KR101066094B1 - New copolymer of terthiophene with 3,4 ethylenedioxypyrrole, method for producing the copolymer, and electrochromic products - Google Patents

Abstract

The present invention relates to an electrochromic material, and more specifically, a novel copolymer of terthiophene and ethylenedioxypyrrole capable of realizing three or more colors according to an applied voltage, a method of preparing the copolymer, and the air The present invention relates to an electrochromic product including coalescence.

TH-co-EDOP copolymer of the present invention can not only implement three or more colors according to the applied voltage, but also has a memory effect of maintaining the color even when no voltage is applied, thereby reducing power consumption and switching time. Has a very good excellent effect.

Tersiophene, ethylenedioxypyrrole, copolymer, electrochromic

Description

New copolymer of terthiophene and ethylenedioxypyrrole, preparation method of the copolymer and electrochromic product comprising the copolymer TECHNICAL FIELD: New copolymer of terthiophene with 3,4 ethylenedioxypyrrole, method for producing the copolymer, and electrochromic products }

The present invention relates to an electrochromic material, and more specifically, a novel copolymer of terthiophene and ethylenedioxypyrrole capable of realizing three or more colors according to an applied voltage, a method of preparing the copolymer, and the air The present invention relates to an electrochromic product including coalescence.

Electrochromic is the reversible control of the color of a material by electrochemical redox reactions, which results in a change in color due to changes in energy absorption due to electron transfer accompanying oxidation or reduction.

Electrochromic materials can be largely divided into inorganic and organic, and until now mainly inorganic (WO ₃ , IrO _2, etc.) has been studied and used. Recently, there is a greater interest in the redevelopment of electrochromic by organic systems, because of the fast switching type and discoloration efficiency. In particular, the electrochromic properties of the conductive polymers have attracted much interest because they can be applied to electrochromic glass windows called smart windows, devices for controlling the transmitted light, and displays for next-generation low voltage displays.

Looking at the known electrochromic technology in more detail are as follows.

First, known electrochromic solution systems contain a pair of redox materials, which color after reduction or oxidation in a solvent and form positive or negatively charged and chemically reactive free radicals, for example for a long time There are known viologen systems. The redox material pairs used herein are respectively reducing and oxidizing materials. Both are colorless or only weak. When voltage is applied, one is reduced and the other is oxidized, at least one of which develops. After the power is cut off, the two original redox materials are re-formed, causing them to discolor or fade.

US Patent US4902108 discloses an electrochromic system in which a suitable pair of redox materials has at least two chemically reversible reducing waves in the cyclic voltammetry, and the oxidizing materials have at least two correspondingly chemically reversible oxidation waves. Doing. This type of system is mainly suitable for automotive rearview mirrors, which can be blurred. Because these are solution based, it is not possible to use them in electrochromic windows under normal circumstances.

In addition, systems are known in which the actual electrochromic redox pairs are dispersed in the polymer matrix (see for example WO 96/03475). In this case, the undesirable effect of sedimentation is suppressed.

Combinations of inorganic electrochromic components such as WO ₃ , NiO or IrO ₂ are likewise known and are possible as components of electrochromic windows (see eg US 5 657 149, Electronique International No. 276, 16 (1997)). ).

Such inorganic electrochromic components can be applied to the conductive material only by vapor deposition, sputtering or sol-gel techniques. As a result, this type of system is very expensive to manufacture.

In the context of efforts to replace inorganic components with organic polymer components, electrochromic systems based on, for example, electrically conductive polymer polyaniline (PANI) and complementary electrochromic material WO ₃ are known (for example , BPJelle, G. Hagen, J. Electrochem. Soc., Vol. 140, No. 12, 3560 (1993)).

Attempts have also been made to use systems without inorganic components, which are expected to function as electrochromic components complementary to substituted poly (3,4-ethylenedioxythiophenes) in which the ITO or SnO ₂ layer (counter electrode) is replaced. (US5187608).

In particular, the electrochromic properties of the conductive polymers have attracted a lot of interest because they can be applied to electrochromic glass windows called smart windows, devices for controlling transmitted light, and displays for next generation low voltage displays.

