阅读说明：本技术 一种多孔聚合物光学薄膜器件及其制备方法 (Porous polymer optical thin film device and preparation method thereof ) 是由 胡志诚 罗威 王鹏飞 于 2020-06-29 设计创作，主要内容包括：本发明公开了一种采用多孔聚合物薄膜制备的可变透过率光学薄膜器件及其制备方法。多孔聚合物光学薄膜器件,依次包括基底、第一导电膜、多孔聚合物薄膜、第二导电膜、保护膜。其中多孔聚合物薄膜(即多孔薄膜层)是夹在两个导电膜之间,其能够对电压作出响应。多孔聚合物薄膜是由多孔聚合物以及内含光控粒子的低聚物组成。多孔聚合物薄膜在施加电压的时候会导致薄膜内孔径发生变化,造成光控粒子发生位移、聚集等,造成对于光线吸收、散射、反射等改变,从而改变薄膜的透光率。本发明所述的多孔薄膜加工可以采用溶剂挥发的方式成孔,简单易操作。所用溶剂可以为较为环保的醇类溶剂,易实现大面积加工。(The invention discloses a variable transmittance optical thin film device prepared by adopting a porous polymer thin film and a preparation method thereof. The porous polymer optical film device sequentially comprises a substrate, a first conductive film, a porous polymer film, a second conductive film and a protective film. In which a porous polymer film (i.e., a porous film layer) is sandwiched between two conductive films, which are capable of responding to a voltage. The porous polymer film is composed of a porous polymer and an oligomer containing light control particles. When voltage is applied to the porous polymer film, the aperture in the film is changed, so that the light-operated particles are displaced, gathered and the like, and the light absorption, scattering, reflection and the like are changed, thereby changing the light transmittance of the film. The porous film can be processed by adopting a solvent volatilization mode to form holes, and is simple and easy to operate. The used solvent can be an alcohol solvent which is relatively environment-friendly, and large-area processing is easy to realize.)

1. A porous polymer optical thin film device is characterized by sequentially comprising a substrate, a first conductive film, a porous polymer thin film, a second conductive film and a protective film.

2. The apertured polymeric optical film device according to claim 1, wherein said substrate is one or more of a glass substrate, a polyethylene terephthalate substrate, and a polymethylmethacrylate substrate.

3. The porous polymeric optical film device of claim 1, wherein the protective film is one or more of a glass substrate, a polyethylene terephthalate substrate, and a polymethyl methacrylate substrate.

4. The porous polymer optical thin film device of claim 1, wherein the first conductive film is one or more of an ITO conductive film, a silver nanowire conductive film, a copper nanowire conductive film, and a ZnO conductive film;

the second conductive film is one or more of an ITO conductive film, a silver nanowire conductive film, a copper nanowire conductive film and a ZnO conductive film.

5. A porous polymeric optical film device according to claim 1, wherein the porous pores on the porous polymeric film have a pore size of 0.5 to 200 μm; the thickness of the porous polymer film is 60 mu m-2 mm.

6. A method of making a porous polymeric optical film device according to any of claims 1 to 5, comprising the steps of:

1) mixing a porous polymer with a pore-forming solvent to obtain a polymer solution;

2) blending the polymer solution and oligomer containing light-operated particles to obtain a pore-forming solution;

3) uniformly coating the pore-forming solution on the substrate plated with the first conductive film, and forming pores by a solvent volatilization method to obtain a substrate with a porous polymer film;

4) and placing the protective film plated with the second conductive film on a substrate with the porous polymer film to obtain the porous polymer optical film device.

7. The method of claim 6, wherein in step 1), the porous polymer is one or more selected from the group consisting of polyhydroxybutyrate-valerate, polyurethane, poly (dimethyl terephthalate), poly (butylene succinate), polystyrene, polysiloxane, polyethylene, polypropylene, polyvinyl alcohol, polyethylene-propylene copolymer, and siloxane.

8. The method of claim 6, wherein in step 1), the pore-forming solvent is one or more of ethanol, butanol, propyl ether, tetrachloroethane, methyltetrahydrofuran, propanol, toluene, and butyl acetate.

9. The method of claim 6, wherein in step 2), the oligomer is one or both of heptylmethacrylate and octylpolyacrylate;

the light control particles are one or more of titanium dioxide, nano carbon black, organic-inorganic hybrid materials and the like.

