CN103012823A - Preparation method of bionic compound micro-sphere thin film of polyaniline and polystyrene - Google Patents
Preparation method of bionic compound micro-sphere thin film of polyaniline and polystyrene Download PDFInfo
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- CN103012823A CN103012823A CN2012105819392A CN201210581939A CN103012823A CN 103012823 A CN103012823 A CN 103012823A CN 2012105819392 A CN2012105819392 A CN 2012105819392A CN 201210581939 A CN201210581939 A CN 201210581939A CN 103012823 A CN103012823 A CN 103012823A
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Abstract
The invention provides a preparation method of a bionic compound micro-sphere thin film of polyaniline and polystyrene and relates to the technical field of preparation of a conductive macromolecular composite material. The preparation method comprises the following steps of: obtaining a polystyrene molecular layer by taking a polystyrene small sphere as a template through a solvent evaporation method; and preparing polyaniline/polystyrene compound micro-spheres on the surface by oxidization and polymerization. The structure of the polyaniline/polystyrene compound micro-spheres is similar with an insect eye; in a surfactant system, the prepared polyaniline/polystyrene compound thin film with tightly-arrayed bionic insect eyes in a hexagonal shape is uniform in shape, has high water contact angle, namely hydrophobicity, and high viscous force, and has conductivity. The preparation method provided by the invention is simple in operation and environment-friendly; and the prepared product has the conductivity of polyaniline and the toughness of polystyrene, and the sequential arraying of polystyrene enables the shape to be similar with an insect eye shape.
Description
Technical field
The present invention relates to the conductive polymer composite preparing technical field.
Background technology
Polyaniline have synthetic easy, mechanism of doping effect is unique, environmental stability good, the advantage such as can produce in a large number, but its electroconductibility, electromagnetic wave shielding etc. are vulnerable to the impact of external environment, therefore need in actual applications to solve the waterproof problem of electro-conductive material.And the polyaniline/polystyrene super hydrophobic surface has the high-performances such as anticorrosive, anti-oxidant, can greatly reduce the impact that its performance is subjected to environment so prepare super-hydrophobic polyaniline surface, thereby improves work-ing life and the practical ranges of material.In addition, polyaniline is because difficult processing treatment has limited the popularization of its practical application.
Summary of the invention
The present invention seeks to propose a kind of have good toughness, super-hydrophobic polyaniline and the bionical complex microsphere thin film technology method of polystyrene.
The present invention includes following steps:
1) the preparation compact arranged polystyrene of hexagonal and polyaniline complex microsphere film:
Behind dehydrated alcohol dispersion polystyrene sphere, through magnetic agitation, supersound process, obtain uniform suspension; Suspension is spread upon on the sheet glass of cleaning, adopt the deposition polymerization auxiliary template method, ready slide vertically inserted in the aniline solution left standstill under the normal temperature 12 ± 1 hours, then adding is the initiator A PS solution of 1:1 with the mol ratio of aniline, after reaction finishes, sheet glass with intermediate water and absolute ethanol washing, is obtained polystyrene and polyaniline complex microsphere film;
2) the super-hydrophobic complex microsphere film of preparation:
After tensio-active agent and intermediate water mixed in magnetic stirring apparatus, regulation system pH value to 2～4, with the polystyrene for preparing and the vertical insertion of polyaniline complex microsphere film wherein, 0 ℃ of lower reaction is to end, with intermediate water and dehydrated alcohol centrifuge washing, then oven dry namely gets super-hydrophobic complex microsphere film.
The present invention is take polystyrene sphere as template, obtain the polystyrene molecular layer by solvent evaporated method, prepare the polyaniline/polystyrene complex microsphere in its surface oxidation polymerization, its similar Compound Eye of Insects, in surfactant system, the compact arranged polyaniline/polystyrene laminated film of the bionic insect compound eye sexangle pattern homogeneous of preparation, the high water contact angle of tool is hydrophobicity, high viscous force, and electroconductibility is arranged.
The present invention is easy and simple to handle, environmental friendliness, and the product of making not only has the electroconductibility of polyaniline but also have the toughness of polystyrene, and the ordered arrangement of polystyrene makes its pattern class Compound Eye of Insects shape simultaneously.The adding of SDBS so that this laminated film with regard to superior performance adds ultra-hydrophobicity again, increases its work-ing life.Again by its 3D model is carried out analog calculation, for the making of super-hydrophobic coat provides strong support and theoretical direction.
Tensio-active agent of the present invention is Sodium dodecylbenzene sulfonate.
Description of drawings
Fig. 1 to Fig. 4 is the scanning electron microscope (SEM) photograph of different diameter polyaniline/polystyrene complex microsphere.
Fig. 5 to 7 is the scanning electron microscope (SEM) photograph of polystyrene/polyaniline unimolecular layer complex microsphere film under the different aniline monomer concentration.
Fig. 8 is the contact angle of different diameter polyaniline/polystyrene complex microsphere film and the graph of relation of SDBS concentration.
Fig. 9 to 12 is the scanning electron microscope (SEM) photograph of different diameter polystyrene/polyaniline individual layer complex microsphere film.
