CN103627107B - A kind of preparation method of polystyrene/silver/Pt/Polypyrrole composite material - Google Patents
A kind of preparation method of polystyrene/silver/Pt/Polypyrrole composite material Download PDFInfo
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- CN103627107B CN103627107B CN201310636169.1A CN201310636169A CN103627107B CN 103627107 B CN103627107 B CN 103627107B CN 201310636169 A CN201310636169 A CN 201310636169A CN 103627107 B CN103627107 B CN 103627107B
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Abstract
The invention discloses a kind of preparation method of polystyrene/silver/Pt/Polypyrrole composite material, it is characterized in that comprising the steps: the preparation of (1) polystyrene particle; (2) preparation of the polystyrene particle of sulfonation; (3) preparation of polystyrene/silver composite microballoon; (4) preparation of polystyrene/silver/Pt/Polypyrrole composite material. This method technique used is simple, reproducible, and the composite making has higher catalytic activity and electric conductivity, is applicable to the suitability for industrialized production of catalysis and conductive material.
Description
Technical field
The present invention relates to the applied technical field of organic/inorganic composite material, is exactly a kind of polystyrene/silver/poly-The preparation method of pyrroles's composite.
Background technology
Organic/Inorganic Composite Nanomaterials both can overcome the difficult processing of simple inorganic particle and organic macromolecule is stablizedProperty when poor, the shortcoming such as intensity is low, can also be under both actings in conjunction, obtain than inorganic particle and organic polymer moreExcellent performance, as the excellent properties of the aspects such as the mechanics at material, electricity, calorifics, optics. Therefore, in view of organic/inorganic is receivedThe distinctive performance of nano composite material, it with aspects such as the Application and Development at optical, electrical, mechanics, biology, magnetics and microdevice allHave broad application prospects.
In recent years, due to metal nanoparticle as silver and golden nano particle under certain condition can be by catalytic actionMake the bond fissions such as C-H, C-C, H-H and C-O, preparation and the application of researcher to it conducts extensive research. RespectivelyPlant in functional polymer, conducting polymer as pyrroles etc. has an obvious advantage as the carrier of metal nanoparticle isThe oxidative polymerization of polymer monomer and the reduction reaction of slaine can complete simultaneously. But this nucleocapsid composite size is non-Often little, use this material as catalyst, after having reacted, adopt conventional isolation technics as filtered and centrifugal etc., very difficult by itFrom reactant liquor, thoroughly remove, caused the pollution of catalyst to reactant liquor, thereby greatly limited the extensive use of this material.Therefore taking nano level polystyrene as template, prepare polystyrene/silver/Pt/Polypyrrole composite material. Both can effectively preventThe reduction of its catalytic performance causing because of the reunion between metal nanoparticle, can make again this composite by centrifugal workWith separating with reactant liquor, can also greatly improve purity and the conductance of polypyrrole, thereby it is wide that this material is hadApplication prospect.
In recent years, have a lot of reports for the polystyrene clad composite material of preparation both at home and abroad, mainly contained as followsPolystyrene clad composite material: (1) Li etc. are at " AppliedMaterials & Interfaces " magazine 2013,5,883-891 have reported polystyrene-poly pyrroles-nickel composite material, and this material has good electromagnetic wave absorbability, in electro-magnetic wave absorptionMaterial Field has broad application prospects; (2) Lam etc. is at " Industrial&EngineeringChemistryResearch " magazine 2009,48,4975-4979 has reported polystyrene-poly glycidol resin composite materials, this material canFor the recycling of precious metal salt; (3) Shi etc. is at " AdvancedMaterials " magazine 2009,21,2170-2173 reportRoad polystyrene-di-iron trioxide composite, this material can be used for imaging and the thermotherapy in organism; (4) Jainae etc.At " ChemicalEngineeringJournal " magazine 2010,160,586-593 has reported that polystyrene-Conjugate ferrite is multipleCondensation material, this material can reclaim noble metal from old metal; (5) Kanwal etc. " ColloidsandSurfacesB:Biointerfaces " magazine 2010,81,549-554 has reported polystyrene-cadmium telluride composite, this material is in medicalizationLearn luminous context of detection and have good application prospect; (6) Hu etc. is at " ChemicalPhysicsLetters " magazine 2010,484,247-253 has reported polystyrene-graphene composite material, and this material demonstrates higher electric conductivity; (7) Xu etc. exists" Langmuir " 2012,28,3271-3278 has reported polystyrene/Fe3O4Complex microsphere, this material has at biomedical aspectWide application prospect.
