CN104693469A - Preparation method of highly ordered flexible colloidal crystal thin film - Google Patents
Preparation method of highly ordered flexible colloidal crystal thin film Download PDFInfo
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- CN104693469A CN104693469A CN201510122775.0A CN201510122775A CN104693469A CN 104693469 A CN104693469 A CN 104693469A CN 201510122775 A CN201510122775 A CN 201510122775A CN 104693469 A CN104693469 A CN 104693469A
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Abstract
The invention relates to a preparation method of a highly ordered flexible colloidal crystal thin film. The colloidal crystal thin film is based on a polyimide-coated substrate and is prepared by adding a crosslinking agent-containing mono-dispersed colloidal microsphere emulsion. The method is easy, quick, low in cost and high in success rate. The area of the polymer colloidal crystal thin film prepared on the surface of the polyimide thin film can reach the centimeter level, is defect-free, and has high reflectiveness and high mechanical strength. The method is used for various fields such as biochemical sensors, solar cells and optical instruments.
Description
Technical field
The invention belongs to crystal film field, relate to a kind of high-sequential flexible polymer colloid crystal film, particularly relate to a kind of preparation method of high-sequential flexible polymer colloid crystal film.
Background technology
To be size in 100 nanometers to issue to the inorganic or organic colloid micro ball of several microns in the effect of motivating force colloidal crystal is conigenous assembly behavior, thus forming two dimension or three-dimensional ordered structure, the colloid micro ball structure of this ordered arrangement is commonly called colloidal crystal, photonic crystal or synthetic proteins stone structure.Colloidal crystal becomes the base mateiral of New Generation Optical electrical part due to its excellent optical property; The ideal model system of some fundamemtal phenomenas can also be used as, may be used for dissolution process, the study mechanism of the hot issues such as phase in version process; In addition, colloidal crystal itself also can be used as template, and evaporation, photoetching technique etc. perfectly merge, for the preparation of patterning photonic crystal.
Just because of colloidal crystal and derivative thereof have broad application prospects, just make it in preparation accuracy controlling, chemical modification and novel application subject crossing, receive very big concern.
Colloid crystal film adopts self-assembling method to prepare usually, and as adopted evaporation-induced self-assembly in substrate of glass, plastic-substrates etc., vertical deposition self-assembly, prepared by the mode such as to spray, be coated with.And film prepared by these methods is usually difficult to big area and produces, and the shortcoming such as thin film mechanical performance is poor, film and substrate caking power are poor, be usually difficult to use in actual production.
Wearing [CN 103409801 A] such as Li Zong in the patent literature utilizes different types of polyalcohol colloid crystal to prepare the photon crystal film of high strength, utilizes and mixes appropriate linking agent to improve between colloidal crystal bonding force to obtaining high strength photon crystal film.Weak point is that adding linking agent strengthens bonding force between microballoon, but the bonding force between film and substrate is still very weak, cannot realize big area and produce.
For addressing these problems, invention has been some technical innovations.The present invention adopts the method for letex polymerization to prepare the good polymer microballoon of monodispersity, and mixes appropriate epoxies or amine monomers in the solution as linking agent, adopts single stage method by colloid crystal film growth on flexible polyimide surface.The invention has the advantages that choosing a kind of linking agent strengthens bonding force between microballoon, select a kind of super flexible substrates simultaneously, also chemically crosslinked can be produced between linking agent and substrate simultaneously, improve the bonding force between colloid crystal film and substrate, more easily realize the big area preparation of flexible photonic crystal film.The method technique is simple, reproducible, can realize the big area preparation of colloidal crystal, simultaneously because the reactive force between polyimide film and linking agent makes colloidal crystal film and polyimide bonding force strengthen.Change applying the crystalline network of colloidal crystal under suitable External Force Acting, thus affect its photon band gap and make colloid crystal film color change.This invention makes the mechanical property of colloid crystal film be improved significantly, and simultaneously big area is prepared colloid crystal film and widened its Application Areas.
Summary of the invention
The object of this invention is to provide a kind of big area, the colloid crystal film that mechanical property is good.Colloid crystal film of the present invention is based on the substrate of polyimide coating, is prepared by the monodisperse latex emulsion added containing linking agent.
The preparation method of crystal film of the present invention comprises the following steps:
(1) preparation of monodisperse latex emulsion
Add initiator and tensio-active agent by after pH buffered soln and polymers soln mixing, heated and stirred obtains monodisperse latex emulsion;
(2) preparation of super flexible colloid crystal film
First polyimide is uniformly coated on the substrate surface handled well, then form homogeneous surface after being applied to polyimide surface after linking agent being added the monodisperse latex emulsion that step (1) obtains, removing substrate obtains flexible colloid crystal film.