10. The method according to claim 6, wherein the step 3) of forming pores by solvent evaporation comprises:

and (3) utilizing the external thin film to be close to the first conductive film at a distance of 1-5mm to volatilize the pore-forming solvent, and continuously drying the porous thin film for 1-3 hours after the pore-forming solvent is completely volatilized.

Technical Field

The invention relates to the technical field of optical thin film devices, in particular to a porous polymer optical thin film device and a preparation method thereof.

Background

The intelligent light adjusting film can provide a plurality of functions such as heat insulation, temperature control, energy conservation and privacy, so that the intelligent light adjusting film is widely applied to the fields of buildings, houses, automobiles and the like, and has high social significance and commercial significance. The intelligent light adjusting film technology is long-term developed and extremely challenging. At present, two intelligent glass technologies based on polymer dispersed liquid crystal color change (PDLC) and an intelligent glass technology based on conductive polymer Electrochromism (EC) are mainly available on the market. The polymer dispersed liquid crystal technology is to disperse liquid crystal small molecular droplets in an organic solid polymer matrix. The free orientation of liquid crystal small molecules is realized through the change of voltage, and an opaque milky white state or a semitransparent state is realized. The PDLC intelligent glass technology has the disadvantages of unsatisfactory minimum transmittance, small maximum/minimum transmittance ratio and limited application scene. Although the conductive polymer electrochromic technology can solve the problem of the lowest transmittance of the PDLC, the conductive polymer electrochromic technology has the advantages of complex processing technology, low color-changing speed, short service life, higher cost and high price, and is only used on a few devices such as high-end sports cars, boeing planes and the like.

Disclosure of Invention

The invention aims to provide a variable transmittance optical thin film device prepared by adopting a porous polymer thin film and a preparation method thereof.

A porous polymer optical film device with adjustable transmittance sequentially comprises a substrate, a first conductive film, a porous polymer film, a second conductive film and a protective film, wherein the structure of the porous polymer optical film device comprises a transparent substrate, a front conductive film, a porous polymer film, a back conductive film and a back protective film. In which a porous polymer film (i.e., a porous film layer) is sandwiched between two conductive films, which are capable of responding to a voltage. The porous polymer film is composed of a porous polymer and an oligomer containing light control particles. When voltage is applied to the porous polymer film, the aperture in the film is changed, so that the light-operated particles are displaced, gathered and the like, and the light absorption, scattering, reflection and the like are changed, thereby changing the light transmittance of the film.

Preferably, the substrate is a transparent substrate, and is one or more of a glass substrate, a polyethylene terephthalate (PET) substrate, and a polymethyl methacrylate (PMMA) substrate.

The protective film is a transparent substrate and is one or a combination of a glass substrate, a polyethylene terephthalate (PET) substrate and a polymethyl methacrylate (PMMA) substrate.

Preferably, the front conductive film and the back conductive film may be one of conductive films of ITO, silver nanowire, copper nanowire, ZnO, etc., and combinations thereof. That is, the first conductive film (front conductive film) is one or more of an ITO conductive film, a silver nanowire conductive film, a copper nanowire conductive film, a ZnO conductive film, and the like. The second conductive film (i.e. the back conductive film) is one or more of an ITO conductive film, a silver nanowire conductive film, a copper nanowire conductive film, a ZnO conductive film and the like.

Preferably, the size of the pore diameter of the porous polymer film is 0.5-200 μm; the thickness of the porous polymer film is 60 mu m-2 mm.

A preparation method of a porous polymer optical thin film device with adjustable transmittance comprises the following steps:

1) mixing a porous polymer with a pore-forming solvent to obtain a polymer solution;

2) blending the polymer solution and oligomer containing light-operated particles to obtain a pore-forming solution;

3) uniformly coating the pore-forming solution on the substrate plated with the first conductive film, and forming pores by a solvent volatilization method to obtain a substrate with a porous polymer film;

4) and placing the protective film plated with the second conductive film on a substrate with the porous polymer film to obtain the porous polymer optical film device with adjustable transmittance.

In the step 1), the porous polymer is one or a combination of more of polyhydroxybutyrate-valerate, polyurethane, dimethyl terephthalate, polybutylene succinate, polystyrene, polysiloxane, polyethylene, polypropylene, polyvinyl alcohol, polyethylene-propylene copolymer and siloxane.

The pore-forming solvent is an organic solvent, preferably one or more of ethanol, butanol, propyl ether, tetrachloroethane, methyltetrahydrofuran, propanol, toluene, butyl acetate and the like.