The preparation of most of polystyrene clad composite materials of existing report need to be in strict laboratory equipment and workUnder skill controlled condition, carry out, and preparation process complexity, thereby greatly limit polystyrene clad composite material at production fieldExtensive use.
Summary of the invention
The object of the present invention is to provide a kind of preparation process simple, repeatability better, and can be good organicParticle and inorganic particulate combine, and have possessed the preparation of the polystyrene/silver/Pt/Polypyrrole composite material of two aspect characteristics simultaneouslyMethod.
The technical scheme that realizes the object of the invention is: a kind of preparation method of polystyrene/silver/Pt/Polypyrrole composite material,It is characterized in that comprising the steps:
(1) preparation of polystyrene particle
Stabilizing agent and distilled water are joined respectively in alcohols solvent, and stirring at room temperature is even, under the protection of logical nitrogen, and willInitator and styrene monomer join respectively in above-mentioned solution, at 50～100 DEG C, react 0～100 DEG C 20～24 hoursLower drying and grinding becomes powder, makes polystyrene seed microballoon, and wherein initator, stabilizing agent, distilled water, cinnamic mass ratio are1:15～20:25～30:75～80；
(2) preparation of sulfonated polystyrene microballoon
Polystyrene particle is joined in sulfonating agent, ultrasonic dispersion 10～30 minutes, at 20～60 DEG C, reaction 3～5Hour, centrifuge washing, drying and grinding becomes powder at 0～100 DEG C, obtains the polystyrene particle of sulfonation;
(3) preparation of polystyrene/silver composite microballoon
The polystyrene particle of sulfonation and stabilizing agent are joined respectively in distilled water, under room temperature, mix, by concentrationThe silver ammino solution that is 0.5～1.0mol/L joins in above-mentioned solution, under room temperature, stirs 1～3 hour, then at 50～100 DEG C,React 5～10 hours, drying and grinding becomes powder at 0～100 DEG C, obtains polystyrene/silver composite microballoon, wherein sulfonated polyphenylThe mass ratio of ethene, stabilizing agent, silver ammino solution is 1:3～3.5:3～3.5;
(4) preparation of polystyrene/silver/Pt/Polypyrrole composite material
Polystyrene/silver composite microballoon and ferric trichloride are joined respectively in distilled water to ultrasonic dispersion 10～30Minute, pyrrole monomer is joined in above-mentioned solution to stirring at room temperature reaction 20～24 hours, the vacuum drying chamber of 50～100 DEG CIn dry 10～12 hours, after taking-up, obtain polystyrene/silver/Pt/Polypyrrole composite material, wherein pyrroles, polystyrene/silverThe mass ratio of composite microballoon, ferric trichloride is 1:2.5～3:4.5～5.
As optimal technical scheme, in the described process of preparing polystyrene particle, described stabilizing agent is poly-secondEnol or polyvinylpyrrolidone, described initator is dibenzoyl peroxide or azodiisobutyronitrile, described alcoholKind solvent is methyl alcohol, ethanol or butanols, and alcohols solvent consumption is 450～500 times of initator quality.
As optimal technical scheme, in the described process of preparing sulfonated polystyrene microballoon, described polystyreneParticle is of a size of 500～800nm, described sulfonating agent be sulfuric acid, sulfur trioxide, oleum, chlorosulfonic acid, sodium sulfite,Sodium hydrogensulfite or sodium pyrosulfite, the consumption of sulfonating agent is 15～20 times of polystyrene microsphere quality.
