KR20130028995A

KR20130028995A - Smart window with reversible surface morphology

Info

Publication number: KR20130028995A
Application number: KR1020110034170A
Authority: KR
Inventors: 조정호; 김주용; 이창환; 구송희; 임호선
Original assignee: 숭실대학교산학협력단
Priority date: 2011-04-13
Filing date: 2011-04-13
Publication date: 2013-03-21

Abstract

The present invention provides a smart window having a reversible surface morphology and a method of manufacturing the same. The present invention is not complicated in the manufacturing process, does not require additional equipment, can be used for a long time stably, has a fast light transmission switching response speed, and has a selective sharpness. The present invention induces a phase separation phenomenon with a reversible solvent, the light transmittance is switched according to the change in surface morphology, the change in reversible morphology is about 90.3-0% light transmittance over the UV-NIR region, very selective control function It has a fast transmittance switching speed (about 4.7 seconds or less in both directions). In addition, the present invention can be applied to next-generation products that can save energy associated with a flexible display, a smart window for a vehicle, heating, cooling, and lighting.

Description

Smart Window with Reversible Surface Morphology

The present invention relates to a smart window having a reversible surface morphology. More specifically, the present invention relates to a smart window comprising a coating layer made of a polymer comprising a silane group and an ionic electrolyte polymer capable of ion exchange with counter ions.

One of the most important issues of the 21st century is the fact that the world will be faced with a serious shortage of energy [1]. According to the annual report of the International Energy Agency (IEA), established by the Organization for Economic Co-operation and Development (OECD), the world's primary energy consumption is an important country, an increase of 2.5% per year with the development of countries in Asia and the Middle East. In 2030, a substantial increase of about 40% will be reached [2]. This means that there is not enough energy in the near future. In particular, because limited fossil fuels provide a major source of energy to meet the world's primary energy needs, fossil fuel consumption will threaten human lives with an overall increase in energy consumption above 75%.

To address the rapidly reaching energy crisis, a number of studies have been undertaken over the last decade to develop renewable energy sources from natural resources such as sun, wind, rain, tides, biomass and geothermal [1]. In addition, current interest has focused on the efficient use of limited energy resources by improving energy efficiency, and has been carried out at lower levels of energy consumption, energy storage and energy conservation. Recently, smart windows, which can adapt light transmission in response to the surrounding environment, have been attracting attention as potential alternatives for saving energy [4].

A window that can freely adjust the transmittance of sunlight is called a smart window. Most solar transmittance control technology in the past was a method of mounting a film having a specific transmittance on the window. However, the smart window has the advantage of providing a high level of convenience to the user while significantly increasing the transmittance of solar light compared to the method of mounting a film by developing a material that can freely control the transmittance of sunlight. Thanks to these advantages, smart windows are currently used in various fields such as transportation, construction and information display, and are mainly used for housing interiors such as housing windows, living rooms, verandas, porches, and shower rooms. In particular, developed countries such as Japan, the United States, and Europe continue to develop their applications, and in some fields, they are actually being commercialized, and the market is expected to expand rapidly in the future.

Smart windows can also be applied in practical applications such as roofs, skylights, architectural or vehicle windows and interior partitions. The smart window can appropriately regulate heat exchange from the sunlight transmitted into the house, thereby suppressing unnecessary energy use through air conditioning or heating. Smart windows, for example, can keep the building from overheating by reflecting away a lot of temporary sunlight in the summer. Smart windows can also help keep the room warm by absorbing solar heat in winter. Importantly, the optical switching of the smart window regulates light bleeding or absorption by stimulating the redox conversion of chromophores in response to liquid crystal arrays, suspended particle distribution, or light irradiation, electrical charge or temperature changes [5]. However, to date, many technologies are not only chemically unstable and difficult to apply for long periods of time, but also require expensive special equipment and complex process conditions.

At present, the method of controlling the transmittance of sunlight through ordinary glass is a method of depositing a metal oxide on the surface of the glass using chemical vapor deposition (CVD) or sputtering and a material exhibiting tinting characteristics within the composition of the glass. There is a method of mixing.

However, smart windows fabricated in this way are passive, with only selective shielding or transmission capability for certain wavelength ranges, and are limited in meeting consumer demands. Therefore, glass windows can be artificially controlled to transmit visible wavelengths. The need for production is emerging.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors have tried to develop a smart window that can be used stably for a long time without using auxiliary equipment (eg, an electric device). As a result, after forming a coating layer made of a cationic electrolyte polymer, an anionic electrolyte polymer, or an ionic electrolyte polymer containing a silane group and a polymer containing a silane group on the smart window substrate, a cationic electrolyte polymer, an anion Coupling counter ions to ionic electrolyte polymers, or ionic electrolyte polymers containing both, by ion exchange reactions can not only reversibly change the surface morphology of the smart window, but also provide fast light transmission response and The present invention has been completed by confirming that a smart window with excellent sharpness can be manufactured.

Accordingly, it is an object of the present invention to provide a smart window having a reversible surface morphology.

Another object of the present invention is to provide a smart window manufacturing method having a reversible surface morphology (morphology).

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to an aspect of the present invention, the present invention provides a coating layer comprising: (a) a coating layer made of a cationic electrolyte polymer, an anionic electrolyte polymer, or a polymer including a silane group and an ionic electrolyte polymer including both thereof; And (b) provides a smart window having a reversible surface morphology (counterions) including the counterions (counterions) in combination with the ionic electrolyte polymer, the cationic electrolyte polymer, anionic electrolyte polymer or both.