In step 2), the oligomer is a polyacrylate derivative with a molecular weight of between 100-10000. The oligomer is one or two of heptyl polymethacrylate and octyl polyacrylate.

The light control particles are one or more of titanium dioxide, carbon black, organic-inorganic hybrid materials and the like.

In the step 3), pore-forming is carried out by a solvent volatilization method, which specifically comprises the following steps:

and (3) utilizing the external thin film to be close to the first conductive film at a distance of 1-5mm to volatilize the pore-forming solvent, and continuously drying the porous thin film for 1-3 hours after the pore-forming solvent is completely volatilized.

A preparation method of a porous polymer optical thin film device with adjustable transmittance comprises the following steps:

1) adding a polypropylene, polyurethane and ethanol/butanol mixed solution into a three-neck flask, fully stirring, and then condensing and refluxing for 20min at 85 ℃ to prepare a uniform solution;

the number average molecular weight of the polypropylene is 67000, and the number average molecular weight of the polyurethane is 38000;

the dosage ratio of the polypropylene to the polyurethane to the ethanol/butanol mixed solution is 2.7 g: 0.3 g: 50 mL;

the volume ratio of ethanol to butanol in the ethanol/butanol mixed solution is 1: 4;

2) blending the prepared solution in the step 1) with the titanium oxide-containing poly (octyl acrylate), and uniformly stirring;

the number average molecular weight of the octyl polyacrylate is 9500;

3) uniformly coating the solution prepared in the step 2) on the surface of a substrate plated with an ITO conductive film, enabling an external film to be close to the ITO film at a distance of 3-5mm, volatilizing an ethanol/butanol mixed solution, and continuously drying a porous film for 2 hours after the solvent is completely volatilized, wherein the aperture of the polymer film obtained by the method is 15-18um, and the porosity is 82%;

4) and (3) placing the protective film with the ITO conductive film on the porous film prepared in step 3), flattening, and exhausting air to obtain the porous polymer optical film device with adjustable transmittance.

The widest device transmittance based on the series of porous films can reach 3.1% -58%, and the transmittance difference can reach 55%, which shows that the series of optical films have better light control quality and good application prospect.

Compared with the traditional optical film with adjustable transmittance, the invention has the advantages that:

firstly, the porous film can be processed by adopting a solvent volatilization mode to form holes, and the method is simple and easy to operate. The used solvent can be an alcohol solvent which is relatively environment-friendly, and large-area rapid processing is easy to realize;

secondly, the optical film based on the porous film has a large change range of transmittance, which exceeds 50%, when voltage is applied, and has a wide application range.

And thirdly, the optical film does not generate oxidation-reduction reaction when voltage is applied, has good stability and is beneficial to practical application.

The response of the porous film under voltage is utilized, and the light transmittance of the porous film is changed to adjust the light. The porous film disclosed by the invention has the advantages of being capable of being processed quickly, wide in application range, good in stability and the like, and is suitable for future large-scale practical application.

Drawings

FIG. 1 is a schematic view of an optical film structure;

FIG. 2 is a graph showing light transmittance of the porous polymer film prepared in example 2 in a closed state and an open state;

FIG. 3 is a graph showing light transmittance of the porous polymer film prepared in example 3 in a closed state and an open state;

FIG. 4 is a graph showing light transmittance of the porous polymer film prepared in example 4 in a closed state and an open state;

FIG. 5 is a graph showing light transmittance of the porous polymer film prepared in example 8 in the closed state and in the open state;

FIG. 6 is a chromatogram and GPC results chart of the polyurethane prepared in example 2;

FIG. 7 is a chromatogram and GPC results chart of the octyl polyacrylate prepared in example 2.

FIG. 8 is a chromatogram and GPC results chart of the octyl polyacrylate prepared in example 4.

Detailed Description

As shown in fig. 1, the porous polymer optical thin film device with adjustable transmittance of the present invention sequentially includes a substrate 1, a first conductive film 2(ITO conductive film), a porous polymer thin film 3 (including light control particles 31 and polymer droplets 31), a second conductive film 4, and a protective film 5. In which a porous polymer film 3 (i.e., a porous film layer) is sandwiched between two conductive films, which are capable of responding to a voltage. The porous polymer film is composed of a porous polymer and an oligomer containing light control particles. When voltage is applied to the porous polymer film, the aperture in the film is changed, so that the light-operated particles are displaced, gathered and the like, and the light absorption, scattering, reflection and the like are changed, thereby changing the light transmittance of the film.