Until now, many researches on organic electrochromic materials have been proposed to realize various colors by using thiophene and pyrrole derivatives, but there are still problems that do not satisfy the characteristics of efficient electrochromic materials.

In other words, organic materials that are likely to be efficient electrochromic materials are low band gap polymers, which are not easily degraded according to the redox switching cycle and operate at the lowest potential possible. Because this is possible.

The present inventors have completed the present invention by synthesizing a novel polymer that satisfies the characteristics as an efficient electrochromic material as a result of research efforts to solve the above problems.

Accordingly, an object of the present invention is to satisfy the characteristics as an efficient electrochromic material, that is, a low band gap polymer, which is not easily degraded according to the redox switching cycle, The present invention provides a novel copolymer of tersiophene and ethylenedioxypyrrole capable of operating at a potential, a method of preparing the copolymer, and an electrochromic product including the copolymer.

Another object of the present invention is to prepare a novel terthiophene and ethylene dioxypyrrole copolymer, a method for preparing the copolymer and the copolymer that can be easily prepared as well as prepared at a low potential in the electrochemical method. It is to provide an electrochromic product containing.

Another object of the present invention is not only to implement three or more colors according to the voltage applied, but also has a memory effect to maintain the color even when voltage is not applied, thereby reducing power consumption and having a very fast switching time. It is to provide a copolymer of tersiophene and ethylenedioxypyrrole, a method for preparing the copolymer, and an electrochromic product including the copolymer.

The objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention provides a TH-co-EDOP copolymer characterized by discoloration when a voltage is applied as a copolymer of terthiophene and 3,4-ethylenedioxypyrrole.

In a preferred embodiment, the copolymer has the structure

constitutional formula

In a preferred embodiment, the copolymer can implement three or more colors depending on the voltage applied.

In a preferred embodiment, the copolymer is sequentially discolored to dark blue, brown and red-orange while voltage is applied to the copolymer and then reduced to OV.

In a preferred embodiment, the copolymer maintains discolored color even when the voltage applied to the copolymer is maintained at 0V.

In a preferred embodiment, discoloration by the voltage applied to the copolymer is reversible.

In addition, the present invention comprises the steps of adding a terceophene and 3,4-ethylene dioxypyrrole after putting the electrolyte solution in the electrolytic cell provided with a three-electrode system; Performing cyclic voltammetry using the three-electrode system; And it provides a TH-co-EDOP copolymer manufacturing method comprising the step of forming a TH-co-EDOP copolymer in the form of a film on the test electrode surface.

In a preferred embodiment, the three-electrode system includes a reference electrode as a platinum electrode, a counter electrode as a silver / silver chloride electrode, and a test electrode as an ITO electrode.

In a preferred embodiment, the electrolyte solution is one or more of tetrabutyl ammonium perchlorate (TBAP), LiClO ₄ , NaClO ₄ is dissolved in a solvent containing acetonitrile at a concentration of 0.05 to 0.2M.

In a preferred embodiment, the molar ratio of terthiophene and 3,4-ethylenedioxypyrrole added to the electrolyte solution is 1: 100.

The present invention also includes a TH-co-EDOP copolymer according to any one of claims 1 to 6 or a TH-co-EDOP copolymer prepared by the method of any one of claims 7 to 10. Provide electrochromic products.

In a preferred embodiment, the electrochromic product is a vehicle glass. It can be applied to any of building glass, mirrors, display elements, optical system elements, or EMI shielding elements.

The present invention has the following excellent effects.

First, the novel terthiophene and copolymer of ethylenedioxypyrrole and the copolymer prepared by the method of the present invention satisfy the characteristics as an efficient electrochromic material, so that a low band gap polymer As a result, it is not easily degraded according to the redox switching cycle and can be operated at a low potential.

In addition, the copolymer can be easily prepared by the method of preparing the copolymer of the present invention, and can be prepared even at a low potential during the preparation by the electrochemical method.