As optimal technical scheme, in the described process of preparing polystyrene/silver composite microballoon, described is steadyDetermining agent is polyvinyl alcohol or polyvinylpyrrolidone, the polystyrene particle quality that the consumption of described distilled water is sulfonation150～200 times.
As optimal technical scheme, in the described process of preparing polystyrene/silver/Pt/Polypyrrole composite material, distillationThe consumption of water is 250～300 times of pyrroles's quality.
Compared with prior art, the invention has the advantages that:
Adopt method of the present invention, manufacturing process is simple, reproducible, can be for large-scale production.
Polystyrene/silver/Pt/Polypyrrole composite material of preparing by the inventive method has improved the purity of polypyrrole greatlyAnd conductance.
Polystyrene/silver/Pt/Polypyrrole composite material of preparing by the inventive method has effectively prevented Nano silver grainBetween reunion.
The catalytic activity of polystyrene/silver/Pt/Polypyrrole composite material of preparing by the inventive method compares traditional catalystCatalytic activity high a lot, and can from reactant liquor, separate by conventional isolation technics, avoided catalyst to reactionThe pollution of liquid.
Polystyrene/silver/Pt/Polypyrrole composite material prepared by the inventive method can be used for catalyst, the necks such as conductive materialTerritory.
Specific implementation method
By specific embodiment, foregoing of the present invention is made to further description below, but this should not managedSeparate and only limit to following example for content of the present invention.
Embodiment mono-
(1) preparation of polystyrene particle
2g polyvinylpyrrolidone and 3g distilled water are joined respectively in 50ml ethanol, and stirring at room temperature is even, at logical nitrogenUnder gas protection, 0.1g azodiisobutyronitrile and 7g styrene are joined respectively in above-mentioned solution, at 60 DEG C, reaction 20 is littleTime, drying and grinding becomes powder at 40 DEG C, obtains polystyrene particle;
(2) preparation of the polystyrene particle of sulfonation
2g polystyrene particle is joined in the concentrated sulfuric acid of 20ml98%, ultrasonic dispersion 10 minutes, at 30 DEG C, reaction3 hours, centrifuge washing, drying and grinding becomes powder at 40 DEG C, obtains the polystyrene particle of sulfonation;
(3) preparation of polystyrene/silver composite microballoon
The polystyrene particle of 0.5g sulfonation and 1.5g polyvinylpyrrolidone are joined respectively in 75ml distilled water to chamberUnder temperature, mix, the silver ammino solution that is 0.5mol/L by 5ml concentration joins in above-mentioned solution, under room temperature, stir 1 hour,At 60 DEG C, react 5 hours, drying and grinding becomes powder at 50 DEG C, obtains polystyrene/silver composite microballoon again;
(4) preparation of polystyrene/silver/Pt/Polypyrrole composite material
0.4g polystyrene/silver composite microballoon and 0.6g ferric trichloride are joined respectively in 20ml distilled water, superSound disperses 10 minutes, 60 μ l pyrrole monomers is joined in above-mentioned solution to stirring at room temperature reaction 20 hours, the vacuum drying of 50 DEG CIn case, be dried 10 hours, after taking-up, obtain polystyrene/silver/Pt/Polypyrrole composite material.
