CN101029141B - Production of de-novo hydrophobic poly-pyrrolidone film - Google Patents
Production of de-novo hydrophobic poly-pyrrolidone film Download PDFInfo
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- CN101029141B CN101029141B CN2007100373331A CN200710037333A CN101029141B CN 101029141 B CN101029141 B CN 101029141B CN 2007100373331 A CN2007100373331 A CN 2007100373331A CN 200710037333 A CN200710037333 A CN 200710037333A CN 101029141 B CN101029141 B CN 101029141B
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Abstract
Production of de novo hydrophobic poly-azole film is carried out by taking wetted conductive poly-azole with switch property as raw material, selecting non-smooth substrate BCP to increase roughness, converting oxygenated hydrophilic property into hydrophobic property, controlling corresponded oxygenated hydrophobic property, depositing poly-azole thin-layer on surface selectively by electrochemical method and changing polymerization time to obtain the final product. It can decrease experimental parameter during process of polymerization and have polymer conductive product.
Description
Technical field
The present invention relates to a kind of preparation method of de-novo hydrophobic poly-pyrrolidone film, be specifically related to utilize chemical process to handle polystyrene-poly isoprene-poly(lactic acid) [synthetic method, and molecular weight and component concentration are referring to S.Guo, Javid Rzayev, Travis S.Bailey, Andrew S.Zalusky, RobertoOlayo-Valles, Marc A.Hillmyer, Chem.Mater.18 (2006) 1719-1721.] film removal poly(lactic acid) phase, thereby obtain having the polystyrene-poly isoprene film surface of nano aperture, adopt the method for electrochemical polymerization technology at this surface selectivity deposition polypyrrole thin layer.
Background technology
Conducting polymer composite has special requirement to its surperficial wetting property when being applied to aspects such as biosensor, corrosion prevention film and artificial muscle.Up to the present, prepared and have different infiltrating conductive polymer materials, the corresponding relation according to wetting property and redox state (or dopant states) can be divided into: oxidation state-wetting ability, go back ortho states-hydrophobicity; Oxidation state-hydrophobicity is gone back ortho states-wetting ability; Oxidation state, go back ortho states-a few class materials such as full wetting ability.Technology as following bibliographical information:
(1)G.Kossmehl，M.Niemitz，Synth.Met.41-43(1991)1065-1071.
(2)L.B.Xu，W.Chen，A.Mulchandani，Y.S.Yan，Angew.Chem.Inter.Ed.44(2005)6009-6012.
(3)R.Hernandez，A.F.Diaz，R.Waltman，J.Bargon，J.Phys.Chem.88(1984)3333-3337.
Obviously, above-mentioned these a few class materials can satisfy some important use, yet, when be applied to these materials anticorrosion or water-repellancy surperficial, and during other hydrophobicity purposes, they just can't be competent fully, therefore be necessary to study a kind of in the redox potential scope omnidistance hydrophobic conducting polymer, be oxidation state, go back ortho states-full hydrophobic material, thereby satisfy above-mentioned requirements.
Summary of the invention
The technical issues that need to address of the present invention are the preparation methods that disclose a kind of de-novo hydrophobic poly-pyrrolidone film, to overcome the above-mentioned defective that prior art exists, satisfy the needs in relevant field.
Technical conceive of the present invention is such:
Contriver's imagination, select for use wetting property to have the electric polypyrrole of switch character, wetting ability when the method that utilization selects for use non-smooth substrate to improve roughness makes its oxidation state (or going back ortho states) changes hydrophobic nature into, control simultaneously its correspondence go back ortho states (or oxidation state) time hydrophobicity, thereby the oxidation state of obtaining, go back the complete hydrophobic polypyrrole material of ortho states, the method that wherein improves roughness is to utilize to have the BCP film of nano level hole as substrate, utilize electrochemical method at its surface selectivity deposition polypyrrole thin layer, control by changing parameters such as polymerization time.
