CN100588680C - Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres - Google Patents
Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres Download PDFInfo
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- CN100588680C CN100588680C CN200710304102A CN200710304102A CN100588680C CN 100588680 C CN100588680 C CN 100588680C CN 200710304102 A CN200710304102 A CN 200710304102A CN 200710304102 A CN200710304102 A CN 200710304102A CN 100588680 C CN100588680 C CN 100588680C
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- oxygenant
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Abstract
The invention relates to a preparation method of polystyrene/polyaniline conductive polymer composite microspheres with controllable shape and appearance, belonging to the polymer composite technicalfield, which is characterized in that: firstly, a plurality of PS microspheres with a certain diameter are prepared by the emulsifier-free emulsion polymerization, the PS microspheres are taken as thehard template and added into deionized water in which a plurality of aniline monomers are dispersed, the mixture is stirred by magnetic force to form homogenous emulsion at the ambient temperature; secondly, oxidant solution is added into the former mixture one-time, the PS microspheres are taken as the hard template and the micelle formed by the aniline monomers are taken as the ''soft template''; at last, the polystyrene/polyaniline conductive polymer composite microspheres are obtained by conventional post-processing. The preparation method of polystyrene/polyaniline conductive polymer composite microspheres with controllable shape and appearance has the advantages that: the shape and appearance of the polystyrene/polyaniline conductive polymer composite microspheres can be controlledjust by regulating the redox ability of the oxidant; meanwhile, the wall thickness of the core-shell structure and the diameter and the length of the nanometer fiber can be controlled by regulating the addition of the aniline monomers and the redox ability and the addition of the oxidant.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to the preparation method of the controlled polystyrene/polyaniline conductive polymeric composite microspheres of a kind of pattern.
Background technology
The research of conductive polymers has important scientific meaning.In short twenties years, conductive polymers has developed into the research field of a novel crossed subject from the research of some simple polymkeric substance.Nobel chemistry Prize in 2000 just has been awarded A.J.Heeger, and A.G.MacDiarmid and three scientists that start conductive polymers of Bai Chuanying tree have also proved absolutely the approval of scientific circles to the research importance of conductive polymers.In numerous conductive polymerss, polyaniline is because the monomer whose low price, polyaniline is owing to have the mechanism of doping effect of diversified structure, uniqueness, it is higher to be easy to synthetic and good environmental stability and electric conductivity, be considered to have one of conductive polymers of actual application prospect most, the electrically conductive polyaniline of nanostructure becomes the research focus of present nanosecond science and technology and Materials science especially with its peculiar chemistry and electrochemical properties.
Yet, high molecular polymer is because molecular weight is big, not molten insoluble characteristics make its processing difficulties, limited the development of its practicability direction to a certain extent, the most effective solution route is exactly a compositing conducting polymer emulsion nano-complex particle material at present, this material can integrate the functional of the electroconductibility of polymer self and nano particle, its colloid dispersive characteristic is expected to improve the shortcoming of the ubiquitous processing difficulties of conducting polymer, also having molecular structure simultaneously can design, specific conductivity can be regulated advantages such as control, thereby at electroluminescent cell, the wave-absorbing and camouflage coated material, rechargeable battery, the bio-medical transmitter, the metallic surface is anticorrosive, aspects such as supramolecule self-assembly have the potential application prospect.The polystyrene particle mature preparation process, and have relative high glass transition, therefore, be nuclear with the polystyrene particle, synthetic polystyrene/polyaniline conductive polymer complex particle material has important theory and is worth and Practical significance.
The common method of polystyrene/polyaniline polymer composite is at present: at first adopt the heterogeneous polymerization method to prepare polystyrene particle, regulate polystyrene emulsion with hydrochloric acid and become strongly-acid, add aniline monomer, add oxygenant initiated oxidation polymerization then, generate the electrically conductive polyaniline layer on the polystyrene particle surface.In order to impel the aniline in the reaction solution to occur in polystyrene surface as far as possible, present existing research is conceived to the surface modification or the finishing of polystyrene particle mostly, make it surface-functionalized, strengthening the interaction between itself and aniline polymerization cationic intermediates and the polyaniline chain, thereby effectively obtain the polystyrene/polyaniline matrix material.But the polystyrene/polyaniline matrix material that this method obtains mostly is nucleocapsid structure greatly, and pattern is single, and is relatively poor to the controllability of the pattern of product and size.
