CN100348650C - Process for preparing hydrophobic polyimide thin film - Google Patents
Process for preparing hydrophobic polyimide thin film Download PDFInfo
- Publication number
- CN100348650C CN100348650C CNB2006100274149A CN200610027414A CN100348650C CN 100348650 C CN100348650 C CN 100348650C CN B2006100274149 A CNB2006100274149 A CN B2006100274149A CN 200610027414 A CN200610027414 A CN 200610027414A CN 100348650 C CN100348650 C CN 100348650C
- Authority
- CN
- China
- Prior art keywords
- kapton
- polyimide film
- mercaptan
- hydrophobic
- hydrophobic polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The present invention discloses a process for preparing a hydrophobic polyimide film. A polyimide film bears surface modification first to obtain a polyimide film binding silver ions on the surface; then a polyimide film whose surface is coated with nanometer silver particles is obtained by heat treatment; the hydrophobic polyimide film is obtained after molecular self-assembly decoration. As a self-assembly method of mercaptan on the nanometer silver particles is adopted, the contact angle of the surface of the polyimide film is increased to more than 125 degrees from 80 degrees; in addition, the surface roughness of the polyimide film whose surface is coated with nanometer silver particles can be controlled by changing the temperature of the polyimide film binding silver ions on the heat-treated surface, and therefore, the contact angle of the surface of the polyimide film can be regulated between 125 degrees and 168 degrees. The method of the present invention has the advantages of easy operation, easy control, simple required devices and large-scale production, and the method can be used for the fields of water prevention, fouling prevention, lossless conveying, microfluid, etc.
Description
Technical field: the present invention relates to the method that a kind of polymer surface is handled, particularly a kind of preparation process of hydrophobic polyimide film.
Background technology: wettability is one of critical nature of solid surface, characterizes with the contact angle of liquid on solid surface usually.Hydrophobicity is meant that generally the contact angle of surface and water is greater than 90 °.So-called super-hydrophobicly be meant that contact angle with water is greater than 150 °.The size of contact angle is relevant with two factors of surface geometry with Solid Surface Free Energy.Simple by reducing the method for surface free energy, as finishing fluorocarbon chain or silane chain, only can make contact angle increase to 120 °.Reach higher contact angle, then need be by making up surface geometry.As far back as 1936, Wenzel just proposed to describe the theoretical formula of quantitative relationship between contact angle and the surfaceness: cos θ '=r cos θ, and θ ' is the contact angle of uneven surface in the formula; θ is the contact angle on the smooth and uniform same material surface of Young equation definition; R is a roughness, is defined as the ratio of actual solid/liquid interfaces contact area with apparent solid/liquid interfaces contact area.Can be drawn by the Wenzel formula, for water repellent surface, roughness is big more, and contact angle is big more.The groove of Wenzel hypothesis liquid on can the complete wetting uneven surface.To nineteen forty-four, Cassie and Baxter proposed to describe liquid on uneven surface with solid the contact angle equation during with air combined the contact: the cos180 °=fcos θ+f-1 of cos θ '=fcos θ+(1-f), f is the shared ratio of the wetting solid surface of liquid in the formula, and 1-f then is the contact area proportion of liquid-to-air; The liquid-to-air contact angle is 180 °.They think the groove of liquid on sometimes can not the complete wetting uneven surface, and can be in groove residual air be arranged, and form the common compound interface of forming of solid and air, thereby the contact angle of uneven surface is increased significantly.When judging the hydrophobic effect on a surface, should consider also whether water droplet tumbles from the surface easily.Wetting for Wenzel, roughness is big more, and it is big more to tumble the angle.After roughness reached certain value, wetting to become Cassie-Baxter wetting from Wenzel for wetting regime, tumbles the angle and sharply reduce, and water droplet very easily tumbles from the surface.
In recent years, super hydrophobic surface has caused people's generally attention because basins such as antifouling in waterproof, harmless conveying, microfluid have application widely.Adopt the template extrusion process to prepare polymer nanofiber as report on magazine such as Angew.Chem.Int.Ed. and Chinese patent CN 1397668A such as Jiang Lei with super hydrophobic surface; Xu Jian etc. report that in Macromol.Rapid Commun. magazine and Chinese patent CN 1611305A utilization is separated into membrane technique and has prepared super-hydrophobic polymeric coating layer.As everyone knows, polyimide is a kind of high performance polymer material, and good insulation performance and stopping property are arranged, and it is low etc. also to have other outstanding properties such as a thermostability height, good mechanical property, specific inductivity.