Embodiment bis-
(1) preparation of polystyrene particle
3g polyvinylpyrrolidone and 5g distilled water are joined respectively in 115ml ethanol, and stirring at room temperature is even, at logical nitrogenUnder gas protection, 0.2g azodiisobutyronitrile and 15g styrene are joined respectively in above-mentioned solution, at 70 DEG C, reaction 22 is littleTime, drying and grinding becomes powder at 50 DEG C, obtains polystyrene particle;
(2) preparation of the polystyrene particle of sulfonation
3g polystyrene particle is joined in the concentrated sulfuric acid of 30ml98%, ultrasonic dispersion 20 minutes, at 40 DEG C, reaction4 hours, centrifuge washing, drying and grinding becomes powder at 50 DEG C, obtains the polystyrene particle of sulfonation;
(3) preparation of polystyrene/silver composite microballoon
The polystyrene particle of 1.0g sulfonation and 3.5g polyvinylpyrrolidone are joined respectively in 100ml distilled water,Under room temperature, mix, the silver ammino solution that is 0.75mol/L by 7.5ml concentration joins in above-mentioned solution, under room temperature, stirs 2Hour, then at 70 DEG C, react 7 hours, drying and grinding becomes powder at 60 DEG C, obtains polystyrene/silver composite microballoon;
(4) preparation of polystyrene/silver/Pt/Polypyrrole composite material
0.8g polystyrene/silver composite microballoon and 1.4g ferric trichloride are joined respectively in 60ml distilled water, superSound disperses 20 minutes, 70 μ l pyrrole monomers is joined in above-mentioned solution to stirring at room temperature reaction 22 hours, the vacuum drying of 60 DEG CIn case, be dried 11 hours, after taking-up, obtain polystyrene/silver/Pt/Polypyrrole composite material.
Embodiment tri-
(1) preparation of polystyrene particle
4g polyvinylpyrrolidone and 8g distilled water are joined respectively in 200ml ethanol, and stirring at room temperature is even, at logical nitrogenUnder gas protection, 0.3g azodiisobutyronitrile and 24g styrene are joined respectively in above-mentioned solution, at 80 DEG C, reaction 24 is littleTime, drying and grinding becomes powder at 60 DEG C, obtains polystyrene particle;
(2) preparation of the polystyrene particle of sulfonation
4g polystyrene particle is joined in the concentrated sulfuric acid of 40ml98%, ultrasonic dispersion 30 minutes, at 50 DEG C, reaction5 hours, centrifuge washing, drying and grinding becomes powder at 60 DEG C, obtains the polystyrene particle of sulfonation;
(3) preparation of polystyrene/silver composite microballoon
The polystyrene particle of 1.5g sulfonation and 6g polyvinylpyrrolidone are joined respectively in 150ml distilled water to chamberUnder temperature, mix, the silver ammino solution that is 1.0mol/L by 10ml concentration joins in above-mentioned solution, under room temperature, stir 3 hours,At 80 DEG C, react 10 hours, drying and grinding becomes powder at 70 DEG C, obtains polystyrene/silver composite microballoon again;
(4) preparation of polystyrene/silver/Pt/Polypyrrole composite material
1.2g polystyrene/silver composite microballoon and 2.4g ferric trichloride are joined respectively in 100ml distilled water, superSound disperses 30 minutes, 80 μ l pyrrole monomers is joined in above-mentioned solution to stirring at room temperature reaction 24 hours, the vacuum drying of 70 DEG CIn case, be dried 12 hours, after taking-up, obtain polystyrene/silver/Pt/Polypyrrole composite material.