The present inventors have tried to develop a smart window that can be used stably for a long time without using auxiliary equipment (eg, an electric device). As a result, after forming a coating layer made of a cationic electrolyte polymer, an anionic electrolyte polymer, or an ionic electrolyte polymer containing a silane group and a polymer containing a silane group on the smart window substrate, the cationic electrolyte polymer, When the counterions are bound to anionic electrolyte polymers or ionic electrolyte polymers including both thereof, the surface morphology of the smart window can be reversibly changed as well as fast light transmission switching response speed and selection. It was confirmed that smart windows with excellent sharpness can be manufactured.

As used herein, the term “salt” refers to a compound that is an ionic substance in which anions of an acid and a cation of a base are bonded by an electrostatic attraction.

The electrolyte polymer in the present invention includes an ionic electrolyte polymer including a cationic electrolyte polymer, an anionic electrolyte polymer or both thereof.

According to a preferred embodiment of the present invention, the ionic electrolyte polymer in the present invention is a cationic electrolyte polymer, more preferably 2-methacryloyloxy-ethyl-trimethylammonium chloride), [3-methacryloylamino-propyl] -trimethylammonium chloride, diallyldimethylammonium chloride, N, N-dimethyl-3 N-N-dimethyl-3,5-dimethylene piperidinium chloride, 4-vinyl-1-methylpyridinium bromide, allyl ammonium fluoride Lylammonium fluoride), N, N, N ′, N′-tetramethyl-N-trimethylenehexanemethylenediammonium dibromide (N, N, N ′, N′-tetramethyl-N-trimethylenehexamethylenediammonium dibromide) , 2-hydroxy-3-methacryloxy 2-hydroxy-3-methacryloxypropyl-trimethylammonium chloride and 3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride (3-chloro-2-hydroxypropyl-2 at least one cationic electrolyte polymer selected from the group consisting of -methacryloxyethyl-dimethylammonium chloride, most preferably 2-methacryloyloxy-ethyl-trimethylammonium chloride.

In the present invention, the polymer having a intermolecular group forming a copolymer with the ionic electrolyte polymer acts as a linker that binds to the substrate.

According to a preferred embodiment of the present invention, the polymer having a silane group in the present invention is 3- (trimethoxysilyl) propyl methacrylate (3- (trimethoxysilyl) propyl methacrylate), (trimethylsilyl) methanol ((trimethylsilyl) methanol) , 1- (trimethylsilyl) ethanol, 2- (trimethylsilyl) ethanol, 2- (trimethylsilyl) ethanol, 3- (trimethylsilyl) -1-propanoltriethylsilanol (3- (trimethylsilyl) -1-propanoltriethylsilanol), t - butyl-dimethyl silanol (t -butyldimethylsilanol), 5- (t - butyldimethylsilyloxy) -1-pentanol 5- (t -butyldimethylsilyloxy) -1-pentanol ), 2 -(Methyldiphenylsilyl) ethanol (2- (methyldiphenylsilyl) ethanol), trimethylsilyl acetate, trimethylsilylmethylacetate, trimethylsilylmethylacetate, methyl (trimethylsilyl) acetate, ethyl (trimethylsilyl) butyl (trimethyl chamber -), t acetate (ethyl (trimethylsilyl) acetate) ) Acetate (t -butyl (trimethylsilyl) acetate), ethyl 3- (trimethylsilyl) -propionate (ethyl 3- (trimethylsilyl) -propionate) , 2 - [( trimethylsilyl) methyl] -2-propen -1 -Yl acetate (2-[(trimethylsilyl) methyl] -2-propen-1-yl acetate), trimethylsilyl methacrylate, 2- (trimethylsilyloxy) ethyl methacrylate (2- (trimethylsilyloxy) ethyl methacrylate, methyltrimethylsilylmalonate, ethyltrimethylsilylmalonate, bis (trimethylsilyl) malonate, N, N-diethyl (trimethylsilylmethyl) amine ( N, N-diethyl (trimethylsilylmethyl) amine), N- t - butyl trimethylsilyl amine (N- t -butyltrimethylsilylamine), N, N- diethyl trimethylsilyl amine (N, N-diethyltrimethylsilylamine), 1,1'- ethylene Bis (N, N, 1,1-tetramethyl) silaneamine (1,1′-ethylenebis (N, N, 1,1-tetramethyl) silaneamine), 1- (trimeth Silyl) pyrrolidine, 4- (trimethylsilyl) morpholine, trimethylsilylacetic acid, trimethylsilylacetic acid silyl) propionic acid (3- (trimethylsilyl) propionic acid) , 3- ( tree silyl ethoxy) propionitrile (3- (triethoxysilyl) propionitrile), t - butyl-diphenyl-silyl cyanide (t -butyldiphenylsilylcyanide) and 3 -(Triethoxysilyl) propyl isocyanate is a polymer having at least one silane group selected from the group consisting of, more preferably 3- (trimethoxysilyl) propyl methacrylate, 3- (Triethoxysilyl) propionitrile, t -butyldiphenylsilylcyanide and 3- (triethoxysilyl) propyl isocyanate, a polymer having at least one silane group selected from the group consisting of, most preferably 3- (tri Methoxysilyl) propyl meth A methacrylate.

The term “copolymer” in the present invention means a polymer formed by combining molecules composed of two or more simple compounds (units forming the polymer).

According to a preferred embodiment of the present invention, the coating layer in the present invention is a copolymer of the ionic electrolyte polymer including a cationic electrolyte polymer, anionic electrolyte polymer, or both thereof and a polymer comprising a silane group is combined (copolymers) It comprises a coating layer made up.