Summary of the invention: the object of the present invention is to provide a kind of preparation process of hydrophobic polyimide film, and can also regulate the size of Kapton surface hydrophobicity.
A kind of preparation process of hydrophobic polyimide film of the present invention is as follows:
(1) Kapton is immersed in the sodium hydroxide or potassium hydroxide solution of 0.5～2M, soaking temperature is 20～80 ℃, soak time is 1～50 minute, the Kapton surface generates imide salts, takes out and uses washed with de-ionized water, and then immerse in the silver nitrate solution of 1～15g/L, soaking temperature is 20～80 ℃, soak time is 5～120 minutes, takes out and uses washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton with the dissimulated electricity silver ions places electrothermal oven, 200～400 ℃ of thermal treatments 30～240 minutes, obtains the Kapton of coated with silver on surface nano particle;
(3) Kapton of coated with silver on surface nano particle was immersed in the organic solvent solution that contains long-chain mercaptan self-assembly 1～72 hour, wherein the concentration of long-chain mercaptan in organic solvent is 1～10mM; Perhaps the Kapton of coated with silver on surface nano particle is used in advance the golden film of vacuum plating unit sputter one deck less than 10nm thickness, immersed in the organic solvent solution contain long-chain mercaptan self-assembly again 1～24 hour, wherein the concentration of long-chain mercaptan in organic solvent is 1～10mM; With the organic solvent flushing, obtain a kind of hydrophobic polyimide thin film then.
The polyimide that the present invention uses is the polymkeric substance that contains imide ring in the molecular structure.
The chain alkyl mercaptan that the present invention uses is the chain alkyl mercaptan of C8-C22, wherein is lauryl mercaptan or Stearyl mercaptan.
The organic solvent that the present invention uses is the alkane of dehydrated alcohol, toluene, tetrahydrofuran (THF), dimethyl formamide or C6-C16.
Preparation process of hydrophobic polyimide film of the present invention, when thermal treatment temp is 200～320 ℃, the surface of the Kapton of coated with silver on surface nano particle is the spheroidal particle of distribution uniform, and diameter is about 40nm, and the contact angle of film and water is 125 °～150 °; When thermal treatment temp is 320～400 ℃, the surface of the Kapton of coated with silver on surface nano particle is the vesicular structure that spheroidal particle is piled into, spherical particle diameters is 50～100nm, the aperture is 50～500nm, the contact angle of film and water is 150 °～168 °, and water droplet tumbles the angle less than 1～30 ° film surface; Owing to will influence hydrophobic two factor Solid Surface Free Energy and surface geometry combines, self-assembly mercaptan on silver nano-grain, the contact angle on Kapton surface is increased to more than 125 ° by 80 °, and the temperature of the Kapton by changing thermal treatment dissimulated electricity silver ions can control surface coated with silver nano particle the surfaceness of Kapton, and then the contact angle that can regulate the Kapton surface changes in 125 °～168 ° scope.
Preparation process of hydrophobic polyimide film of the present invention, the hydrophobic property of the hydrophobic polyimide thin film that obtains can not disappear through reaching bimestrial placement, and less than 200 ℃ thermal treatment its hydrophobic property all there is not influence through one hour ultraviolet lighting and temperature, its hydrophobic property is stable, and this preparation method easy and simple to handle, be easy to control, required equipment simple, can scale operation, can be used for basins such as antifouling, the harmless conveying of waterproof, microfluid.
Description of drawings
Fig. 1 is the electron scanning micrograph of the hydrophobic polyimide thin film that obtains of embodiment 1.
Fig. 2 is the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that water droplet obtains at embodiment 1.
Fig. 3 is the optics enlarged photograph that water droplet tumbles on the hydrophobic polyimide thin film surface that embodiment 1 obtains.
Fig. 4 is the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that water droplet obtains at embodiment 2.
Fig. 5 is the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that water droplet obtains at embodiment 3.
Fig. 6 is the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that water droplet obtains at embodiment 4.