Figure 13 is the electron micrograph of polyaniline/polystyrene complex microsphere.
Figure 14 is the transmission electron microscope photo of polyaniline/polystyrene complex microsphere.
Figure 15 is the infrared spectrogram of polyaniline/polystyrene complex microsphere.
Figure 16 be the polyaniline/polystyrene complex microsphere the ultraviolet-visible light spectrogram.
Figure 17 is the size distribution figure of simple PS bead and PANI/PS complex microsphere.
Figure 18 is the roll angle state graph of water on bionic thin film.
Figure 19 is bionic thin film three-phase line of contact and Wenzel state model thereof.
Embodiment
One, step of preparation process:
1, the preparation of polystyrene sphere
8ml vinylbenzene is added in the 140ml intermediate water, fully stirred 1 hour on magnetic stirring apparatus under 70 ℃ of constant temperatures, after solution fully mixed, disposable adding 10ml contained initiator A PS (KPS) aqueous solution in the system.Keep 70 ℃ of constant temperatures, fully stirring reaction is 24 hours.After reaction finishes, use respectively intermediate water, dehydrated alcohol centrifuge washing repeatedly, it is colourless to be washed till supernatant liquor, and it is for subsequent use then product (being lower floor's white solid precipitates) to be positioned in 60 ℃ of vacuum drying ovens freeze-day with constant temperature 24 hours.
2, hexagonal close-packed arrays polystyrene/polyaniline complex microsphere thin film technology
Accurately take by weighing a certain amount of polystyrene sphere, to wherein adding dehydrated alcohol, on magnetic stirring apparatus, fully stirred 1 hour, after solution mixes, in ultrasonic device ultrasonic 15 minutes again, obtain uniform suspension.Get above-mentioned suspension with microsyringe and spread upon on the clean sheet glass dry for standby.Get a certain amount of aniline and add aqueous hydrochloric acid, fully stirred 1 hour on the magnetic stirring apparatus, after solution mixed, the vertical insertion of ready slide wherein, 0 ℃ left standstill 12 hours.Add initiator A PS solution, 0 ℃ was continued to leave standstill 12 hours.Reaction is used respectively intermediate water, absolute ethanol washing repeatedly with slide after finishing, and obtains polystyrene/polyaniline complex microsphere film.
3, super-hydrophobic complex microsphere thin film technology
Take by weighing a certain amount of tensio-active agent Sodium dodecylbenzene sulfonate in intermediate water, on magnetic stirring apparatus, fully stirred 1 hour, after solution fully mixes, regulation system pH value is with vertical the insertion wherein of hexagonal close-packed arrays polystyrene/polyaniline complex microsphere film for preparing, 0 ℃ of lower reaction 24 hours, after reaction finishes, use respectively intermediate water, dehydrated alcohol centrifuge washing repeatedly, then place under the incandescent light and dry, namely get the bionical complex microsphere film of polyaniline and polystyrene.
Two, simultaneous test:
1, fixedly the aniline amount is that 0.015M carries out compound with the different diameter polystyrene sphere respectively:
Synthesis condition: aniline [aniline]: 0.015mol ﹒ L
-1The mol ratio of initiator ammonium persulfate APS and aniline [aniline] is 1:1; The tensio-active agent Sodium dodecylbenzene sulfonate is 0.01 mol ﹒ L
-1PH=2; 25 ℃ of temperature.
From the Electronic Speculum figure of scanning as seen: the polyaniline/polystyrene complex microsphere diameter of Fig. 1 is 300 nm, and contact angle is measured WCA=158.1 °; The polyaniline/polystyrene complex microsphere diameter of Fig. 2 is 460 nm, and contact angle is measured WCA=161.1 °; The polyaniline/polystyrene complex microsphere diameter of Fig. 3 is 670 nm, and contact angle is measured WCA=149.5 °; The polyaniline/polystyrene complex microsphere diameter of Fig. 4 is 1um, and contact angle is measured WCA=144 °.
As seen: this concentration of aniline can obtain super-hydrophobic complex microsphere behind polystyrene microsphere diameter 300nm, 460 nm surface aggregates, and the hydrophobicity of 1um slightly a little less than.
2, by changing the amount of aniline monomer, aniline monomer is at same diameter polystyrene sphere surface aggregate, the electron scanning micrograph of products therefrom pattern.
Synthesis condition: PS=520nm; [APS]/[aniline]=1:1, [HCl]=2 mol/L; 0 ℃ of temperature.
The aniline monomer concentration that Fig. 5 to 7 adopts is followed successively by: 0.015M, 0.10M, 0.20M.
From Fig. 5 to 7 as seen: along with the increase of aniline monomer concentration, Surfaces of Polystyrene Microparticles polyaniline burr increases gradually.
3, the effect of Fig. 8 display surface promoting agent in the ultra-hydrophobicity regulation and control.