Summary of the invention
The objective of the invention is to: overcome prior art synthetic polystyrene/single limitation of polyaniline composite material pattern, a kind of novel method for preparing the controlled polystyrene/polyaniline conductive polymeric composite microspheres of pattern easily is provided.
The objective of the invention is to realize by the following technical solutions:
The preparation method of the polystyrene/polyaniline conductive polymeric composite microspheres that pattern provided by the invention is controlled, at first select for use the method for emulsifier-free emulsion polymerization to prepare the monodispersed PS microballoon of certain diameter, and be " hard template " with it, it is joined in the deionized water that is dispersed with aniline monomer, because aniline has parents' molecular structure (hydrophilic amino and hydrophobic phenyl ring), this is similar to surfactant structure and makes its spontaneous formation micella in the aqueous solution, the room temperature lower magnetic force is stirred to even milk sap, under the effect of electrostatic force, the aniline monomer micella can be adsorbed in the outside surface of PS microballoon equably, then, the aqueous solution of disposable adding oxygenant, with the PS microballoon is hard template, the micella " soft template " that aniline monomer forms is because oxygenant is water miscible, so at the oxidative polymerization of generation at the interface of micella and water, pass through conventional aftertreatment at last, obtain the polystyrene/polyaniline conductive polymeric composite microspheres.Power according to selected oxygenant oxidation reducing power, can effectively control the pattern of product, not only can obtain the matrix material of nucleocapsid structure, can also obtain the complex microsphere of the lichee shape that assembles by the one dimension polyaniline nano fiber, and the diameter of nanofiber and length can be regulated by the amount of aniline monomer and the power of oxygenant.
Preferably, the preparation method of the nano structural conductive polyaniline of controllable size provided by the invention selects ammonium persulphate (hereinafter to be referred as APS), Fe (NO for use
3)
3, FeCl
3, or Fe
2(SO
4)
3Be oxygenant.
Use the invention provides method and prepares the controlled polystyrene/polyaniline conductive polymeric composite microspheres of pattern, combines with PS ball " soft template " method for " hard template " and aniline monomer formation, obtains through emulsion polymerization.
Concrete steps are as follows:
1) at first the method by emulsifier-free emulsion polymerization prepares monodispersed polystyrene (being called for short PS) microballoon;
2) with synthetic PS microballoon in the step 1), be dissolved in the deionized water, magnetic agitation is to forming even milk sap, and controlling concn is at 10～30g/L;
3) accurately measure aniline monomer with the injection tolerance and join in the above-mentioned milk sap, 10～40 ℃ of lower magnetic forces stir 10～15 hours to forming uniform milk sap;
4) select different oxygenants for use, the ratio of oxygenant and aniline monomer is 1: 1～1: 10, oxygenant is dissolved in the distilled water, and 0～5 ℃ of refrigeration 30～60 minutes;
Select for use the different amounts of different oxygenants and oxygenant can directly control the pattern of combination product;
5) aqueous solution of the oxygenant in the step (4) is joined once in the solution that is dissolved with aniline monomer and PS microballoon in the step 3), continue magnetic agitation, solution colour is deepened gradually, reacts 12～24 hours, finally forms blackish green;
6) mixing solutions in the step 5) is centrifugal, the solid after centrifugal with distilled water, dehydrated alcohol and ether washing, at last 10～60 ℃ of vacuum-dryings 18～24 hours, obtains blackish green polystyrene/polyaniline powder successively.