Claims (5)
1. a preparation method for polystyrene/silver/Pt/Polypyrrole composite material, is characterized in that, comprises the following steps:
(1) prepare polystyrene particle
Polyvinylpyrrolidone and distilled water are joined respectively in alcohols solvent, and stirring at room temperature is even, under logical nitrogen protection,Azodiisobutyronitrile and styrene are joined respectively in above-mentioned solution, under 50～100 DEG C, react 20～24 hours, 0～At 100 DEG C, drying and grinding becomes powder, obtains polystyrene particle, wherein azodiisobutyronitrile, polyvinylpyrrolidone, distilled water,Cinnamic mass ratio is 1:15～20:25～30:75～80;
(2) prepare the polystyrene particle of sulfonation
The polystyrene particle of preparation in step (1) is joined in the concentrated sulfuric acid to the wherein quality of polystyrene particle and dense sulphurThe mass ratio of acid is 1:15～20, and ultrasonic dispersion 10～30 minutes, at 20～60 DEG C, reacts centrifuge washing, 0 3～5 hoursAt～100 DEG C, drying and grinding becomes powder, obtains the polystyrene particle of sulfonation;
(3) prepare polystyrene/silver composite microballoon
Polystyrene particle and the polyvinylpyrrolidone of the sulfonation of preparation in step (2) are joined respectively in distilled water to chamberUnder temperature, mix, the silver ammino solution that is 0.5～1.0mol/L by concentration joins in above-mentioned solution, stirs 1～3 little under room temperatureTime, then at 50～100 DEG C, react 5～10 hours, drying and grinding becomes powder at 0～100 DEG C, obtains polystyrene/silver composite woodMaterial microballoon, wherein the mass ratio of sulfonated polystyrene, polyvinylpyrrolidone, silver ammino solution is 1:3～3.5:3～3.5;
(4) prepare polystyrene/silver/Pt/Polypyrrole composite material
Polystyrene/silver composite microballoon and the ferric trichloride of preparation in step (3) are joined respectively in distilled water, ultrasonicDisperse 10～30 minutes, pyrrole monomer is joined in above-mentioned solution, stirring at room temperature reaction 20～24 hours, 50～100 DEG CIn vacuum drying chamber, be dried 10～12 hours, after taking-up, obtain polystyrene/silver/Pt/Polypyrrole composite material, wherein pyrroles, poly-The mass ratio of styrene/silver composite material microballoon, ferric trichloride is 1:2.5～3:4.5～5.
2. preparation method as claimed in claim 1, is characterized in that the described alcohols solvent of step (1) is methyl alcohol, ethanol or fourthAlcohol, alcohols solvent consumption is 450～500 times of azodiisobutyronitrile quality.
3. preparation method as claimed in claim 1, is characterized in that the described polystyrene particle of step (2) is of a size of 500～800nm, the mass fraction of the described concentrated sulfuric acid is 97%～98%.
4. preparation method as claimed in claim 1, the polyphenyl that the consumption that it is characterized in that the described distilled water of step (3) is sulfonation150～200 times of ethene mass particle.
5. preparation method as claimed in claim 1, the consumption that it is characterized in that the described distilled water of step (4) is pyrroles's quality250～300 times.
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| CN104181144A (en) * | 2014-09-10 | 2014-12-03 | 齐鲁工业大学 | Preparation method of ferroferric oxide/polystyrene/titanium dioxide/silver nanometer composite material |
| CN105521745B (en) * | 2014-10-21 | 2018-10-16 | 中国科学院深圳先进技术研究院 | The preparation method of organic polymer-based heat conduction microballoon |
| CN105315565B (en) * | 2015-11-27 | 2018-08-03 | 湖北大学 | A kind of sulfonated polystyrene/polyaniline/nano silver complex microsphere and preparation method thereof |
| CN105806830B (en) * | 2015-12-10 | 2019-01-29 | 北京联众泰克科技有限公司 | A kind of stable HRP enzyme-catalyzed chemical luminescence substrate liquid, preparation method and application |
| CN106076413A (en) * | 2016-06-05 | 2016-11-09 | 王金明 | A kind of iso-butane produces the preparation method of metering system acid catalyst |
| CN106433406B (en) * | 2016-09-27 | 2018-09-28 | 河北工业大学 | A kind of strawberry shape hybrid microballoon and its application |
| CN107602880A (en) * | 2017-09-21 | 2018-01-19 | 上海理工大学 | A kind of preparation method of the polystyrene compound particle of poly- (2 aminothiazole) cladding |
| CN113462363A (en) * | 2021-06-22 | 2021-10-01 | 广西民族大学 | Preparation method of photo-thermal phase change energy storage micro-nano multi-scale super-hydrophobic anti-freezing particle material |
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