In addition, the copolymer of the present invention and the electrochromic product including the copolymer may not only realize three or more colors according to the applied voltage, but also have a memory effect of maintaining color even when voltage is not applied, thereby reducing power consumption. It can be reduced and has a good function because the switching time is very fast.

The terms used in the present invention were selected as general terms as widely used as possible, but in some cases, the terms arbitrarily selected by the applicant are included. In this case, the meanings described or used in the detailed description of the present invention are considered, rather than simply the names of the terms. The meaning should be grasped.

Hereinafter, with reference to the accompanying drawings and preferred embodiments will be described in detail the technical configuration of the present invention.

However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals designate like elements throughout the specification.

First, the present invention relates to a copolymer of tersiophene and 3,4-ethylenedioxypyrrole, that is, a TH-co-EDOP copolymer, which is stable because it has an electron donor and an acceptor at the same time.

[Reaction Scheme]

Where TH = terthiophene and EDOP = 3,4-ethylenedioxypyrrole.

The scheme shows the structural formula of TH-co-EDOP copolymer obtained by copolymerizing terthiophene and 3,4-ethylenedioxypyrrole by electrochemical method.

In addition, the TH-co-EDOP copolymer of the present invention is characterized in that the organic electrochromic compound having a characteristic that changes color when a voltage is applied, in particular, the color change generated by the application of voltage is reversible.

TH-co-EDOP copolymer of the present invention can implement three or more colors according to the applied voltage, in detail, the voltage is applied to the TH-co-EDOP copolymer of the present invention is reduced to OV after 1.5V applied The copolymers are sequentially discolored to dark blue, brown and red-orange.

In addition, even when the voltage applied to the copolymer is maintained at 0V, that is, even when no voltage is applied, the color not only can reduce power consumption, but also has an excellent characteristic that the response time, that is, switching time is 0.5 seconds is very fast.

Such TH-co-EDOP copolymer of the present invention comprises the steps of adding the tersiophene and 3,4-ethylenedioxypyrrole after putting the electrolyte solution in the electrolytic cell with a three-electrode system; Performing cyclic voltammetry using the three-electrode system; And it may be obtained through the step of forming a TH-co-EDOP copolymer in the form of a film on the test electrode surface.

In the three-electrode system, the reference electrode is a platinum electrode, the counter electrode is a silver / silver chloride electrode, and the test electrode is an ITO electrode, and the electrolyte solution is one or more of tetrabutylammonium perchlorate (TBAP), LiClO ₄ , and NaClO ₄ . Although dissolved in a solvent containing acetonitrile at a concentration of 0.05 to 0.2M, it is more preferable to have a concentration of 0.1M. In addition, the molar ratio of terthiophene and 3,4-ethylenedioxypyrrole added to the electrolyte solution is not limited as long as it is within the range in which the copolymer can be formed. It is preferable that it is: 100.

On the other hand, the TH-co-EDOP copolymer of the present invention may be prepared by the electrochemical method exemplified in the above description and the examples described later, but it is limited to manufacturing by other known methods including chemical methods. no.

Example

After cleaning the ITO electrode in an electrolytic cell equipped with a three-electrode system in which the reference electrode is a platinum electrode, the counter electrode is a silver / silver chloride electrode, and the test electrode is an ITO electrode, and then the MeCN solution [0.1M Tetrabutylammonium perchlorate (TBAP) ) Using acetonitrile as a solvent, 0.1 mM terthiophen and 10 mM 3,4-ethylenedioxypyrrole were added thereto. The film-form TH-co-EDOP copolymer was obtained on the ITO electrode by concentration diffusion using the cyclic voltammetry between the electrode range 1.6V and -1.2V.

Comparative Example 1

A terthiophene polymer was obtained under the same conditions and methods as in Example except that only terthiophene was used.

Comparative Example 2

A 3,4-ethylenedioxypyrrole polymer was obtained under the same conditions and methods as in Example except that only 3,4-ethylenedioxypyrrole was used.