In the present invention, the copolymer is a copolymer including linear copolymers, branched copolymers, or both, but is not limited thereto. Information on copolymers is described in detail in the following literature: Jenkins, AD meat al , “Glossary of Basic Terms in Polymer Science”, Pure Appl . Chem . 68: 22872311 (1996); Painter P. C et al , Fundamentals of Polymer Science , CRC Press, p. 14 (1997); Polymer Research Laboratory (Princeton.edu accessed Aug 15, (2008); Hadjichristidis N., Pispas S., Floudas G. Block copolymers: synthetic strategies, physical properties, and applications Wiley (2003); Bellas et al, “Universal Methodology for Block Copolymer Synthesis ”, Macromolecular Rapid Communications , 28: 1415 (2007); Bellas et al , “Block Copolymer Synthesis via Chemoselective Stepwise Coupling Reactions”, Macromolecular Chemistry and Physics , 210: 320 (2009); Self-growing material promises chip, storage advances (NetworkWorld accessed Aug 15 (2008).

When the copolymers in the present invention have a linear copolymer form, the linear copolymers in the present invention may be alternating copolymers, periodic copolymers, or stastatal copolymers. And one or more linear copolymers selected from the group consisting of block copolymers.

When the copolymer in the present invention has a branched copolymer form, the branched copolymer in the present invention may be star copolymers, brush copolymers, comb copolymers, and grafts. At least one branched copolymer selected from the group consisting of copolymers.

The term “reversible surface morphology” used in expressing the smart window in the present invention is used to express the function of recovering the opposite (ie, original morphology) after changing the morphology of the substrate surface into a specific shape. do.

In the present invention, the term "counterion" refers to an ionic molecule that exhibits a positive or negative charge that binds through ionic bonds with ions having opposite charges in order to maintain neutral charges.

The present invention has the feature that the surface morphology of the substrate can be reversibly changed by the ion exchange reaction between the cationic electrolyte polymer, the anionic polymer or both, and the ion ion reversible ion exchange reaction.

According to a preferred embodiment of the present invention, the counterion in the present invention is bis-trifluoromethane sulfonimide, thiocyanate, alkylsulfates, tosylates ), Methanesulfonate, trifluoromethanesulfonate, tetrafluoroborate, trifluoroacetate, trifluoromethane sulfonate, tetrafluoroborate (tetrafluoroborate), tetrabenzylborate, hexafluorophosphate, hexafluorophosphate, bis-pentafluoroethane sulfonimide, bis-pentafluoroethane carbonylimide pentafluoroethane carbonylimide, bis-perfluorobutane sulfonimide, bis-perfluorobutane At least one selected from the group consisting of bis-perfluorobutane carbonylimide, tris-trifluoromethane sulfonylmethide and tris-trifluoromethane carbonylmethide Counter-ion, more preferably bis-trifluoromethane sulfonide, thiocyanate, trifluoromethanesulfonate, tetrafluoroborate, trifluoroacetate, trifluoromethane sulfonate, tetrafluoroborate And at least one counterion selected from the group consisting of tetrabenzylborate, even more preferably bis-trifluoromethane sulfonide, thiocyanate, trifluoromethanesulfonate, tetrafluoroborate and trifluoroacetate One selected from the group consisting of The above counterions are most preferred and include bis-trifluoromethane sulfonide, thiocyanate or both.

The present invention can reversibly block or transmit light in all wavelength ranges without limiting the wavelength range of light (light).

According to a preferred embodiment, the present invention is 1 x 10 ² - is a smart window, the transmittance of light having a 0-91% 2 x 10 ³ ㎚ wavelength.

According to another aspect of the present invention, there is provided a smart window manufacturing method having a reversible surface morphology comprising the following steps:

(a) forming a coating layer on the substrate with a polymer comprising a ionic group and an ionic electrolyte polymer comprising a cationic electrolyte polymer, an anionic electrolyte polymer, or both thereof; And

(b) preparing a smart window having a reversible surface morphology after an ion exchange reaction with the ionic electrolyte polymer including the cationic electrolyte polymer, the anionic electrolyte polymer, or both and counterions.

The smart window having the present invention reversible surface morphology can be manufactured by the following method.

In the present invention, before performing step (a), it is preferable to use a strong oxidizing agent (for example, a pyrana solution in which sulfuric acid and hydrogen peroxide are mixed) to form a confectionary OH group on the organic material on the substrate surface.

When performing the said step (a), it is preferable to use a glass substrate or a synthetic resin substrate, More preferably, a glass substrate is used, Most preferably, a transparent glass substrate is used.

According to a preferred embodiment of the present invention, in step (a) of the present invention, the coating layer is a copolymer in which a polymer including a silane group and an ionic electrolyte polymer including a cationic electrolyte polymer, an anionic electrolyte polymer, or both thereof is combined. It includes a coating layer consisting of (copolymers). More specifically, step (a) of the present invention is a step of preparing copolymers in which a ionic electrolyte polymer including a cationic electrolyte polymer, an anionic electrolyte polymer, or both thereof and a polymer including a silane group are combined. It includes, and then the step of coating the prepared copolymer on the substrate is carried out.

In the step (a) of the present invention, the step of bonding the copolymer to the substrate to form a coating layer may be a coating method available in the art, but in the present invention, it is preferable to use a spray-casting method. desirable.

Forming the coating layer through the condensation reaction of the ionic electrolyte polymer and the substrate in the step (a) is preferably carried out for 5 to 24 hours at 50-80 ℃, more preferably at 65-70 ℃ 10-14 hours, most preferably at 70 ° C. for 12 hours.

The counter ion in step (b) of the present invention is preferably subjected to an ion exchange reaction with the ionic electrolyte polymer in the form of a salt.

In addition, in the step (b) of the present invention, when the ion exchange reaction is performed with the ionic electrolyte polymer including the cationic electrolyte polymer, the anionic electrolyte polymer, or both thereof and the counterions, the counter ions are mixed with the organic solvent. It is preferable to make it react.

According to a preferred embodiment of the present invention, step (b) in the present invention comprises the step of mixing the counter ion with the organic solvent and then carrying out an ion exchange reaction.