Fig. 7 places water droplet optics enlarged photograph thereon after two months with the hydrophobic polyimide thin film that embodiment 4 obtains in atmosphere.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
(1) Kapton is immersed in the potassium hydroxide solution of 1M, soaking temperature is 45 ℃, soak time is 8 minutes, take out and use washed with de-ionized water, and then immerse in the silver nitrate solution of 6g/L, soaking temperature is 25 ℃, soak time is 60 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton with the dissimulated electricity silver ions places electrothermal oven, 360 ℃ of thermal treatments 120 minutes, obtains the Kapton of coated with silver on surface nano particle;
(3) with the Kapton of coated with silver on surface nano particle with vacuum plating unit in advance sputter one deck less than the golden film of 10nm thickness, immersed in the ethanolic soln contain Dodecyl Mercaptan self-assembly then 24 hours, wherein the concentration of Dodecyl Mercaptan in ethanol is 10mM, use alcohol flushing then, obtain a kind of hydrophobic polyimide thin film; Fig. 1 is the electron scanning micrograph of the hydrophobic polyimide thin film that obtains of embodiment 1, as we can see from the figure, the vesicular structure that be piled into for spheroidal particle on the surface, spherical particle diameters is 50～100nm, the aperture is 50～500nm; Fig. 2 be water droplet at the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that embodiment 1 obtains, illustrate that the hydrophobic polyimide thin film that obtains and the contact angle of water are 162 °; Fig. 3 is the optics enlarged photograph that water droplet tumbles on the hydrophobic polyimide thin film surface that embodiment 1 obtains, wherein Fig. 3 a, b, c, d are respectively water droplet 120 milliseconds of photos of being taken in every interval when tumbling, and illustrate that water droplet is 7 ° at the lip-deep angle that tumbles of hydrophobic polyimide thin film that embodiment 1 obtains.
(1) Kapton is immersed in the sodium hydroxide solution of 1.5M, soaking temperature is 40 ℃, soak time is 20 minutes, take out and use washed with de-ionized water, and then immerse in the silver nitrate solution of 2g/L, soaking temperature is 35 ℃, soak time is 100 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton with the dissimulated electricity silver ions places electrothermal oven, 200 ℃ of thermal treatments 60 minutes, obtains the Kapton of coated with silver on surface nano particle;
(3) Kapton of coated with silver on surface nano particle was immersed in the toluene solution that contains stearylmercaptan self-assembly 12 hours, wherein the concentration of stearylmercaptan in toluene is 5mM, with the toluene flushing, obtains a kind of hydrophobic polyimide thin film then; Fig. 4 be water droplet at the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that embodiment 2 obtains, illustrate that the hydrophobic polyimide thin film that obtains and the contact angle of water are 128 °.
(1) Kapton is immersed in the potassium hydroxide solution of 1M, soaking temperature is 50 ℃, soak time is 5 minutes, take out and use washed with de-ionized water, and then immerse in the silver nitrate solution of 4g/L, soaking temperature is 20 ℃, soak time is 120 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton with the dissimulated electricity silver ions places electrothermal oven, 320 ℃ of thermal treatments 120 minutes, obtains the Kapton of coated with silver on surface nano particle;
(3) Kapton of coated with silver on surface nano particle was immersed in the hexane solution that contains stearylmercaptan self-assembly 12 hours, wherein the concentration of stearylmercaptan in normal hexane is 2mM, with the normal hexane flushing, obtains a kind of hydrophobic Kapton then; Fig. 5 be water droplet at the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that embodiment 3 obtains, illustrate that the hydrophobic polyimide thin film that obtains and the contact angle of water are 145 °.With the hydrophobic polyimide thin film ultraviolet lighting 1 hour that obtains or 200 ℃ of following thermal treatments 1 hour, contact angle still was 145 °.
Embodiment 4
(1) Kapton is immersed in the potassium hydroxide solution of 1M, soaking temperature is 45 ℃, soak time is 8 minutes, take out and use washed with de-ionized water, and then immerse in the silver nitrate solution of 4g/L, soaking temperature is 30 ℃, soak time is 60 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton with the dissimulated electricity silver ions places electrothermal oven, 340 ℃ of thermal treatments 120 minutes, obtains the Kapton of coated with silver on surface nano particle;
(3) with the Kapton of coated with silver on surface nano particle with vacuum plating unit in advance sputter one deck less than the golden film of 10nm thickness, immersed in the ethanolic soln contain Dodecyl Mercaptan self-assembly then 12 hours, wherein the concentration of Dodecyl Mercaptan in ethanol is 10mM, use alcohol flushing then, obtain a kind of hydrophobic Kapton; Fig. 6 be water droplet at the lip-deep optics enlarged photograph of hydrophobic polyimide thin film that embodiment 4 obtains, illustrate that the hydrophobic polyimide thin film that obtains and the contact angle of water are 152 °; Fig. 7 places water droplet optics enlarged photograph thereon after two months with the hydrophobic polyimide thin film that embodiment 4 obtains in atmosphere, measure to such an extent that contact angle is 150 °, illustrates that the hydrophobic polyimide thin film hydrophobic property that obtains is stable.