Experimental Example 1

The surface morphology of the TH-co-EDOP copolymer obtained in the Example and the terthiophene polymer obtained in Comparative Example 1 was observed by SEM, and the photographs are shown in FIGS. 1A and 1B, respectively.

Referring to FIG. 1A, which shows a picture of a TH-co-EDOP copolymer, and FIG. 1B, which shows a polymer picture of tersiophene, it can be seen that the tersiophene polymer is in a form that can easily fall off the surface of the ITO electrode. TH-co-EDOP copolymer in which tersiophene forms a copolymer with 3,4-ethylenedioxypyrrole is excellent in stability because it forms a film on the surface of the ITO electrode as shown in FIG. Able to know.

Experimental Example 2-1

Cyclic voltammetry of a copolymer of 0.1 mM terthiophene and 10 mM 3,4-ethylenedioxypyrrole under a 0.1 M TBAP electrolyte / acetonitrile solution, ie, TH-co-EDOP copolymer, was measured. It is shown in Figure 2a. At this time, the voltage range was +1.6 to -1.2 and repeated 20 times. The scanning speed was 0.1 V / s and the scanning direction was-direction.

Experimental Example 2-2

As in Comparative Example 1, 0.1 mM terthiophene polymer cyclic voltammetry was measured under 0.1 M TBAP electrolyte / acetonitrile solution, and the result is shown in FIG. 2B. At this time, the experimental conditions were the same as in Experimental Example 2-1 except that the number of repetitions was 10 times.

Experimental Example 2-3

As in Comparative Example 2, 10 mM 3,4-ethylenedioxypyrrole cyclic voltammetry was measured under a 0.1 M TBAP electrolyte / acetonitrile solution, and the graph is shown in FIG. 2C. At this time, the experimental conditions were the same as in Experimental Example 2-1 except that the number of repetitions was 10 times.

Referring to Figure 2a, as shown in the present invention, when tersiophene and 3,4-ethylenedioxy pyrrole form a TH-co-EDOP copolymer it can be seen that the graph shows an increase in oxidation, reduction.

On the other hand, as shown in FIG. 2B, the terthiophene polymer shows an increase in reduction at 1 V and an increase in oxidation of 1 V to 1.5 V. As shown in FIG. 2C, an increase in reduction and -0.5 V to 0.5 V to -1.2 V are shown. At -1.5V, there is a large increase in oxidation around 1V.

On the other hand, when the TH-co-EDOP copolymer of the present invention is applied at a voltage of ?? 1.4V at a voltage of + 1.6V, the TH-co-EDOP copolymer changes color from dark blue to orange-red, On the contrary, when the voltage was applied, the color changed from orange-red to dark blue.

That is, it can be seen that the TH-co-EDOP copolymer reversibly changes color depending on the applied voltage. This reversible color change is a big advantage in applicability, and can reduce power loss by maintaining color even when no voltage is applied.

As a result, the present invention has a great advantage that, unlike the conventionally known 3,4-ethylenedioxypyrrole polymer, it is possible to implement R & B of blue and red color using only organic copolymers, as well as various complex thiophene derivatives. It is not easy to remove because it is not used.

Experimental Example 3

In order to characterize the TH-co-EDOP copolymer obtained in Example, UV-vis spectrum according to the voltage of ITO forming TH-co-EDOP copolymer under 0.1 M TBAP electrolyte / acetonitrile solution was obtained (a) It was measured by changing to 1.5 V-(p) 0.0 V, the results are shown in FIG. 3 is a result of measuring the absorption spectrum of the ITO formed TH-co-EDOP copolymer according to the voltage.

Referring to FIG. 3, when 1.5V is applied, dark blue (spectrum a) to brown to 0.0V is applied to orange-red color, and the result can be observed as an absorption spectrum.

As a result, since the TH-co-EDOP copolymer of the present invention has a low band gap of 1.65 eV, it can be seen that it is an effective electrochromic compound. In addition, the TH-co-EDOP copolymer of the present invention is very likely to be applied to solar cells through such a low band gap.