The organic solvent that can be used in the present invention can be used without limitation as long as it is an organic solvent that can be used in the ion exchange reaction in the art.

According to a preferred embodiment of the present invention, the organic solvent that can be used in step (b) of the present invention is one selected from the group consisting of toluene, benzene, methanol, ethanol, acetone, isopropanol, 2-methoxyethanol and acetonitrile It includes at least one organic solvent, more preferably at least one organic solvent selected from the group consisting of methanol, acetone, 2-methoxyethanol and acetonitrile.

Since the method of the present invention is an invention for manufacturing the smart window, the contents common between the two are omitted in order to avoid excessive complexity of the present specification.

The features and advantages of the present invention are summarized as follows:

(Iii) The present invention provides a smart window having a reversible surface morphology and a method of manufacturing the same.

(Ii) The present invention is not complicated in manufacturing process, does not require additional equipment, can be used stably for a long time, has a fast light transmission switching response speed, and has selective sharpness.

(Iii) The present invention induces phase separation with the reversible solvent, and the light transmittance is switched according to the change in the surface morphology. The reversible change in the morphology is selectively controlled to have a light transmittance of about 90.3-0% over the UV-NIR region. Function and very fast transmittance switching speed (less than about 4.7 seconds in both directions).

(Iii) In addition, the present invention can be applied to next-generation products that can save energy associated with flexible displays, smart windows for vehicles, heating, cooling, and lighting.

1 is a schematic of the reaction for the polymerization of poly [2- (methacryloyloxy) ethyltrimethylammonium chloride- co- 3- (tritetoxysilyl) propyl methacrylate (poly (METAC- co- TSPM)) to be.
Figure 2 shows the reversible shape change of a poly (METAC- co- TSPM) -coated smart window with switching light transmission by direct counterions exchange.
3 is an optical image of poly (METAC- co- TSPM) -deposited glass overlaid with printed paper. The reversible switching of transmittance from opaque (top) to transparent (bottom) was consistent with ion exchange from TFSI ⁻ to SCN ⁻ ions.
4 shows the glass substrate transmission spectrum in incident light through direct ion exchange. The horizontal axis represents the wavelength range and the vertical axis represents the transmittance.
Figure 5 shows the change over time of the light transmittance of the glass film according to the ion exchange between TFSI ^- and SCN ^- ions. The inner graph shows the enlarged transmittance spectrum at the initial stage.
6 shows the reversible optical switching at 550 nm of the glass sheet during 50 ion exchanges.
7 is TFSI used to OM (Optical microscopy), SEM (scanning electron microscopy) and a tapping mode AFM (atomic force microscopy) ^- is an image showing the (right) ions and the height of combined glass surface ^(L) and SCN.
8 is TFSI ^- an image represented by the (right) ions and the cut surface of the glass sheets bound SEM ^(left) and SCN.
FIG. 9 shows the results for Fourier transform infrared (FT-IR) of glass sheets bound with TFSI ⁻ (left) and SCN ⁻ (right) ions. The horizontal axis represents the wavenumber of the wavelength, and the vertical axis represents the intensity.
FIG. 10 shows the results for XPS spectra of glass coated with poly (METAC- co- TSPM) via direct ion exchange from TFSI ⁻ to SCN ⁻ ions. The horizontal axis represents binding energy and the vertical axis represents intensity.
FIG. 11 shows the light transmission spectrum of a glass substrate modified with poly (METAC- co- TSPM) bound to TFSI ^- ions in incident light simultaneously with solvent exchange.
FIG. 12 shows SEM images of glass sheets precipitated in acetone (top) and methanol (bottom), respectively.
Figure 13 shows the ¹ H-NMR spectral results of poly (METAC- co -TSPM).
FIG. 14 shows the reflectance and absorptance spectral results of glass deposited with poly (METAC- co- TSPM) coordinating with TFSI ⁻ ions. The horizontal axis represents wavelength, and the vertical axis represents reflectance (left vertical axis) and absorption (right vertical axis).
FIG. 15 shows variable transmission spectra of glass deposited with poly (METAC- co- TSPM) coordinated with TFSI ^- ions with exchange of solvent in normal incident light. The horizontal axis represents the wavelength range and the vertical axis represents the transmittance.
FIG. 16 shows SEM images of the glass surface when selectively precipitated in 2-ME (top) and methanol (bottom).

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Throughout this specification, "%" used to denote the concentration of a particular substance is intended to include solids / solids (wt / wt), solid / liquid (wt / The liquid / liquid is (vol / vol)%.

Experimental Method

All reagents and starting materials were purchased from Aldrich Chemical. After evaporating the water, METAC was purified on aluminum colum. TSPM was used without further purification. AIBN (α, -Azobisisobutyronitrile) was recrystallized from methanol.

A solution of METAC (16.56 g, 80 mmol), TSPM (4.96 g, 20 mmol) and AIBN (0.16 g, 0.1 mmol) dissolved in anhydrous 2-methoxyethanol (150 g) was placed in a round bottom flask. The solution was degassed using the freeze-thaw method and repeated three times. The sealed reaction bottle was heated at 60 ° C. and maintained for 12 hours. The polyized mixture was precipitated twice in large amounts of tetrahydrofuran (THF) and then vacuum filtered. The solid powder product was lyophilized for 24 hours in vacuo and then stored in a desiccator. The prepared polymers were dissolved in 80 wt% methanol and then deposited in micro thickness on a clean glass substrate.