Advantage of the present invention is: can be by regulating the power of oxygenant oxidation reducing power simply, effectively control the pattern of polystyrene/polyaniline conductive polymeric composite microspheres, can not only obtain common nucleocapsid structure, also can obtain the sea urchin shape that assembles by one dimension fibre, lichee shape complex microsphere, and the wall thickness of nucleocapsid structure and sea urchin shape, the diameter of the nanofiber in the lichee shape complex microsphere shell and length can effectively be regulated and control by the amount of aniline monomer and the power and the consumption of oxygenant.
Description of drawings
Fig. 1 is the SEM photo of the polystyrene microsphere template that uses of the present invention.
Fig. 2 is to be oxygenant with ammonium persulphate (APS) among the embodiment 1, obtains the polystyrene/polyaniline conductive polymeric composite microspheres SEM photo of nucleocapsid structure.
Fig. 3 is with iron nitrate (Fe (NO among the embodiment 2
3)
3) be oxygenant, obtain the SEM photo of the polystyrene/polyaniline conductive polymeric composite microspheres of class sea urchin shape structure.
Fig. 4 is with iron(ic) chloride (FeCl among the embodiment 3
3) be oxygenant, obtain the SEM photo of the polystyrene/polyaniline conductive polymeric composite microspheres of class sea urchin shape structure.
Embodiment
Embodiment 1, be oxygenant, obtain the polystyrene/polyaniline conductive polymeric composite microspheres of nucleocapsid structure with ammonium persulphate (APS).
1) at first the method by emulsifier-free emulsion polymerization prepares monodispersed polystyrene microsphere;
2) with synthetic PS ball in the 0.3g step 1), be dissolved in the 20ml deionized water, magnetic agitation is to forming even milk sap;
3) accurately measure 2ml aniline monomer (0.02mol) is joined in the above-mentioned milk sap with the injection tolerance, the room temperature lower magnetic force stirs 10 hours to forming uniform solution;
4) with the ammonium persulphate (E of 0.02mol
Ox=2.0V) be dissolved in the distilled water of 15ml, and place the interior refrigeration of refrigerator 30 minutes, the optimum molar ratio of test determination ammonium persulphate and aniline monomer is 1: 1;
5) aqueous solution of the oxygenant in the 5ml step 4) is joined once in the solution that is dissolved with aniline and PS microballoon in the step 3), continue magnetic agitation, solution colour is deepened gradually, reacts 12 hours, finally forms blackish green;
6) mixing solutions in the step 5) is centrifugal, with distilled water, dehydrated alcohol and ether washing three times, vacuum-drying at room temperature at last 24 hours obtains blackish green polystyrene/polyaniline powder to the solid after centrifugal successively.
This cyan product is through infrared/ultraviolet structural characterization, polystyrene/polyaniline matrix material for typical doping attitude, its pattern is a nucleocapsid structure, as shown in Figure 2, can control the thickness of polyaniline shell effectively by the ratio of regulating aniline monomer and PS microballoon.
Embodiment 2, with iron nitrate (Fe (NO
3)
3) be oxygenant, obtain the polystyrene/polyaniline conductive polymeric composite microspheres of class sea urchin shape structure.
1) at first prepares the monodispersed polystyrene microsphere of certain diameter by the method for emulsifier-free emulsion polymerization;
2) with synthetic PS ball in the 0.3g step 1), be dissolved in the 20ml deionized water, magnetic agitation is to forming even milk sap;
3) accurately measure 2ml aniline monomer (0.02mol) is joined in the above-mentioned milk sap with the injection tolerance, the room temperature lower magnetic force stirs 10 hours to forming uniform solution;
4) iron nitrate with 0.08mol is dissolved in the distilled water of 15ml, and places the interior refrigeration of refrigerator 30 minutes, and the optimum molar ratio of test determination ammonium persulphate and aniline monomer is 1: 4;
5) aqueous solution of the oxygenant in the 5ml step 4) is joined once in the solution that is dissolved with aniline and PS microballoon in the step 3), continue magnetic agitation, solution colour is deepened gradually, reacts 12 hours, finally forms blackish green;
6) mixing solutions in the step 5) is centrifugal, with distilled water, dehydrated alcohol and ether washing three times, vacuum-drying at room temperature at last 24 hours obtains blackish green polystyrene/polyaniline powder to the solid after centrifugal successively.