Experimental Example 4

In order to characterize the TH-co-EDOP copolymer obtained in the Example, a three-dimensional UV-vis spectrum according to the voltage of ITO forming the TH-co-EDOP copolymer under 0.1 M TBAP electrolyte / acetonitrile solution ( a) 1.5 V-(p) was measured by changing to 0.0 V, the results are shown in Figure 4.

FIG. 4 is a three-dimensional graph of FIG. 3 obtained from Experimental Example 3 according to voltage, absorbance, and wavelength. FIG. 4 shows a portion where the wavelength is absorbed according to the voltage applied to the copolymer ITO electrode. Easy to see in dimension

Experimental Example 5

To characterize the TH-co-EDOP copolymer obtained in the examples, TH-co-EDOP air in the 800 nm wavelength range under application of step voltage (1.4 V and -0.4 V) under 0.1 M TBAP electrolyte / acetonitrile solution. The absorbance change and the current change of the coalesced ITO were measured and the results are shown in FIG. 5.

5, the optical contrast of 800 nm according to the step voltage is applied to show the change in absorbance at about 30%, and it can be seen that there is no change in absorbance and current even in a repeated process, and thus it is very stable as an electrochromic material. .

Therefore, it can be seen that the TH-co-EDOP copolymer according to the present invention has not only high stability but also an environmentally friendly and fast switching time as an electrochromic material by organic type.

As such, the electrochromic product including the TH-co-EDOP copolymer of the present invention having excellent properties as an organic electrochromic compound may be applied to various aspects, for example, there may be the followings.

1.vehicle glass (window glass or sunroof)

Electrochromic products comprising the TH-co-EDOP copolymer of the present invention is suitable for blocking sunlight or preventing glare in automobiles including front windows, side windows and rear windows or glass roofs of automobiles. The degree of darkening can be tailored without zones and steps depending on the driver's needs, sunlight conditions and current driving conditions, which can be integrated into a computer control system.

2. Building glass (electrochromic windows)

The electrochromic product including the TH-co-EDOP copolymer of the present invention is applied to the side windows and skylights of buildings, residential spaces, offices or greenhouses to control the blocking of sunlight (visible light region) and heat (infrared region). It is suitable for darkening the room or protecting the eyes (visible light area). Press the button to dim the bank counter's glass or display window to prevent unauthorized entry. Also, when a person comes to a glass door, it can be made automatically visible to avoid injury. If you can actually achieve all the shades of color, you can make the glass match the exterior of the building. Electrochromic products can also contribute to limiting and controlling the energy needed to control the air in buildings.

3. Display Element

Provides advertising through interesting media if you can create attractive colors and plot large areas in any form (for example, letters, pictures, symbols and symbols (created by appropriate structured techniques)). Decorative and informational effects can be easily achieved.

In addition to the possibility of placing an electrochromic system between the windows, there is an alternative of using two or even only one transparent plastic film as the substrate. This can be a wall advertising media that can change information.

Electrochromic products comprising TH-co-EDOP copolymers of the present invention are small display elements, such as dials on watches or dials of measuring instruments, displays for various uses and information displays in train stations, airports or parking indication systems, traffic It can be used for large display elements such as signs, advertising columns. Likewise, it can be used as a variable design display system (such as a race zone boundary) in a stadium. In general, you can use it anywhere you want your information to stand out.

4. Optical

In optics, the electrochromic product comprising the TH-co-EDOP copolymer of the present invention may be used in combination with filters, glasses and lenses of other optical instruments, or may be used as an active element alone. It is likewise possible to use for the lab dissolve prevention for optical detection systems.

5. Mirror

Electrochromic products comprising the TH-co-EDOP copolymer of the present invention may be blurred mirrors, for example, an external mirror that can be darkened by applying voltage in an automobile to prevent glare from other vehicle headlights or You can also use it as a rearview mirror.

6. EMI shielding element

Electrochromic products comprising TH-co-EDOP copolymers of the invention may also be used as variable filter elements for the control of electromagnetic radiation in specific wavelength ranges.