Preparation method of the present invention comprises the steps:
(1) be conductive substrates with conductive glass (ITO), adopt spin coating method or method of pulling up to apply segmented copolymer polystyrene-poly isoprene-poly(lactic acid) on its surface, obtain the surface and have the conductive substrates of segmented copolymer polystyrene-poly isoprene-polylactic acid membrane, thickness is 50～300 nanometers;
Preferably, the spin speed of spin coating method employing is 500～2000 rev/mins;
Preferably, the pull rate of method of pulling up employing is 1 mm/min～30 mm/min;
(2) product that step (1) is obtained under less than 0.1 atmospheric condition, 120～170 ℃ of anneal 10～20 hours, cooling;
(3) product that step (2) is obtained be immersed in the mixing of alkaline matter, first alcohol and water molten in, corrode 20 minutes～2 hours, remove poly(lactic acid), and formation has the polystyrene-poly isoprene of nano aperture;
Said alkaline matter is selected from NaOH, KOH a kind of or its mixture wherein;
During the mixing of said alkaline matter, first alcohol and water was molten, the concentration of alkaline matter was 0.01～0.1M, and the volume ratio of first alcohol and water is: 1: 9～9: 1;
(4) product with step (3) is a working electrode, with the three-electrode system of reference electrode and supporting electrode in, in KCl and pyrroles's mixed aqueous solution, carry out polymerization by potentiostatic method, current potential is 0.6～0.9V, the time is 30 seconds～30 hours;
The preferred saturated calomel electrode of said reference electrode, the preferred platinum filament of said supporting electrode;
Or
Product with step (3) is a working electrode, with the three-electrode system of reference electrode and supporting electrode in, in KCl and pyrroles's mixed aqueous solution, scan 30 seconds～20 hours, carry out polymerization by the current potential periodic scan method;
The preferred saturated calomel electrode of said reference electrode, the preferred platinum filament of said supporting electrode;
Be limited to 0.9V on the current potential, be limited to 0.1V down;
Or
Product with step (3) is a working electrode, with two electrode systems of supporting electrode in, in KCl and pyrroles's mixed aqueous solution, carry out polymerization by galvanostatic method, current density is 1 * 10
-6～5 * 10
-4A/cm
2, the time is 30 seconds～30 hours;
The preferred platinum filament of said supporting electrode;
(5) product that obtains of cleaning step (4), obtain different aperture and roughness with the de-novo hydrophobic poly-pyrrolidone film of block copolymer film as base material;
In said KCl and pyrroles's the mixed aqueous solution, pyrroles's concentration is 0.1-1.0M, and the concentration of KCl is 0.1～0.5M.
Adopt following method to detect:
With the product that obtains 0.4～0.6V (corresponding oxidation state) and-0.4～-bias voltage of 0.65V (correspondence is gone back ortho states) under after constant 5～30 minutes, measure its contact angle to water, the result shows, oxidation state with go back ortho states and be hydrophobicity.
The invention has the advantages that: utilize the influence of substrate, reduced the degree that requires that other experiment parameter is controlled in the polymerization process the surface film growth.The product that is obtained, whole process is hydrophobic conducting polymer in the redox potential scope, promptly oxidation state, go back ortho states-full hydrophobic material, therefore, can satisfy the needs in relevant field.
Description of drawings
Fig. 1 is at the SEM picture of the polypyrrole thin layer of polystyrene-poly isoprene film surface preparation.
The contact angle test result that Fig. 2 obtains after polymerization just at polystyrene-poly isoprene film surface polypyrrole thin layer.
Embodiment
Embodiment 1
(1) is conductive substrates with conductive glass (ITO), adopts method of pulling up to apply segmented copolymer polystyrene-poly isoprene-poly(lactic acid), obtain the surface and have the conductive substrates of segmented copolymer polystyrene-poly isoprene-polylactic acid membrane on its surface; Pull rate is 5 mm/min, and thickness is 200 nanometers;
(2) product that step (1) is obtained is cooled to room temperature less than 0.1 normal atmosphere and 150 ℃ of anneal 15 hours;
(3) product that step (2) is obtained be immersed in the mixing of NaOH that concentration is 0.05M, first alcohol and water molten in (volume ratio of first alcohol and water is: 5: 5), corrode 40 minutes, remove poly(lactic acid), and formation has the PS-PI film of nano aperture;
(4) product with step (3) is a working electrode, with the three-electrode system of reference electrode saturated calomel electrode and supporting electrode platinum filament in, in 0.5M Repone K+0.1M pyrroles's the aqueous solution, carry out polymerization by the current potential periodic scan method, the electric potential scanning scope is 0.1-0.8V, scan round 10 circles; Take out, clean, dry up, obtain product.