Claims (5)
1. preparation process of hydrophobic polyimide film is characterized in that its preparation method is as follows:
(1) Kapton is immersed in the sodium hydroxide or potassium hydroxide solution of 0.5～2M, soaking temperature is 20～80 ℃, soak time is 1～50 minute, the Kapton surface generates imide salts, takes out and uses washed with de-ionized water, and then immerse in the silver nitrate solution of 1～15g/L, soaking temperature is 20～80 ℃, soak time is 5～120 minutes, takes out and uses washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton with the dissimulated electricity silver ions places electrothermal oven, 200～400 ℃ of thermal treatments 30～240 minutes, obtains the Kapton of coated with silver on surface nano particle;
(3) Kapton of coated with silver on surface nano particle was immersed in the organic solvent solution that contains long-chain mercaptan self-assembly 1～72 hour, wherein the concentration of long-chain mercaptan in organic solvent is 1～10mM; Perhaps the Kapton of coated with silver on surface nano particle is used in advance the golden film of vacuum plating unit sputter one deck less than 10nm thickness, immersed in the organic solvent solution contain long-chain mercaptan self-assembly again 1～24 hour, wherein the concentration of long-chain mercaptan in organic solvent is 1～10mM; With the organic solvent flushing, obtain a kind of hydrophobic polyimide thin film then.
2. preparation process of hydrophobic polyimide film according to claim 1 is characterized in that polyimide is the polymkeric substance that contains imide ring in the molecular structure.
3. preparation process of hydrophobic polyimide film according to claim 1 is characterized in that mercaptan is the chain alkyl mercaptan of C8-C22.
4. preparation process of hydrophobic polyimide film according to claim 1 is characterized in that mercaptan is lauryl mercaptan or Stearyl mercaptan.
5. preparation process of hydrophobic polyimide film according to claim 1 is characterized in that organic solvent is the alkane of dehydrated alcohol, toluene, tetrahydrofuran (THF), dimethyl formamide or C6-C16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100274149A CN100348650C (en) | 2006-06-08 | 2006-06-08 | Process for preparing hydrophobic polyimide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100274149A CN100348650C (en) | 2006-06-08 | 2006-06-08 | Process for preparing hydrophobic polyimide thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1858089A CN1858089A (en) | 2006-11-08 |
| CN100348650C true CN100348650C (en) | 2007-11-14 |
Family
ID=37297048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100274149A Expired - Fee Related CN100348650C (en) | 2006-06-08 | 2006-06-08 | Process for preparing hydrophobic polyimide thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100348650C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173998B (en) * | 2011-12-23 | 2016-01-13 | 中国科学院兰州化学物理研究所 | For the preparation method of the superhydrophobic woven fabric of water-oil separating |
| CN105344252B (en) * | 2015-10-27 | 2018-07-03 | 华中科技大学 | A kind of method and product for improving polyimide film antifouling property |
| CN106905556B (en) * | 2015-12-22 | 2019-09-13 | 北京奥润联创微电子科技开发有限公司 | The preparation method of hydrophobic polyimide film |
| CN105771699B (en) * | 2016-03-30 | 2018-11-02 | 华中科技大学 | It is grafted method and product that amphoteric ion improves polyimide film antifouling property |
| CN106750292A (en) * | 2016-12-28 | 2017-05-31 | 杭州福斯特光伏材料股份有限公司 | A kind of polyimides for printed electronic |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421490A (en) * | 2002-12-19 | 2003-06-04 | 中国科学院兰州化学物理研究所 | Prepn process of polyimide film |
| CN1462291A (en) * | 2001-02-27 | 2003-12-17 | 钟渊化学工业株式会社 | Polyimide film and process for producing the same |
| CN1156617C (en) * | 2001-07-18 | 2004-07-07 | 中国科学院化学研究所 | Nano polymer fibre two with super-hydrophobic surface and its preparing process |