The concrete steps of step of the present invention (1) are: after passing into nitrogen 20 ~ 200min in three-necked bottle, add the pH buffered soln of 100 ~ 300ml, continue to pass into nitrogen 20 ~ 200min, add 10 ~ 50ml mixed with polymers solution, after continuing logical nitrogen 30 ~ 60min, add 5 ~ 50ml initiator solution and 0.001 ~ 0.01g tensio-active agent, control suitable stirring velocity, after being warming up to 50 ~ 150 DEG C, Keep agitation 5 ~ 10h discharging obtains monodisperse latex emulsion at this temperature.
The concrete steps of step of the present invention (2) are: get 5 ~ 50ml polyimide and be uniformly coated on the substrate surface handled well, be that 2% ~ 20% monodisperse latex emulsion is applied to polyimide surface by the concentration being mixed with 0.001 ~ 0.01g linking agent after 1 ~ 10h, cover to form homogeneous surface with slide glass afterwards, remove substrate after 5 ~ 50h, obtain flexible colloid crystal film.
PH buffer solvent of the present invention is selected from one or more the solution in monoammonium sulfate, sodium bicarbonate, saleratus and bicarbonate of ammonia.
Polymkeric substance of the present invention is selected from (methyl) vinylformic acid, (methyl) methyl acrylate, one or more in (methyl) butyl acrylate, vinylbenzene and trifluoroethyl methacrylate.
Linking agent of the present invention is selected from oxyethane, one or more in polydimethylsiloxane and ethylene glycol.
Initiator solution of the present invention is the aqueous solution of initiator, and its strength of solution is 20-30%; Described initiator be selected from Potassium Persulphate, ammonium persulphate one or more.
Tensio-active agent of the present invention be selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate one or more.
The above reagent that the present invention uses is as analytical pure.
Whole technological process of the present invention is simple, and without the need to specific installation and technique, obtained colloid crystal film surfacing, film-substrate cohesion is strong.Because film is flexible, the change of colloidal crystal color can be there is under suitable pulling force.The polymer colloid crystal film area of Kapton surface preparation can reach centimetre-sized zero defect, and reflectivity is high, and physical strength is high.Can be used for multiple fields such as biochemical sensor, solar cell, opticinstrument.Other features and advantages of the present invention will be set forth in the following description, and, becoming apparent from specification sheets of part, or understand by implementing the present invention.Object of the present invention and other advantages realize by structure specifically noted in write specification sheets, claims and accompanying drawing and obtain.
Accompanying drawing explanation
Accompanying drawing only for illustrating the object of specific embodiment, and does not think limitation of the present invention, and in whole accompanying drawing, identical reference symbol represents identical parts.
Fig. 1: the scanning electron microscope (SEM) photograph of colloidal crystal microsphere
Embodiment
Specifically describe the preferred embodiments of the present invention below in conjunction with accompanying drawing, wherein, accompanying drawing forms the application's part, and together with embodiments of the present invention for explaining principle of the present invention.
Embodiment 1
(1) preparation of monodisperse latex emulsion
180ml ammonium bicarbonate aqueous solution is joined in 250ml there-necked flask, logical nitrogen 30min, under constantly stirring, temperature is elevated to 85 DEG C, logical nitrogen 30min is continued after adding vinylbenzene 15ml, n-butyl acrylate 5ml, vinylformic acid 2ml, add 20% potassium persulfate solution 7ml and 0.009g Sodium dodecylbenzene sulfonate, at this temperature Keep agitation 10h discharging.
(2) preparation of super flexible colloid crystal film
Get 5ml polyimide and be uniformly coated on the substrate surface handled well, will be mixed with after 3h 0.05g epoxy resin concentration be 10% monodisperse latex emulsion even spread to polyimide surface, rear slide glass covers to form homogeneous surface.After end to be dried, substrate is removed, obtain flexible colloid crystal film.
Embodiment 2
(1) preparation of monodisperse latex emulsion
150ml ammonium bicarbonate aqueous solution is added in 250ml there-necked flask, logical nitrogen 60min, under constantly stirring, temperature is elevated to 80 DEG C, add vinylbenzene 18ml, butyl methacrylate 5ml, Acrylic Acid Monomer 1ml, logical nitrogen 60min, add 30% ammonium persulfate solution 10ml and 0.005g sodium lauryl sulphate, at this temperature Keep agitation 8h discharging.
(2) preparation of super flexible colloid crystal film
Get 10ml polyimide and be uniformly coated on the substrate surface handled well, after 5h by be mixed with 2ml glycol concentration be 5% monodisperse latex emulsion be applied to polyimide surface, rear slide glass covers to form homogeneous surface.After end to be dried, substrate is removed, obtain flexible colloid crystal film.