Film morphology was imaged using an optical microscope (SOMTECH I-MEGASCOPE), SEM (scanning electron microscopy; JEOL JSM-6360) and AFM (atomic force microscopy; Digital Instrument Nanoscope IIIa). Fourier transform infrared (FT-IR) spectra were recorded with the FTIR-6300 spectrometer in transmittance mode with 4 cm ^-1 resolution. The light transmittance of the glass was measured using a UV-VIS-NIR spectrophotometer (JASCO V-670 spectrometer). Ion-exchange was characterized using SHIMADZU UV-3600. X-ray photoelectron spectroscopy (XPS) was performed on a Pohang Accelerator Laboratory 4B1 beam line.

Experiment result

In order to manufacture a smart window with variable light transmittance properties, poly-alkoxysilane crosslinkable polyelectrolyte copolymers were prepared by polymerizing free radicals at 60 ° C 2-methoxyethanol (2-ME). [2- (methacryloyloxy) ethyl ammonium chloride - co -3- (te tree ethoxy silyl) propyl methacrylate (poly [2- (methacryloyloxy) ethyltrimethylammonium chloride- co -3- (trimethoxysilyl) propyl methacrylate] : poly (METAC- co -TSPM)) was prepared (FIG. 1). ^[8]

The copolymer contained 22 mol% of TSPM (3- (trimethoxysilyl) propyl methacrylate) monomer (FIG. 13). PMETAC (Poly [2- (methacryloyloxy) ethyltrimethyl ammonium chloride]) was selected as a polymer electrolyte for binding and reconstitution of polymer chains reacting with organic solvents. TSPM was used as the sol-gel precursor to form a polymer network for intramolecular crosslinking. The polymer prepared in 80 wt% methanol was dissolved and then scattered to form a micron thick optically clear film on a clean glass substrate.

The spray coating method is a method for producing fine print functional materials in a wide range or curved area because it has a relatively good range with general printing technology. The transmittance of the glass coordinated with Cl ⁻ anion as the counter ion was 91.3% due to the uniformly curved surface shape (data not shown). It was very transparent to the naked eye, especially the functionalized glass, even in the vicinity of the IR region.

Reversible optical switching of smart windows is easily accomplished by counter-ion exchange selected from an array of various hydration energies. (Trifluoromethanesulfonyl) 2.5 mM lithium bis sulfone imide: by (lithium bis (trifluoromethane) sulfonimide LiTFSI) as soon as the wall geuja the methanol solution containing the salts transmitted through the polymer gel coordinated with Cl ^- ions TFSI ^- (bis ( It gradually changed to trifluoromethane) sulfonimide) ion. As shown in FIG. 3, the glass modified with poly (METAC- co- TSPM) disappeared optical transparency. These results are due to incident light blocking by the micron-sized surface structure. ^[10]

In contrast to films modified with TFSI ^- ion-coordinated polyelectrolytes, a transparent glass sheet was immersed in a 2.5 mM sodium thiocyanate (NaSCN) salt solution, resulting in a progressively transparent poly (METAC- co- TSPM) -modified glass substrate. The transmittance of the substrate has reached a wide bandwidth of more than 90.9% connecting the infrared spectrum near the ultraviolet-visible light. Poly (METAC- co -TSPM) polyelectrolyte is well dissolved SCN (thiocyanate) in ^methanol to form a uniform dull surface structure in combination with the ion.

These variable optical properties can be said to be achieved by phase separation of poly (METAC- co- TSPM) polymers coordinated with TFSI ^- ions in methanol as a result of ion exchange (Figure 2). ^[11] Importantly, the polymer electrolyte chain in the solvent is formed by the balance of the repulsive coulomb and the friendly solubility interaction. ^[12] As shown in Figure 7, OM (optical microscopy) through the image SCN ^- as the ions are present coated with a polymer electrolyte to the glass in contrast, confirmed that the surface of the glass substrate type represents a microcellular network structure of the tiered It was. In addition, it was confirmed by scanning electron microscopy (SEM) that micropores having a diameter of 510 μm on the surface apex were consistent with the OM image. AFM (Atomic force microscopy) images showed that the SCN ^- ion-containing window film exhibited a very perfect surface morphology. However, the glass sheet containing TFSI ^- ions was caused by micropores due to phase separation of the polymer electrolyte. It was confirmed that a rough surface structure was shown.

As shown in the high profile AFM image, the peak-to-peak height means the height difference at the highest and lowest pixels, increasing from 0, the height at SCN ^- ions, to 4.5 nm or less at the height at TFSI ^- ions. It became. As shown in FIG. 8, the internal structure in the cross-sectional image of the film on which the polymer electrolyte was deposited was composed of a porous network layered on the substrate. On the inner structure of the glass sheet, several holes formed by phase separation of the polymer electrolyte were clearly identified. The film thickness was extended by 2.5 times to accommodate SCN ⁻ ions due to the sponge-like structure generated by the phase separation of the polymer. This aspect can be inferred from the fact that phase separation in thin polymer films forms porous network-like structures with micron-sized pores, because the polymers incorporating TFSI ^- ions exhibit poor solubility in methanol. have. As a result, different counter anions alter specific interactions between poly (METAC- co- TSPM) and solvents, and these interactions affect the binding of the polymer electrolyte, and the smart windows exhibit variable optical properties. do.

Manipulation of light transmission through this shape change across all visible light spectra increases the basic notion of developing smart windows with optical switching properties that can transfer from sunlight to the room to block or move heat. The reversible optical switching of poly (METAC- co- TSPM) bonded glass substrates was expressed by measuring the UV-bis transmittance of the film with SCN ^- or TFSI ^- ions (FIG. 4). When the poly (METAC- co- TSPM) polyelectrolyte combines with TFSI ^- ions, scattering by microporous surface texture reflects almost 100% of the incident light, whereas the substitution with SCN ^- ions results in a window of 350-1400. Spectra of nm were allowed to pass. Such smart windows have absorbed more than 90% of the available sunlight.