As described above, the present invention has been illustrated and described with reference to preferred embodiments, but is not limited to the above-described embodiments, and is provided to those skilled in the art without departing from the spirit of the present invention. Various changes and modifications will be possible.

Figure 1a is a photograph of the TH-co-EDOP copolymer according to an embodiment of the present invention, Figure 1b is a photo of the polymer of terthiophene,

Figure 2a is a TH-co-EDOP copolymer cyclic voltammogram of 0.1 mM terthiophene and 10 mM 3,4-ethylenedioxypyrrole under 0.1 M TBAP electrolyte / acetonitrile solution according to an embodiment of the present invention,

FIG. 2B is a graph of 0.1 mM terthiophene polymer cyclic voltammetry under 0.1 M TBAP electrolyte / acetonitrile solution,

2c is a graph of 10 mM 3,4-ethylenedioxypyrrole cyclic voltammetry under 0.1 M TBAP electrolyte / acetonitrile solution,

FIG. 3 shows UV-vis according to the voltage of ITO in which terthiophene and 3.4-ethylenedioxypyrrole form TH-co-EDOP copolymer under 0.1 M TBAP electrolyte / acetonitrile solution according to one embodiment of the present invention. Spectrum measurement result graph,

Figure 4 is a three-dimensional UV according to the voltage of the ITO in which terthiophene and 3.4-ethylenedioxypyrrole formed TH-co-EDOP copolymer under 0.1 M TBAP electrolyte / acetonitrile solution according to an embodiment of the present invention -vis Spectrum measurement graph,

FIG. 5 shows ITO in which terthiophene and 3,4-ethylenedioxypyrrole form TH-co-EDOP copolymer in a 800 nm wavelength region under a 0.1 M TBAP electrolyte / acetonitrile solution according to an embodiment of the present invention. Graph of optical and current response versus step voltage (1.4 V and -0.4 V)

Claims (12)

TH-co-EDOP copolymer which has the following structural formula as a copolymer of terthiophene and 3, 4- ethylene dioxy pyrrole. [constitutional formula]

delete The method of claim 1, TH-co-EDOP copolymer, characterized in that the copolymer can implement three or more colors according to the applied voltage. The method of claim 1, TH-co-EDOP copolymer, characterized in that the copolymer is sequentially changed to dark blue, brown, red-orange while the voltage is reduced to OV after applying a voltage to the copolymer 1.5V. The method of claim 1, TH-co-EDOP copolymer, characterized in that the copolymer maintains the discolored color even when the voltage applied to the copolymer is maintained at 0V. The method of claim 1, TH-co-EDOP copolymer, characterized in that the discoloration by the voltage applied to the copolymer is reversible. Adding an electrolyte solution into an electrolytic cell equipped with a three-electrode system and then adding terthiophene and 3,4-ethylenedioxypyrrole; Performing cyclic voltammetry using the three-electrode system; And TH-co-EDOP copolymer manufacturing method comprising the step of forming a TH-co-EDOP copolymer in the form of a film on the test electrode surface. The method of claim 7, wherein In the three-electrode system, a reference electrode is a platinum electrode, a counter electrode is a silver / silver chloride electrode, and a test electrode is composed of an ITO electrode. The method of claim 7, wherein The electrolyte solution is TH-co-EDOP copolymer characterized in that one or more of TBAP (tetrabutylammonium perchlorate), LiClO ₄ , NaClO ₄ dissolved in a solvent containing acetonitrile at a concentration of 0.05 to 0.2M Way. The method of claim 7, wherein TH-co-EDOP copolymer production method characterized in that the molar ratio of tersiophene and 3,4-ethylenedioxypyrrole added to the electrolyte solution is 1: 100. Claim 1, wherein the electric containing a TH-co-EDOP copolymer of any one of claims 3 to 6 or a TH-co-EDOP copolymer prepared by the method of any one of claims 7 to 10 Discoloration products. The glass of claim 11, wherein the electrochromic product is a vehicle. Electrochromic product, characterized in that applied to any one of the building glass, mirrors, display elements, optical system elements, or EMI shielding elements.

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