Embodiment 3
(1) preparation of monodisperse latex emulsion
The 180ml monoammonium sulfate aqueous solution is added in 250ml there-necked flask, logical nitrogen 30min, under constantly stirring, temperature is elevated to 70 DEG C, add vinylbenzene 16ml, butyl methacrylate 3ml, Acrylic Acid Monomer 1ml, logical nitrogen 30min, add 20% potassium persulfate solution 8ml and 0.002g Sodium dodecylbenzene sulfonate, whole system is Keep agitation 10h discharging at this temperature.
(2) preparation of super flexible colloid crystal film
Get 5ml polyimide and be uniformly coated on the substrate surface handled well, after 4h by be mixed with 3ml glycol concentration be 5% monodisperse latex emulsion be applied to polyimide surface, rear slide glass covers to form homogeneous surface.After end to be dried, substrate is removed, obtain flexible colloid crystal film.
Embodiment 4
(1) preparation of monodisperse latex emulsion
The 150ml monoammonium sulfate aqueous solution is added in 250ml there-necked flask, logical nitrogen 30min, under constantly stirring, temperature is elevated to 70 DEG C, add vinylbenzene 10ml, butyl methacrylate 5ml, Acrylic Acid Monomer 1ml, logical nitrogen 30min, add 20% ammonium persulfate solution 8ml and 0.002g Sodium dodecylbenzene sulfonate, whole system is Keep agitation 10h discharging at this temperature.
(2) preparation of super flexible colloid crystal film
Get 10ml polyimide and be uniformly coated on the substrate surface handled well, after 4h by be mixed with 5ml glycol concentration be 5% monodisperse latex emulsion be applied to polyimide surface, rear slide glass covers to form homogeneous surface.After end to be dried, substrate is removed, obtain flexible colloid crystal film.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a flexible polymer colloid crystal film for high-sequential, is characterized in that, described colloid crystal film is based on the substrate of polyimide coating, is prepared by the monodisperse latex emulsion added containing linking agent.
2. crystal film as claimed in claim 1, it is characterized in that, described crystal film is prepared by following steps:
(1) preparation of monodisperse latex emulsion
Add initiator and tensio-active agent by after pH buffered soln and polymers soln mixing, heated and stirred obtains monodisperse latex emulsion;
(2) preparation of super flexible colloid crystal film
First polyimide is uniformly coated on the substrate surface handled well, then form homogeneous surface after being applied to polyimide surface after linking agent being added the monodisperse latex emulsion that step (1) obtains, removing substrate obtains flexible colloid crystal film.
3. crystal film as claimed in claim 2, it is characterized in that, the concrete steps of step (1) are: after passing into nitrogen 20 ~ 200min in three-necked bottle, add the pH buffered soln of 100 ~ 300ml, continue to pass into nitrogen 20 ~ 200min, add 10 ~ 50ml mixed with polymers solution, after continuing logical nitrogen 30 ~ 60min, add 5 ~ 50ml initiator solution and 0.001 ~ 0.01g tensio-active agent, control suitable stirring velocity, after being warming up to 50 ~ 150 DEG C, Keep agitation 5 ~ 10h discharging obtains monodisperse latex emulsion at this temperature.
4. crystal film as claimed in claim 2, it is characterized in that, the concrete steps of step (2) are: get 5 ~ 50ml polyimide and be uniformly coated on the substrate surface handled well, be that 2% ~ 20% monodisperse latex emulsion is applied to polyimide surface by the concentration being mixed with 0.001 ~ 0.01g linking agent after 1 ~ 10h, cover to form homogeneous surface with slide glass afterwards, remove substrate after 5 ~ 50h, obtain flexible colloid crystal film.
5. crystal film as claimed in claims 3 and 4, it is characterized in that, described pH buffer solvent is selected from one or more the solution in monoammonium sulfate, sodium bicarbonate, saleratus and bicarbonate of ammonia.
6. crystal film as claimed in claims 3 and 4, it is characterized in that, described polymkeric substance is selected from (methyl) vinylformic acid, (methyl) methyl acrylate, one or more in (methyl) butyl acrylate, vinylbenzene and trifluoroethyl methacrylate.
7. crystal film as claimed in claims 3 and 4, it is characterized in that, described linking agent is selected from oxyethane, one or more in polydimethylsiloxane and ethylene glycol.
8. crystal film as claimed in claims 3 and 4, it is characterized in that, described initiator solution is the aqueous solution of initiator, and its strength of solution is 20-30%; Described initiator be selected from Potassium Persulphate, ammonium persulphate one or more.
9. crystal film as claimed in claims 3 and 4, is characterized in that, described tensio-active agent be selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate one or more.