In addition, we investigated the dynamics of the ion exchange reaction by in - situ measurement of UV-vis transmittance when counteranions bound to the polymer electrolyte were exchanged with TFSI ^- and SCN ^- ions or their counters. 5). The time required for the conversion of TFSI ^- ions to SCN ^- ions was faster than the reverse reaction. As TFSI ⁻ ions were replaced with SCN ⁻ ions, the light transmittance at 550 nm increased slowly to 80% within 3.8 seconds and then slowly saturated to 90.3%.

However, even at 80% transmittance, the transparent glass film could be sufficiently visually confirmed, so that the ion-exchange process was finally completed in less than 4 seconds. In contrast, the optical properties suddenly deteriorated as SCN ^- ions were replaced by TFSI ^- ions, but it took 4.7 seconds to reach 20% transmission, the point of transition from transparent to opaque. As shown in FIG. 7, the surface shape formed in the presence of TFSI ^- ions consists of a three-dimensional microporous structure, whereas the smooth surface shape formed by the bonding of SCN ^- ions is caused by the difference in time taken for conversion. I think that. Therefore, in the surface area in contact with the solution, the case where the solution containing TFSI ^- ion was contacted was larger than the solution containing the SCN ^- ion. The coordination surface of the curved SCN ^- ions had a significantly longer time for ion exchange. In addition, as shown in FIG. 6, the change in light transmittance was reversibly changed without causing significant damage even after 50 exchanges. This smart window showed a change in the transmittance at the extreme end from 88.2% transmission in SCN ^- ions to 0% transmission in TFSI ^- ions.

Measurements of water contact angles (CA), FT-IR spectra and X-ray photoemission spectroscopy (XPS) were used to confirm the ion exchange behavior of the glass substrates modified with poly (METAC- co- TSPM) brushes. Due to the fluoro atoms in the counter anions, TFSI ^- ions and poly (METAC- co -TSPM) bonds formed a hydrophobic surface. The water CA for this surface was 90 ± 2 ° and the surface was smooth. The water CA was changed to 65 ± 1 ° when TFSI ⁻ ions were replaced with SCN ⁻ ions, which showed somewhat hydrophilicity. Depending on the hydration properties of TFSI ^- and SCN ^- ions, the wettability of the curved surface on which poly (METAC- co -TSPM) was fixed was reversibly changed.

Specific FT-IR signals were measured to verify chemical changes in poly (METAC- co- TSPM) brushes simultaneously with ion exchange (FIG. 9). The presence of TFSI ^- ions in the poly (METAC- co -TSPM) brush was confirmed through the appearance of a new signal at 1356 cm ^-1 and coincided with the stretching vibration of the CF ₃ group. When the TFSI ⁻ ions were replaced with SCN ⁻ ions, the peak at 1356 cm ¹ disappeared and a new absorption peak corresponding to the SCN group appeared at 2082 cm ¹ . Reversible IR spectral change means that the ion exchange reaction occurs simultaneously with immersion in a solution containing other counter anions.

Similarly, the peaks of F 1s , C 1s and N 1s of glass coated with poly (METAC- co- TSPM) were identified by XPS measurement as a function of ion exchange (FIG. 10). ^{[13] The} F 1s spectrum is consistent with a single peak at 687.5 eV binding energy indicating the presence of fluoro atoms, with Cl ⁻ ions in the polymer brush completely replaced by TFSI ⁻ ions. The N 1s peak of the glass substrate after TFSI ⁻ ion exchange coincides with two peak components at 399.7 and 403.3 eV, and these two peaks are positive in the neutral nitrogen atom and QA ⁺ group in TFSI ⁻ ion, respectively. This is due to the charged nitrogen atom. These results indicate that Cl ⁻ coordinated polyelectrolyte gels were converted to TFSI ⁻ coordinated gels. The introduction of an ^ion-then TFSI ^- ions after the ion exchange, TFSI ^- the S 2p peak at 687.5 eV F 1s peak and 169.0 eV in the ion-alcohol corresponding to the sulfonyl group disappeared, TFSI ^- ions fall SCN Supported and appeared a new S 2p peak at the binding energy of 163.2 eV corresponding to SCN ^- ions. These results indicate that the optical switching of the anode end in the smart window originates from the exchange of counter anions, which can be reversibly exchanged with anions of different hydration energy without damaging the polymer electrolyte film.

In addition, the researchers found that dipping in acetone increases the transmittance of glass slides coated with poly (METAC- co- TSPM) containing TFSI ^- ions to almost 90.3%, and optical adjustment by solubility of smart windows through solvent exchange. It was confirmed that it means sex (Figs. 11 and 12). Even if the remaining polymer electrolyte coordinates with TFSI ^- ions, it tends to exhibit high transparency similar to that of a film coordinated with SCN ^- ions in methanol.

Surface morphology induced by phase separation is highly influenced not only by the solubility of the polymer but also by the evaporation rate of the solvent. When a glass sheet deposited with TFSI ^- ion containing poly (METAC- co- TSPM) is in contact with 2-methoxyethanol, the surface rises unevenly due to the volatility of 2-methoxyethanol that is slow and irregular with respect to the entire surface. The sheet became cloudy and translucent as covered by the ridges (FIGS. 15 and 16). However, acetone not only dissolves well in polymer electrolytes coordinated with TFSI ^- ions, but also quickly releases vapor from the top layer of the surface, resulting in a monotonous surface structure when dipping glass slides into acetone. In addition, immersion of the glass slide in ethyl acetate, which exhibited a relatively low vapor pressure, showed a similar transparency to that seen in acetone. These results indicate that the use of solvents with fast latencies can make the smart window optically transparent or opaque.