This cyan product is through infrared/ultraviolet structural characterization, polystyrene/polyaniline matrix material for typical doping attitude, conformal looks are the class sea urchin shape structure that one dimension fibre assembles, as shown in Figure 3, the mean diameter of fiber is 50nm, can control the length of polyaniline shell fiber effectively by the ratio of regulating aniline monomer and PS microballoon.
Embodiment 3, with iron(ic) chloride (FeCl
3) be oxygenant, obtain the polystyrene/polyaniline conductive polymeric composite microspheres of class sea urchin shape structure.
1) at first prepares the monodispersed polystyrene microsphere of certain diameter by the method for emulsifier-free emulsion polymerization;
2) with synthetic PS ball in the 0.3g step 1), be dissolved in the 20ml deionized water, magnetic agitation is to forming even milk sap;
3) accurately measure 2ml aniline monomer (0.02mol) is joined in the above-mentioned milk sap with the injection tolerance, the room temperature lower magnetic force stirs 10 hours to forming uniform solution;
4) iron(ic) chloride with 0.1mol is dissolved in the distilled water of 15ml, and places the interior refrigeration of refrigerator 30 minutes, and the optimum molar ratio of test determination ammonium persulphate and aniline monomer is 1: 5;
5) aqueous solution of the oxygenant in the 5ml step 4) is joined once in the solution that is dissolved with aniline and PS microballoon in the step 3), continue magnetic agitation, solution colour is deepened gradually, reacts 12 hours, finally forms blackish green;
6) mixing solutions in the step 5) is centrifugal, with distilled water, dehydrated alcohol and ether washing three times, vacuum-drying at room temperature at last 24 hours obtains blackish green polystyrene/polyaniline powder to the solid after centrifugal successively.
This cyan product is through infrared/ultraviolet structural characterization, polystyrene/polyaniline matrix material for typical doping attitude, its pattern is the class lichee shape structure that one dimension fibre assembles, as shown in Figure 4, the mean diameter of fiber is 30nm, can control the length of polyaniline shell fiber effectively by the ratio of regulating aniline monomer and PS microballoon.
Embodiment 4, with ferric sulfate (Fe
2(SO
4)
3) be oxygenant, obtain the polystyrene/polyaniline conductive polymeric composite microspheres of class sea urchin shape structure.
1) at first prepares the monodispersed polystyrene microsphere of certain diameter by the method for emulsifier-free emulsion polymerization;
2) with synthetic PS ball in the 0.3g step 1), be dissolved in the 20ml deionized water, magnetic agitation is to forming even milk sap;
3) accurately measure 2ml aniline monomer (0.02mol) is joined in the above-mentioned milk sap with the injection tolerance, the room temperature lower magnetic force stirs 10 hours to forming uniform solution;
4) iron(ic) chloride with 0.12mol is dissolved in the distilled water of 15ml, and places the interior refrigeration of refrigerator 30 minutes, and the optimum molar ratio of test determination ammonium persulphate and aniline monomer is 1: 6;
5) aqueous solution of the oxygenant in the 5ml step 4) is joined once in the solution that is dissolved with aniline and PS microballoon in the step 3), continue magnetic agitation, solution colour is deepened gradually, reacts 12 hours, finally forms blackish green;
6) mixing solutions in the step 5) is centrifugal, with distilled water, dehydrated alcohol and ether washing three times, vacuum-drying at room temperature at last 24 hours obtains blackish green polystyrene/polyaniline powder to the solid after centrifugal successively.
This cyan product is through infrared/ultraviolet structural characterization, polystyrene/polyaniline matrix material for typical doping attitude, its pattern is the class lichee shape structure that one dimension fibre assembles, the mean diameter of fiber is 15nm, can control the length of polyaniline shell fiber effectively by the ratio of regulating aniline monomer and PS microballoon.
