The objective of the invention is to propose the novel method that a kind of preparation has the conductive, high molecular compound particles of polystyrene/polyaniline of nucleocapsid structure.
The process of method proposed by the invention is: at first prepare polystyrene particle, again with aniline in advance swelling in polystyrene particle, to be added drop-wise in the system diffusion and polymerization place thereof then as the slow acid of doping agent, thereby obtain coating evenly, the polystyrene/polyaniline core-shell type composite particles of controllable structure with control monomer aniline.
Technological core of the present invention is: the control that (1) distributes in system to aniline: with aniline and polystyrene emulsion thorough mixing, because aniline is the good solvent of polystyrene, but the solubleness in water lower (being 3.6wt% down) as 18 ℃, therefore, aniline is more prone to swell in the polystyrene particle.Before the polymerization, except that the minute quantity aniline that is dissolved in the water, most aniline monomers are present in the polystyrene particle.(2) to aniline diffusion and polymeric control thereof: disposable adding water-soluble oxidizers is arranged in the polystyrene emulsion of aniline in swelling.At this moment, monomer aniline is in the polystyrene particle basically, and oxygenant then is in aqueous phase.Slowly drip aqueous acid in this system, acid produces aniline salt with aniline reaction, and it spreads to water to utilize its water-soluble promotion, and diffusion by way of particle and the interface of water on carry out chemical oxidising polymerisation with oxidant reaction.Along with the carrying out of reaction, aniline is keeping constantly diffusion and the polymeric process on the polystyrene particle interface, thereby obtains homogeneous, complete polyaniline layer, forms the polystyrene/polyaniline composite particles.
Thought of the present invention and characteristics are: 1. the seed particles that is adopted need not through finishing, functionalization or other special design; 2. aniline before polymerization at first by swelling in polystyrene particle; 3. in polymerization process, the doping agent of polyaniline is not only in the acid of employing, also has been endowed the function of control aniline diffusion; 4. can regulate the diffusion of aniline and the speed of relative movement between its polymerization by the interpolation speed that changes acid, and then the polymerization place of control aniline, play the effect of control composite particles structure.This method can make aniline form the composite particles shell effectively, and the acquisition shell is evenly complete, the core-shell type polystyrene/polyaniline composite particles of controllable thickness.
The synthetic method and the concrete steps thereof of polystyrene/polyaniline core-shell particles proposed by the invention are as follows:
1. the preparation of polystyrene seed particle: adopt methods such as letex polymerization, emulsifier-free emulsion polymerization, dispersion polymerization to prepare polystyrene emulsion.
2. the swelling of aniline monomer in polystyrene particle: aniline is joined in the pure water, and ultra-sonic dispersion adds polystyrene emulsion after about 15 minutes, continues ultrasonic and stir about 15 minutes.
In the system, the weight percent that polystyrene particle accounts for whole system is 1.5～5.0wt%, and the weight percent of aniline and polystyrene particle is not more than 70wt%.
3. aniline forms composite particles at the polystyrene particle surface aggregate: under mechanical stirring, the emulsion that makes in the step 2 is transferred in the three-necked bottle.System continues to stir the aqueous solution of disposable then adding oxygenant 30 minutes after ice-water bath is cooled to 0 ℃.In emulsion, drip aqueous acid, dropwise the back and keep 0 ℃ of reaction 5 hours, remove ice-water bath then, rise to room temperature, continue reaction 18-24 hour.With dilute hydrochloric acid solution centrifuge washing repeatedly, till upper solution becomes colorless, obtain Powdered polystyrene/polyaniline composite particles through centrifugation, vacuum-drying again behind the stopped reaction.
In the system, the mol ratio of oxygenant and aniline is about 1: 1, and acid is 1 with the molar ratio range of aniline: 1-1: 2.Wherein, the concentration of aqueous oxidizing agent solution is 1.0mol/L; The concentration range of acid is 0.25-1.00mol/L.
Among the present invention, used oxygenant can be a kind of in ammonium persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate, the potassium bichromate etc.