In conclusion, we demonstrated that functional smart windows can reversibly switch optical properties by making them highly opaque or transitioning to highly transparent states through the exchange of counterion ions with different hydration energies. Unprecedented anodic optical transitions are generated by the formation of microporous structure due to phase separation of the polymer electrolyte. The researchers considered two switches for the control of light propagation on smart windows: (i) direct exchange of counterions with diversified hydration energy, and (ii) control of solvophobicity in polymers. . This type of light control system can provide new options for saving heating, cooling and lighting costs through solar control delivered inside the home. Such windows are also applicable to a wide range of applications such as roof tiles, automotive and architectural windows.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

References

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Claims

(a) a coating layer comprising a ionic electrolyte polymer including a cationic electrolyte polymer, an anionic electrolyte polymer or both thereof and a polymer including a silane group; And (b) a reversible surface morphology comprising counterions that bind to the ionic electrolyte polymer comprising the cationic electrolyte polymer, the anionic electrolyte polymer, or both.

The method of claim 1, wherein the cationic electrolyte polymer is 2-methacryloyloxy-ethyl-trimethylammonium chloride, [3-methacryloylamino-propyl] -trimethyl [3-methacryloylamino-propyl] -trimethylammonium chloride, diallyldimethylammonium chloride, N, N-dimethyl-3,5-dimethylene piperidinium chloride (N, N-dimethyl- 3,5-dimethylene piperidinium chloride), 4-vinyl-1-methylpyridinium bromide, allylmonium fluoride, N, N, N ′, N ′ -Tetramethyl-N-trimethylenehexanemethylenediammonium dibromide (N, N, N ', N'-tetramethyl-N-trimethylenehexamethylenediammonium dibromide), 2-hydroxy-3-methacryloxypropyl-trimethylammonium Chloride (2-hydroxy-3-methacryloxypropyl-trimethylammonium chlor ide) and one or more cationic electrolytes selected from the group consisting of 3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride (3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride) Smart window, characterized in that the polymer.

According to claim 1, wherein the polymer having a silane group is 3- (trimethoxysilyl) propyl methacrylate (3- (trimethoxysilyl) propyl methacrylate), (trimethylsilyl) methanol ((trimethylsilyl) methanol), 1- (trimethyl 2- (trimethylsilyl) ethanol, 2- (trimethylsilyl) ethanol, 3- (trimethylsilyl) -1-propanoltriethylsilanol (3- (trimethylsilyl) -1 -propanoltriethylsilanol), t - butyl-dimethyl silanol (t -butyldimethylsilanol), 5- (t - butyldimethylsilyloxy) -1-pentanol 5- (t -butyldimethylsilyloxy) -1-pentanol ), 2- ( methyl-diphenyl Silyl) ethanol (2- (methyldiphenylsilyl) ethanol), trimethylsilylacetate, trimethylsilylmethylacetate, methyl (trimethylsilyl) acetate, ethyl (trimethylsilyl) acetate trimethylsilyl) acetate), t - butyl (trimethylsilyl) acetate (t -butyl (trimethy lsilyl) acetate), ethyl 3- (trimethylsilyl) -propionate, 2-[(trimethylsilyl) methyl] -2-propen-1-yl acetate (2- [ (trimethylsilyl) methyl] -2-propen-1-yl acetate), trimethylsilyl methacrylate, 2- (trimethylsilyloxy) ethyl methacrylate, methyltrimethylsilyl Malonate (methyltrimethylsilylmalonate), ethyltrimethylsilylmalonate, bis (trimethylsilyl) malonate, bis (trimethylsilyl) malonate, N, N-diethyl (trimethylsilylmethyl) amine (N, N-diethyl (trimethylsilylmethyl ) amine), N- t - butyl trimethylsilyl amine (N- t -butyltrimethylsilylamine), N, N- diethyl trimethylsilyl amine (N, N-diethyltrimethylsilylamine), 1,1'- ethylene bis (N, N, 1 , 1-tetramethyl) silaneamine (1,1′-ethylenebis (N, N, 1,1-tetramethyl) silaneamine), 1- (trimethylsilyl) pyrrolidine (1- (trimethylsily l) pyrrolidine), 4- (trimethylsilyl) morpholine, (trimethylsilyl) acetic acid, 3- (trimethylsilyl) propionic acid (3- ( trimethylsilyl) propionic acid), 3- (triethoxy silyl) propionitrile (3- (triethoxysilyl) propionitrile), t - butyl-diphenyl-silyl cyanide (t -butyldiphenylsilylcyanide) and 3- (triethoxysilyl) propyl isocyanate Smart window, characterized in that the polymer having at least one silane group selected from the group consisting of (3- (triethoxysilyl) propyl isocyanate).

The method of claim 1, wherein the coating layer is characterized in that it comprises a coating layer consisting of copolymers (polymers) in which the ionic electrolyte polymer including the cationic electrolyte polymer, the anionic electrolyte polymer or both thereof and the polymer comprising a silane group are combined. Smart windows.

The method of claim 1, wherein the counter ion is bis-trifluoromethane sulfonimide, thiocyanate, alkylsulfates, tosylates, methanesulfonate ( methanesulfonate, trifluoromethanesulfonate, tetrafluoroborate, trifluoroacetate, trifluoromethane sulfonate, tetrafluoroborate, tetrabenzyl Borate (tetrabenzylborate), hexafluorophosphate, bis-pentafluoroethane sulfonimide, bis-pentafluoroethane carbonylimide, bis-pentafluoroethane carbonylimide Bis-perfluorobutane sulfonimide, bis-perfluorobutane carbonylimide tane carbonylimide), tris-trifluoromethane sulfonylmethide and tris-trifluoromethane carbonylmethide, characterized in that at least one counter ion selected from the group consisting of Smart windows.

The method of claim 1, wherein the smart window is ^{1 x 10 2 - 2 x 10} 3 ㎚ smart windows, characterized in that the transmittance of light having a wavelength of 0-91%.