Provided a kind of typical selective growth figure of resulting polypyrrole thin layer among Fig. 1.Adopt contact angle instrument, measure the static contact angle of this polypyrrole thin layer, wherein the size of contact angle is 101 °.
Embodiment 2
Adopt the method for embodiment 1, utilize the method (rotating speed is 2000 rev/mins) of spin coating to prepare the film of polystyrene-poly isoprene-poly(lactic acid) at conductive glass surface, and obtained polystyrene-poly isoprene-poly(lactic acid)/conductive glass combined electrode after handling 15 hours under less than 0.1atm and 150 ℃ of conditions, obtain polystyrene-poly isoprene/conductive glass combined electrode after handling in alkaline solution then, the thickness of film is 56 nanometers;
With this electrode as working electrode, respectively with saturated calomel electrode and platinum filament as reference and supporting electrode, adopt three-electrode system in 0.5M Repone K+0.1M pyrroles's solution, scan round 5 circles take out under 0.1-0.8V, clean, dry up, carry out the water infiltration property testing, provided the figure of water droplet on polypyrrole thin layer surface among Fig. 2, wherein the size of contact angle is 109.99 °.
Embodiment 3
Adopt the method for embodiment 1, utilize the method (rotating speed is 2000 rev/mins) of spin coating to prepare the film of polystyrene-poly isoprene-poly(lactic acid) at conductive glass surface, and obtained polystyrene-poly isoprene-poly(lactic acid)/conductive glass combined electrode after handling 15 hours under less than 0.1atm and 150 ℃ of conditions, obtain polystyrene-poly isoprene/conductive glass combined electrode after handling in alkaline solution then, the thickness of film is 56 nanometers;
With this electrode as working electrode, respectively with saturated calomel electrode and platinum filament as reference and supporting electrode, adopt three-electrode system in 0.1M pyrroles's solution, at 0.1-0.65V scan round 2000 circles, the time is 920 minutes, take out, clean, dry up, carry out the water infiltration property testing, wherein the size of contact angle is 95 °, and this material has hydrophobicity.
Embodiment 4
Adopt the method for embodiment 1, utilize the method (rotating speed is 2000 rev/mins) of spin coating to prepare the film of polyisoprene-polystyrene-poly lactic acid at conductive glass surface, and obtained the PI-PS-PLA/ITO combined electrode after handling 15 hours under less than 0.1atm and 170 ℃ of conditions, obtain polyisoprene-polystyrene/conductive glass combined electrode after in alkaline solution, handling then.The thickness of film is 60 nanometers;
With this electrode as working electrode, respectively with saturated calomel electrode and platinum filament as reference and supporting electrode, adopt three-electrode system in 0.1M pyrroles's solution, 0.3-0.9V scan round 2 times, the time is 30 seconds, cleans, obtain coarse polypyrrole, carry out the water infiltration property testing, wherein the size of contact angle is 98 °, and this material has hydrophobicity.