Claims (1)
1, the preparation method of the controlled polystyrene/polyaniline conductive polymeric composite microspheres of pattern is characterized in that technology is:
(1) at first the method by emulsifier-free emulsion polymerization prepares monodispersed polystyrene microsphere (PS microballoon);
(2) with synthetic PS microballoon in the step (1), be dissolved in the deionized water, magnetic agitation is to forming even milk sap, and controlling concn is at 10～30g/L;
(3) measure accurate amount aniline monomer with syringe and join in the above-mentioned milk sap, 10～40 ℃ of lower magnetic forces stir 10～15 hours to forming uniform milk sap;
(4) select different oxygenants for use, the ratio of oxygenant and aniline monomer is 1: 1, oxygenant is dissolved in the distilled water, and 0～5 ℃ of refrigeration 30～60 minutes; Described oxygenant is ammonium persulphate, Fe (NO
3)
3, FeCl
3, or Fe
2(SO
4)
3
(5) aqueous solution of the oxygenant in the step (4) is joined once in the solution that is dissolved with aniline monomer and polystyrene microsphere in the step (3), continue magnetic agitation, solution colour is deepened gradually, reacts 12～24 hours, finally forms blackish green;
(6) mixing solutions in the step (5) is centrifugal, the solid after centrifugal with distilled water, dehydrated alcohol and ether washing, at last 10～60 ℃ of vacuum-dryings 18～24 hours, obtains blackish green polystyrene/polyaniline powder successively.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020811A (en) * | 2010-11-15 | 2011-04-20 | 北京师范大学 | Method for preparing polystyrene/conductive polymer composite hollow microspheres |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503489B (en) * | 2009-02-26 | 2010-12-29 | 扬州大学 | Preparation of ultra-hydrophobic property polyaniline / polystyrene composite micro-nano material |
| CN101838641B (en) * | 2010-03-12 | 2012-07-04 | 清华大学 | Method for preparing conducting polyaniline immobilized enzyme with nanometer structure |
| CN102206356B (en) * | 2011-03-31 | 2012-10-24 | 南京大学 | Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof |
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-
2007
- 2007-12-25 CN CN200710304102A patent/CN100588680C/en not_active Expired - Fee Related
Non-Patent Citations (7)
| Title |
|---|
| Controlling the structure and morphology ofmonodisperse polystyrene/polyaniline composite particles. Qian Wu,et al.Advanced Functional Materials,Vol.17 . 2007 |
| Controlling the structure and morphology ofmonodisperse polystyrene/polyaniline composite particles. Qian Wu,et al.Advanced Functional Materials,Vol.17. 2007 * |
| Morphology and characterization of conductive films basedon polyaniline-coated polystyrene latexes. Wen-Bin Liau,et al.Journal of Applied Polymer Science,Vol.102 . 2006 |
| Morphology and characterization of conductive films basedon polyaniline-coated polystyrene latexes. Wen-Bin Liau,et al.Journal of Applied Polymer Science,Vol.102. 2006 * |
| Preparation of polystyrene/polyaniline core/shellstructured particles and their epoxy-based conductivecomposites. Yangyong Wang,et al.Polymer International,Vol.56 . 2006 |
| Preparation of polystyrene/polyaniline core/shellstructured particles and their epoxy-based conductivecomposites. Yangyong Wang,et al.Polymer International,Vol.56. 2006 * |
| SPS/PANI复合颗粒的制备与性能研究. 张东华等.功能材料，第35卷第6期. 2004 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020811A (en) * | 2010-11-15 | 2011-04-20 | 北京师范大学 | Method for preparing polystyrene/conductive polymer composite hollow microspheres |
| CN102020811B (en) * | 2010-11-15 | 2013-03-27 | 北京师范大学 | Method for preparing polystyrene/conductive polymer composite hollow microspheres |
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