10. a preparation method for the flexible polymer colloid crystal film of high-sequential according to claim 1, is characterized in that, the concrete operation step of described method is as follows:
(1) preparation of monodisperse latex emulsion
Add initiator and tensio-active agent by after pH buffered soln and polymers soln mixing, heated and stirred obtains monodisperse latex emulsion;
(2) preparation of super flexible colloid crystal film
First polyimide is uniformly coated on the substrate surface handled well, then form homogeneous surface after being applied to polyimide surface after linking agent being added the monodisperse latex emulsion that step (1) obtains, removing substrate obtains flexible colloid crystal film.
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| CN201510122775.0A CN104693469B (en) | 2015-03-19 | 2015-03-19 | A kind of preparation method of the flexible colloid crystal film of high-sequential |
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| CN201510122775.0A CN104693469B (en) | 2015-03-19 | 2015-03-19 | A kind of preparation method of the flexible colloid crystal film of high-sequential |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106351023A (en) * | 2016-08-25 | 2017-01-25 | 浙江理工大学 | Method for increasing stability of photonic crystal structures on textiles |
| CN106547040A (en) * | 2016-11-23 | 2017-03-29 | 大连理工大学 | A kind of high intensity crystal film with photon and preparation method thereof |
| CN106891634A (en) * | 2017-03-15 | 2017-06-27 | 大连理工大学 | A kind of inkjet printing prepares large area structure and adds lustre to the method for pattern |
| CN111363393A (en) * | 2020-03-24 | 2020-07-03 | 珠海光驭科技有限公司 | Coating composition for preparing photonic crystal film, photonic crystal film and preparation method |
| CN113433727A (en) * | 2021-06-18 | 2021-09-24 | 珠海光驭科技有限公司 | Electrochromic optical film and preparation method thereof |
| CN114002422A (en) * | 2021-10-15 | 2022-02-01 | 乐凯医疗科技有限公司 | Multilayer film dry chemical reagent sheet for biochemical analysis |
| CN115453666A (en) * | 2022-09-21 | 2022-12-09 | 上海工程技术大学 | Full-spectrum photonic crystal film with easily-regulated color and preparation method thereof |
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| CN101338447A (en) * | 2008-08-29 | 2009-01-07 | 哈尔滨工业大学 | Method for self-assembling photonic crystal |
| CN103409801A (en) * | 2013-08-13 | 2013-11-27 | 厦门大学 | Preparation method of high-strength crosslinked polymer photonic crystal film |
| CN104018141A (en) * | 2014-06-13 | 2014-09-03 | 哈尔滨工业大学 | Preparation method and application of flexible and durable super-hydrophobic coating |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101338447A (en) * | 2008-08-29 | 2009-01-07 | 哈尔滨工业大学 | Method for self-assembling photonic crystal |
| CN103409801A (en) * | 2013-08-13 | 2013-11-27 | 厦门大学 | Preparation method of high-strength crosslinked polymer photonic crystal film |
| CN104018141A (en) * | 2014-06-13 | 2014-09-03 | 哈尔滨工业大学 | Preparation method and application of flexible and durable super-hydrophobic coating |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106351023A (en) * | 2016-08-25 | 2017-01-25 | 浙江理工大学 | Method for increasing stability of photonic crystal structures on textiles |
| CN106547040A (en) * | 2016-11-23 | 2017-03-29 | 大连理工大学 | A kind of high intensity crystal film with photon and preparation method thereof |
| CN106547040B (en) * | 2016-11-23 | 2019-02-12 | 大连理工大学 | A kind of high intensity crystal film with photon and preparation method thereof |
| CN106891634A (en) * | 2017-03-15 | 2017-06-27 | 大连理工大学 | A kind of inkjet printing prepares large area structure and adds lustre to the method for pattern |
| CN106891634B (en) * | 2017-03-15 | 2019-04-16 | 大连理工大学 | A kind of inkjet printing prepares large area structure and adds lustre to the method for pattern |
| CN111363393A (en) * | 2020-03-24 | 2020-07-03 | 珠海光驭科技有限公司 | Coating composition for preparing photonic crystal film, photonic crystal film and preparation method |
| CN111363393B (en) * | 2020-03-24 | 2021-05-11 | 珠海光驭科技有限公司 | Coating composition for preparing photonic crystal film, photonic crystal film and preparation method |
| CN113433727A (en) * | 2021-06-18 | 2021-09-24 | 珠海光驭科技有限公司 | Electrochromic optical film and preparation method thereof |
| CN114002422A (en) * | 2021-10-15 | 2022-02-01 | 乐凯医疗科技有限公司 | Multilayer film dry chemical reagent sheet for biochemical analysis |
| CN114002422B (en) * | 2021-10-15 | 2024-03-29 | 乐凯医疗科技有限公司 | Multi-layer membrane dry chemical reagent tablet for biochemical analysis |
| CN115453666A (en) * | 2022-09-21 | 2022-12-09 | 上海工程技术大学 | Full-spectrum photonic crystal film with easily-regulated color and preparation method thereof |
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