| CN1611305A (en) * | 2003-10-28 | 2005-05-04 | 中国科学院化学研究所 | Method for preparing super hydrophobic polymeric coating using non-crystalline polymer |
| JP2006034042A (en) * | 2004-07-20 | 2006-02-02 | Yaskawa Electric Corp | Thermosetting resin composite for vacuum and its production |
-
2006
- 2006-06-08 CN CNB2006100274149A patent/CN100348650C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1462291A (en) * | 2001-02-27 | 2003-12-17 | 钟渊化学工业株式会社 | Polyimide film and process for producing the same |
| CN1156617C (en) * | 2001-07-18 | 2004-07-07 | 中国科学院化学研究所 | Nano polymer fibre two with super-hydrophobic surface and its preparing process |
| CN1421490A (en) * | 2002-12-19 | 2003-06-04 | 中国科学院兰州化学物理研究所 | Prepn process of polyimide film |
| CN1611305A (en) * | 2003-10-28 | 2005-05-04 | 中国科学院化学研究所 | Method for preparing super hydrophobic polymeric coating using non-crystalline polymer |
| JP2006034042A (en) * | 2004-07-20 | 2006-02-02 | Yaskawa Electric Corp | Thermosetting resin composite for vacuum and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1858089A (en) | 2006-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tadanaga et al. | Formation of superhydrophobic alumina coating films with high transparency on polymer substrates by the sol-gel method | |
| CN100348650C (en) | Process for preparing hydrophobic polyimide thin film | |
| CN102345127B (en) | Surface treatment method of superhydrophobic aluminum foil | |
| CN101948574B (en) | Hydrophobic chitosan film containing hydrophobic nano silicon dioxide particles and preparation method thereof | |
| Wang et al. | A robust transparent and anti-fingerprint superhydrophobic film | |
| CN109276998B (en) | High-performance Janus forward osmosis membrane and preparation method thereof | |
| CN107321583B (en) | In-situ construction method and application of micro-nano hierarchical structure super-hydrophobic surface | |
| WO2022021815A1 (en) | Embedded high-temperature-resistant transparent conductive thin film, preparation method therefor and use thereof | |
| CN101531469B (en) | Transparent lyophobic alumina film and preparation method thereof | |
| CN102702553A (en) | Method for preparing inorganic particle/epoxy resin super hydrophobic film | |
| CN104497853A (en) | Preparation method of polydimethylsiloxane (PDMS)/zinc oxide super-hydrophobic composite coating | |
| Xi et al. | A facile strategy to form three-dimensional network structure for mechanically robust superhydrophobic nanocoatings with enhanced transmittance | |
| CN114016300B (en) | Coated textile with passive radiation cooling function and preparation method thereof | |
| CN102219523B (en) | Low-temperature co-firing ceramic wave-absorbing material and preparation method thereof | |
| CN107158968B (en) | A kind of composite semipermeable membrane containing semiconductor chalcogenide, preparation method and the usage for light evaporation water | |
| CN107032634B (en) | Preparation method of glass hydrophobic film | |
| CN101891144A (en) | Titanium dioxide film with nanoscale patterns and preparation method thereof | |
| CN103212528B (en) | Preparation method for metallic titanium surface super-hydrophobic thin film | |
| Dong et al. | A Stretchable Electromagnetic Interference Shielding Fabric with Dual‐Mode Passive Personal Thermal Management | |
| CN103084321B (en) | Preparation process for nanometer perfluorocarbon composite coating | |
| Tian et al. | Mussel-inspired fabrication of an environment-friendly and self-adhesive superhydrophobic polydopamine coating with excellent mechanical durability, anti-icing and self-cleaning performances | |
| Wu et al. | Photothermal superhydrophobic cotton fabric based on silver nanoparticles cross-linked by polydopamine and polyethylenimide | |
| CN100588519C (en) | A kind of preparation method of super-hydrophobic timber | |
| CN102774085B (en) | Hydrophobic substrate and preparation method thereof | |
| CN115073016B (en) | Preparation method of high-transmittance superhydrophobic antireflection film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071114 Termination date: 20110608 |