Among the present invention, used acid can be a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, the methacrylic acid etc.
(4) embodiment:
Embodiment 1:
N
2Protection joins 20g vinylbenzene in the 180ml water down, is warming up to 70 ℃, stirs after 15 minutes, adds the aqueous solution that 20g is dissolved with the 0.6g Potassium Persulphate, and 70 ℃ of constant temperature reacted 24 hours down.The gained polystyrene particle is monodispersed sphere, and it is 600nm that dynamic light scattering is measured its particle diameter, and polydispersity coefficient is 0.005.Through regulating the acquisition solid content is the polystyrene emulsion of 6.60wt%.
0.1g aniline is joined in the 20ml distilled water, and ultra-sonic dispersion added the polystyrene emulsion of 18.2g after 15 minutes, continued ultra-sonic dispersion while stirring after 15 minutes, was transferred in the three-necked bottle, and ice-water bath is cooled to 0 ℃, continues to stir 30 minutes.Adding 1.1ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, begins to drip the hydrochloric acid that 1.1ml concentration is 1mol/L, dropwises in 30 minutes.System keeps 0 ℃ of reaction 5 hours, removes ice-water bath, rises to room temperature, continues reaction 18 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal again with supernatant liquid, after vacuum-drying obtains powdered samples.The gained sample appearance is blackish green, is viewed as core-shell structure particle under the transmission electron microscope, and shell thickness is about 10nm.The composite particles specific conductivity is 0.08S/cm.
Embodiment 2:
N
2Protection joins 20g vinylbenzene in the 180ml water down, is warming up to 70 ℃, stirs after 15 minutes, adds the aqueous solution that 20g is dissolved with the 0.6g Potassium Persulphate, and 70 ℃ of constant temperature reacted 24 hours down.The gained polystyrene particle is monodispersed sphere, and it is 600nm that dynamic light scattering is measured its particle diameter, and polydispersity coefficient is 0.005.Through regulating the acquisition solid content is the polystyrene emulsion of 6.60wt%.
0.4g aniline is joined in the 20ml distilled water, and ultra-sonic dispersion added the polystyrene emulsion of 9.10g after 15 minutes, continued ultra-sonic dispersion while stirring after 15 minutes, was transferred in the three-necked bottle, and ice-water bath is cooled to 0 ℃, continues to stir 30 minutes.Adding 4.4ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, begins to drip the hydrochloric acid that 4.4ml concentration is 1mol/L, dropwises in 100 minutes.Keep 0 ℃ of reaction 5 hours, remove ice-water bath, rise to room temperature, continue reaction 24 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal again with supernatant liquid, after vacuum-drying obtains the powdery sample.The gained sample appearance is blackish green, is viewed as core-shell structure particle under the transmission electron microscope, and shell thickness is about 50nm.The composite particles specific conductivity is 0.56S/cm.
Embodiment 3:
N
2Protection joins 20g vinylbenzene in the 180ml water down, is warming up to 70 ℃, stirs after 15 minutes, adds the aqueous solution that 20g is dissolved with the 0.6g Potassium Persulphate, and 70 ℃ of constant temperature reacted 24 hours down.The gained polystyrene particle is monodispersed sphere, and it is 600nm that dynamic light scattering is measured its particle diameter, and polydispersity coefficient is 0.005.Through regulating the acquisition solid content is the polystyrene emulsion of 6.60wt%.
0.2g aniline is joined in the 20ml distilled water, and ultra-sonic dispersion added the polystyrene emulsion of 9.10g after 15 minutes, continued ultra-sonic dispersion while stirring after 15 minutes, was transferred in the three-necked bottle, and ice-water bath is cooled to 0 ℃, continues to stir 30 minutes.Adding 2.2ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, begins to drip the hydrochloric acid that 4.4ml concentration is 0.5mol/L, dropwises in 100 minutes.Keep 0 ℃ of reaction 5 hours, remove ice-water bath then, rise to room temperature, continue reaction 20 hours.Stopped reaction, colourless with dilute hydrochloric acid centrifuge washing repeatedly until upper solution, and through centrifugal throw out is separated with supernatant liquid, after vacuum-drying obtains the powdery sample.The gained sample appearance is blackish green, is viewed as core-shell structure particle under the transmission electron microscope, and shell thickness is about 35nm.The composite particles specific conductivity is 0.093S/cm.