As shown in Figure 8: when tensio-active agent SDBS is increased to a certain degree; will form more closely hydrophobicity protective layer on polyaniline molecule chain surface; point of contact when water and Surface Contact is the hydrophobic chain of SDBS; it forms protective layer at polyaniline molecule chain surface close-packed arrays; because doping SDBS negatively charged ion increases the provide protection of SDBS hydrophobic chain and strengthens; so that bill of material mask super-hydrophobicity obtains super hydrophobic material.
Three, detect
1, the present invention utilizes polystyrene sphere to pile up layer by layer, and becomes the polyaniline nano structure array at its surface aggregate, the composite structure of preparation bionic insect compound eye.
Synthesis condition: Fig. 9 and 10 PS diameter are respectively 1 um; Figure 11 and 12 PS diameter are respectively 460 nm; [An]=0.02 M; [APS]/[An]=1:1; 0 ℃ of temperature.
By scanning electron microscope processed the product pattern is observed and the contact angle measurement, consistent with expected result.
2, Figure 13 is electron microscope and the transmission electron microscope photo of polyaniline/polystyrene complex microsphere, and Figure 14 is transmission electron microscope observation pattern photo, and Figure 15 is infrared spectrogram, and Figure 16 is ultraviolet spectrogram, and Figure 17 is size distribution figure.
3, such as Figure 18, by each state graph of the roll angle of water on bionic thin film, as seen: the higher CAO of polyaniline/polystyrene complex microsphere film (bionic thin film) hydrophobicity is up to 166 degree.
In addition, polyaniline/polystyrene complex microsphere film (bionic thin film) also has electroconductibility, and the simulation by model and energy spectrometer calculate, and draws theoretical contact angle and residing super-hydrophobic state is the Wenzel state.
Claims (2)
1. the preparation method of the bionical complex microsphere of polyaniline and polystyrene is characterized in that may further comprise the steps:
1) the preparation compact arranged polystyrene of hexagonal and polyaniline complex microsphere film:
Behind dehydrated alcohol dispersion polystyrene sphere, through magnetic agitation, ultrasonic must managing, obtain uniform suspension; Suspension is spread upon on the sheet glass of cleaning, utilize the deposition polymerization auxiliary template method, ready slide vertically inserted in the aniline solution left standstill under the normal temperature 12 ± 1 hours, then adding is the initiator A PS solution of 1:1 with the mol ratio of aniline, after reaction finishes, sheet glass with intermediate water and absolute ethanol washing, is obtained polystyrene and polyaniline complex microsphere film;
2) the super-hydrophobic complex microsphere film of preparation:
After tensio-active agent and intermediate water mixed in magnetic stirring apparatus, regulation system pH value to 2～4, with the polystyrene for preparing and the vertical insertion of polyaniline complex microsphere film wherein, 0 ℃ of lower reaction is to end, with intermediate water and dehydrated alcohol centrifuge washing, then oven dry obtains super-hydrophobic complex microsphere film.
2. the preparation method of the bionical complex microsphere of described polyaniline and polystyrene according to claim 1, it is characterized in that: described tensio-active agent is Sodium dodecylbenzene sulfonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254185A (en) * | 2015-09-15 | 2016-01-20 | 中国建材国际工程集团有限公司 | Method for preparing porous-structure VO2 film with polystyrene bead as soft template |
| CN105601958A (en) * | 2015-12-28 | 2016-05-25 | 江南大学 | Preparation of Janus polymer particle |
| CN106634351A (en) * | 2016-12-26 | 2017-05-10 | 山东精工电子科技有限公司 | Superhydrophobic coating applied to surfaces of lithium-ion battery and supercapacitor and preparation method of superhydrophobic coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225204A (en) * | 2007-12-25 | 2008-07-23 | 北京科技大学 | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres |
| CN101503489A (en) * | 2009-02-26 | 2009-08-12 | 扬州大学 | Preparation of ultra-hydrophobic property polyaniline / polystyrene composite micro-nano material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225204A (en) * | 2007-12-25 | 2008-07-23 | 北京科技大学 | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres |
| CN101503489A (en) * | 2009-02-26 | 2009-08-12 | 扬州大学 | Preparation of ultra-hydrophobic property polyaniline / polystyrene composite micro-nano material |
Non-Patent Citations (1)
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| 夏冬祥: "阴离子表面活性剂体系中超疏水聚苯胺复合材料的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 02, 15 February 2011 (2011-02-15), pages 020 - 4 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254185A (en) * | 2015-09-15 | 2016-01-20 | 中国建材国际工程集团有限公司 | Method for preparing porous-structure VO2 film with polystyrene bead as soft template |
| CN105254185B (en) * | 2015-09-15 | 2020-04-28 | 中国建材国际工程集团有限公司 | Preparation of porous structure VO by using polystyrene pellets as soft template2Method for making thin film |
| CN105601958A (en) * | 2015-12-28 | 2016-05-25 | 江南大学 | Preparation of Janus polymer particle |
| CN106634351A (en) * | 2016-12-26 | 2017-05-10 | 山东精工电子科技有限公司 | Superhydrophobic coating applied to surfaces of lithium-ion battery and supercapacitor and preparation method of superhydrophobic coating |
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Application publication date: 20130403 |