Smart window manufacturing method with reversible surface morphology comprising the following steps:
(a) forming a coating layer on the substrate with a polymer comprising a ionic group and an ionic electrolyte polymer comprising a cationic electrolyte polymer, an anionic electrolyte polymer, or both thereof; And
(b) preparing a smart window having a reversible surface morphology after an ion exchange reaction with the ionic electrolyte polymer including the cationic electrolyte polymer, the anionic electrolyte polymer, or both and counterions.

The method of claim 7, wherein the cationic electrolyte polymer in step (a) is 2-methacryloyloxy-ethyl-trimethylammonium chloride, [3-methacryloylamino [3-methacryloylamino-propyl] -trimethylammonium chloride, diallyldimethylammonium chloride, N, N-dimethyl-3,5-dimethylene piperidinium chloride (N , N-dimethyl-3,5-dimethylene piperidinium chloride), 4-vinyl-1-methylpyridinium bromide, allylmonium fluoride, N, N, N ', N'-tetramethyl-N-trimethylenehexanemethylenediammonium dibromide (N, N, N', N'-tetramethyl-N-trimethylenehexamethylenediammonium dibromide), 2-hydroxy-3-methacryloxy Propyl-trimethylammonium chloride (2-hydroxy-3-methacryloxypropyl-trimet hylammonium chloride) and at least one cationic group selected from the group consisting of 3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride (3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride) Smart window manufacturing method, characterized in that the electrolyte polymer.

The method of claim 7, wherein the polymer having a silane group in step (a) is 3- (trimethoxysilyl) propyl methacrylate, (trimethylsilyl) methanol , 1- (trimethylsilyl) ethanol, 2- (trimethylsilyl) ethanol, 2- (trimethylsilyl) ethanol, 3- (trimethylsilyl) -1-propanoltriethylsilanol (3- (trimethylsilyl) -1-propanoltriethylsilanol), t - butyl-dimethyl silanol (t -butyldimethylsilanol), 5- (t - butyldimethylsilyloxy) -1-pentanol 5- (t -butyldimethylsilyloxy) -1-pentanol ), 2 -(Methyldiphenylsilyl) ethanol (2- (methyldiphenylsilyl) ethanol), trimethylsilyl acetate, trimethylsilylmethylacetate, trimethylsilylmethylacetate, methyl (trimethylsilyl) acetate, ethyl (trimethylsilyl) Acetate (ethyl (trimethylsilyl) acetate), t -butyl (trimethylsilyl) acetate t- butyl (trimethylsilyl) acetate, ethyl 3- (trimethylsilyl) -propionate, 2-[(trimethylsilyl) methyl] -2-propen-1-yl acetate (2-[(trimethylsilyl) methyl] -2-propen-1-yl acetate), trimethylsilyl methacrylate, 2- (trimethylsilyloxy) ethyl methacrylate , Methyltrimethylsilylmalonate, ethyltrimethylsilylmalonate, bis (trimethylsilyl) malonate, N, N-diethyl (trimethylsilylmethyl) amine (N, N -diethyl (trimethylsilylmethyl) amine), N- t -butyltrimethylsilylamine (N- t -butyltrimethylsilylamine), N, N-diethyltrimethylsilylamine (N, N-diethyltrimethylsilylamine), 1,1'-ethylenebis (N , N, 1,1-tetramethyl) silaneamine (1,1′-ethylenebis (N, N, 1,1-tetramethyl) silaneamine), 1- (trimethylsilyl) pyrrolidine (1- (trimethylsilyl) pyrrolidine), 4- (trimethylsilyl) morpholine, (trimethylsilyl) acetic acid, 3- (trimethylsilyl) propionic acid (3- (trimethylsilyl) propionic acid), 3- (tri-ethoxy-silyl) propionitrile (3- (triethoxysilyl) propionitrile), t - butyl-diphenyl-silyl cyanide (t -butyldiphenylsilylcyanide) and 3- (tri-ethoxy Smart silyl) isocyanate (3- (triethoxysilyl) propyl isocyanate) Smart window manufacturing method characterized in that the polymer having at least one silane group selected from the group consisting of.

The method of claim 7, wherein the coating layer in step (a) is a coating layer consisting of a copolymer of a combination of a ionic electrolyte polymer containing a cationic electrolyte polymer, an anionic electrolyte polymer or both, and a polymer comprising a silane group (copolymers) Smart window manufacturing method comprising a.

8. The method of claim 7, wherein the counter ion in step (b) is bis-trifluoromethane sulfonimide, thiocyanate, alkylsulfates, tosylates. , Methanesulfonate, trifluoromethanesulfonate, tetrafluoroborate, trifluoroacetate, trifluoromethane sulfonate, tetrafluoroborate tetrafluoroborate, tetrabenzylborate, hexafluorophosphate, bis-pentafluoroethane sulfonimide, bis-pentafluoroethane carbonylimide carbonylimide), bis-perfluorobutane sulfonimide, bis-perfluorobutane carbonylimide bis-perfluorobutane carbonylimide, tris-trifluoromethane sulfonylmethide and tris-trifluoromethane carbonylmethide Smart window manufacturing method characterized in that.

The method of claim 7, wherein the step (b) comprises a step of mixing the counter ion with the organic solvent and then performing an ion exchange reaction.

The method of claim 12, wherein the organic solvent is at least one organic solvent selected from the group consisting of toluene, benzene, methanol, ethanol, acetone, isopropanol, 2-methoxyethanol and acetonitrile.

The method of claim 7, wherein the smart window is ^{1 x 10 2 - 2 x 10} 3 ㎚ smart window method, characterized in that the transmittance of light having a wavelength of 0-91%.