Claims (2)
1. the preparation method of conductive, high molecular compound particles of polystyrene/polyaniline, at first prepare polystyrene emulsion, it is characterized in that polystyrene emulsion is joined in the mixed solution of aniline and water, in the formed system, the weight percent that polystyrene particle accounts for whole system is 1.5～5.0%, the weight percent of aniline and polystyrene particle is not more than 70%, ultra-sonic dispersion also stirs, make the aniline swelling in polystyrene particle, after being cooled to 0 ℃, the aqueous solution of disposable adding oxygenant stirs, and drips aqueous acid then, acid is 1 with the scope of the mol ratio of aniline: 1-1: 2, the concentration range of aqueous acid is 0.25-1.00mol/L, and acid is hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, a kind of in the methacrylic acid, 0 ℃ of reaction 5 hours down, continue reaction 18-24 hour under the room temperature, with dilute hydrochloric acid centrifuge washing to upper strata solution becomes be colourless till, through separating and vacuum-drying, product is Powdered polystyrene/polyaniline composite particles.
2. according to the preparation method of the described conductive, high molecular compound particles of polystyrene/polyaniline of claim 1, it is characterized in that, the mol ratio of oxygenant and aniline is 1: 1, and oxygenant is a kind of in ammonium persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate, the potassium bichromate.
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Families Citing this family (14)
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| CN101186750B (en) * | 2007-11-16 | 2010-09-15 | 辽宁大学 | Method for preparing polyaniline/MCM-48 mesoporous molecular screen composition |
| CN100500700C (en) * | 2007-12-13 | 2009-06-17 | 厦门大学 | Method for preparing grain size monodispersed core-shell structural conductive polymer microspheres |
| CN101205266B (en) * | 2007-12-13 | 2010-06-02 | 厦门大学 | Method for preparing spherical shell structure conducting polymer nano material |
| CN101503489B (en) * | 2009-02-26 | 2010-12-29 | 扬州大学 | Preparation of ultra-hydrophobic property polyaniline / polystyrene composite micro-nano material |
| CN101775111B (en) * | 2010-01-25 | 2011-09-28 | 吉林大学 | Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments |
| CN102206356B (en) * | 2011-03-31 | 2012-10-24 | 南京大学 | Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof |
| CN102702636A (en) * | 2012-06-14 | 2012-10-03 | 南京大学 | Polystyrene/polyaniline/magnetic nanoparticle composite particle and preparation method thereof |
| CN104693634A (en) * | 2015-03-05 | 2015-06-10 | 苏州经贸职业技术学院 | Composite conducting engineering plastic and preparation method thereof |
| CN104795247B (en) * | 2015-04-28 | 2017-08-25 | 中科院广州化学有限公司南雄材料生产基地 | A kind of loose structure polyaniline nano combination electrode material and preparation method and application |
| CN105399879B (en) * | 2015-11-19 | 2018-02-13 | 苏州大学 | A kind of preparation method of water-soluble Properties of Polystyrene Nano Particles |
| CN105504565A (en) * | 2015-12-25 | 2016-04-20 | 成都新柯力化工科技有限公司 | Graphene-containing conducting material used for 3D printing and preparation method of graphene-containing conducting material |
| CN108144590B (en) * | 2018-01-05 | 2021-02-05 | 云南大学 | Method for preparing polyaniline @ polystyrene composite microspheres and application of polyaniline @ polystyrene composite microspheres as Cr (VI) adsorbent |
| CN110473654B (en) * | 2019-06-11 | 2021-08-06 | 惠科股份有限公司 | Conductive particle, preparation method thereof and display panel |
| CN110498921A (en) * | 2019-08-05 | 2019-11-26 | 江南大学 | A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing |
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