Claims (4)
1. the preparation method of de-novo hydrophobic poly-pyrrolidone film comprises the steps:
(1) is conductive substrates with conductive glass ITO (tin indium oxide),, obtains the surface and have the conductive substrates of segmented copolymer polystyrene-poly isoprene-polylactic acid membrane in its surface-coated triblock copolymer polystyrene-poly isoprene-poly(lactic acid);
(2) product that step (1) is obtained be lower than under the 0.1 atmospheric condition, 120～170 ℃ of anneal 10～20 hours, cooling;
(3) product that step (2) is obtained be immersed in the mixing of alkaline matter, first alcohol and water molten in, corrode 20 minutes～2 hours, remove poly(lactic acid), and formation has the polystyrene-poly isoprene of nano aperture;
(4) product with step (3) is a working electrode, with the three-electrode system of reference electrode and supporting electrode in, in Repone K and pyrroles's mixed aqueous solution, carry out polymerization by potentiostatic method, current potential is 0.6～0.9V, the time is 30 seconds～30 hours;
Or
Product with step (3) is a working electrode, with the three-electrode system of reference electrode and supporting electrode in, in Repone K and pyrroles's mixed aqueous solution, scan 30 seconds～20 hours, carry out polymerization by the current potential periodic scan method;
Be limited to 0.9V on the current potential, be limited to 0.1V down;
Or
Product with step (3) is a working electrode, with two electrode systems of supporting electrode in, in Repone K and pyrroles's mixed aqueous solution, carry out polymerization by galvanostatic method, current density is 1 * 10
-6～5 * 10
-4A/cm
2, the time is 30 seconds～30 hours;
(5) product that obtains of cleaning step (4), obtain different aperture and roughness with the de-novo hydrophobic poly-pyrrolidone film of block copolymer film as base material.
2. method according to claim 1 is characterized in that, adopts spin coating method or method of pulling up in conductive substrates surface-coated segmented copolymer polystyrene-poly isoprene-poly(lactic acid);
The spin speed that spin coating method adopts is 500～2000 rev/mins; The pull rate that method of pulling up adopts is 1 mm/min～30 mm/min.
3. method according to claim 1 is characterized in that, said alkaline matter is selected from a kind of or its mixture among NaOH or the KOH;
During the mixing of said alkaline matter, first alcohol and water was molten, the concentration of alkaline matter was 0.01～0.1M, and the volume ratio of first alcohol and water is: 1: 9～9: 1.
4. according to claim 1,2 or 3 described methods, it is characterized in that in said Repone K and pyrroles's the mixed aqueous solution, pyrroles's concentration is 0.1-1.0M, the concentration of Repone K is 0.1～0.5M.
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| CN101225180B (en) * | 2008-01-28 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing soakage polymer switch film based on polymer transformation temperature responsiveness |
| CN102416269A (en) * | 2011-08-23 | 2012-04-18 | 北京航空航天大学 | Micro/nano interface separation net as well as preparation method and application thereof |
| CN105478235A (en) * | 2016-01-08 | 2016-04-13 | 福建紫荆环境工程技术有限公司 | Wet electric dust precipitator and water repelling and electric conducting electrode thereof |
| CN106024414A (en) * | 2016-05-31 | 2016-10-12 | 华东理工大学 | Manganese dioxide/polypyrrole composite electrode free of binder, preparation method and application of manganese dioxide/polypyrrole composite electrode |
| CN113307969A (en) * | 2021-02-05 | 2021-08-27 | 北京航空航天大学 | Conductive polymer porous membrane and preparation method thereof |
| CN114259886A (en) * | 2021-12-28 | 2022-04-01 | 北京林业大学 | Preparation method of electrogenerated hydrophilic-hydrophobic reversible regulation composite membrane based on micron structure substrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058031A (en) * | 1991-03-26 | 1992-01-22 | 中国纺织大学 | With the polyamide-polyolefin complex is the electro-conductive material of matrix |
| CN1237652A (en) * | 1998-06-03 | 1999-12-08 | 南京大学 | Laminated composite magnetic conductive polymer film and its preparation method |
| CN1597733A (en) * | 2004-07-21 | 2005-03-23 | 东莞理工学院 | Method for preparing high-conductivity polypyrrole material |
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2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058031A (en) * | 1991-03-26 | 1992-01-22 | 中国纺织大学 | With the polyamide-polyolefin complex is the electro-conductive material of matrix |
| CN1237652A (en) * | 1998-06-03 | 1999-12-08 | 南京大学 | Laminated composite magnetic conductive polymer film and its preparation method |
| CN1597733A (en) * | 2004-07-21 | 2005-03-23 | 东莞理工学院 | Method for preparing high-conductivity polypyrrole material |
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Application publication date: 20070905 Assignee: Shanghai Bangzhong New Material Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2011310000074 Denomination of invention: Production of de-novo hydrophobic poly-pyrrolidone film Granted publication date: 20100825 License type: Exclusive License Record date: 20110526 |
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