KR20140052518A

KR20140052518A - Electrochromic material, process for preparing the same and electrochromic device comprising the material

Info

Publication number: KR20140052518A
Application number: KR1020120118667A
Authority: KR
Inventors: 노창호; 손성욱; 고주홍; 여수정
Original assignee: 삼성전자주식회사; 성균관대학교산학협력단
Priority date: 2012-10-24
Filing date: 2012-10-24
Publication date: 2014-05-07

Abstract

Provided is an electrochromic material which includes a polymer obtained by polymerizing a phenothiazine compound. The electrochromic material is polymerized by being arranged through self-assembly and is polymerized on an electrode material like graphene at low temperatures, thereby producing the electrochromic device with improved properties with a simple process.

Description

TECHNICAL FIELD The present invention relates to an electrochromic material, a method of manufacturing the electrochromic material, and an electrochromic material including the material,

An electrochromic material, a method for producing the same, and an electrochromic device including the material.

Electrochromism refers to a phenomenon in which the color reversibly changes due to an electric field when a voltage is applied. The electrochromic material refers to a material capable of reversibly changing the optical characteristics of a material by an electrochemical oxidation and reduction reaction.

Such an electrochromic material may display a color when an electric field is not applied when the electric field is not applied, or may display a color when the electric field is not applied. Alternatively, when the electric field is not applied, . The electrochromic device having such characteristics can be applied to an electrochromic device that changes its light transmission characteristics according to a voltage.

The electrochromic device is applied not only to a device using light transmission characteristics such as a smart window but also to a display such as an electronic paper due to its excellent light weight and portability.

However, research on materials having improved electrochromic properties has been continuously requested, and electrochromic devices having flexible characteristics are also required.

One aspect provides an electrochromic material that forms an electrochromic layer by photopolymerization.

Another aspect provides an electrochromic device comprising graphene and the electrochromic material.

Another aspect is to provide a method for producing the electrochromic material.

According to one aspect,

The present invention provides an electrochromic material comprising a photopolymerization product of a compound represented by the following formula

&Lt; Formula 1 >

In the formula,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same or different and each represents a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 A substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 hetero A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 oxyaryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a phosphonic acid group, a carboxyl group, A sulfonic acid group, a hydroxyl group, a thiol group, or a combination thereof,

And n is an integer of 1 to 30. [

The electrochromic material may display a color close to black such as black, deep green, deep violet, and the like.

According to another aspect,

A first electrode and a second electrode facing each other, an electrochromic material disposed on one of the first electrode and the second electrode, and an electrolyte layer disposed between the first electrode and the second electrode, The electrochromic material includes the photopolymerization result of the compound of formula (1) described above.

The electrochromic device may have an operating voltage higher than about 0.9V.

The electrochromic device may have a potential window of about 1.2V to about 2V.

The electrochromic material may display different colors in different voltage ranges and may display a color similar to black or black.

According to one aspect, the electrochromic material is a novel material that changes from an oxidized state to a dark red color and has excellent reversibility. In addition, since the discoloration film can be introduced onto the surface of various flexible materials such as graphene through a photopolymerization process, it can be used for a flexible display device and the like.

1 is a cross-sectional view showing an electrochromic device according to one embodiment.
FIG. 2 is a graph showing the results of cyclic voltammogram measurement of the electrochromic device according to Example 7. FIG.
Fig. 3 shows a color development photograph of the electrochromic device according to the seventh embodiment according to the applied voltage.
4 is a graph showing the results of cyclic voltammogram measurement of the electrochromic device according to Example 8. FIG.
5 shows a color development photograph of the electrochromic device according to the eighth embodiment in accordance with the applied voltage.
Description of the Related Art
10, 20: insulating substrate
12: first electrode
22: second electrode
14: Electrochromic layer
30: electrolyte

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless otherwise defined herein, a hydrocarbon group has the indicated number of carbons and has a valence of that represented by the formula.

"Alkyl group" means a straight or branched chain, saturated monovalent group (e. G., Methyl or hexyl) having the indicated number of carbons.

Means a straight or branched chain hydrocarbon group having at least one carbon-carbon double bond and "alkynyl group" means straight or branched chain having at least one carbon-carbon unsaturated bond (at least one of which is a triple bond) &Lt; / RTI > The alkenyl group and the alkynyl group may be an alkenyl group having 2 to 15 carbon atoms or an alkynyl group having 2 to 15 carbon atoms.

"Alkoxy group" means the above-mentioned alkyl group (ie, -O-alkyl group) bonded through oxygen, such as methoxy, ethoxy, sec-butoxy, and the like.

"Aryl group" means a cyclic structure in which at least one ring of carbon is aromatic. One or more of these rings may be present and the additional rings may be independently aromatic, saturated or partially unsaturated and may be a fused ring, pendant, spirocyclic, or a combination thereof.

"Aryloxy" means an aryl group (-O-aryl) linked through oxygen.

Unless defined otherwise, "substituted" means that the hydrogen atom in the compound is a halogen (F, Cl, Br or I), a hydroxy group, a C1 to C9 alkoxy group, a C1 to C9 haloalkoxy group, A thio group, a thio group, a tosyl group, an ester group, a carbamoyl group, an acyl group, an acyl group, an acyl group, an acyl group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkyl group (-C (= O) OR An aryl group of C6 to C20, an arylalkyl group of C6 to C20, an arylalkyl group of C7 to C13, a C1 to C4 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 C20 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 Roal key group, it means substituted with a heterocycloalkyl group, and a substituent selected from a combination of the two.

"Hetero" means one to three heteroatoms selected from N, O, S, Si and P, unless otherwise defined below.

Then, the electrochromic material according to one embodiment will be described.

The electrochromic material may be a single electrochromic material or a mixture of two or more electrochromic materials.

The electrochromic material according to one embodiment comprises the polymerization product of a compound represented by the following formula:

&Lt; Formula 1 >

In the formula,

And n is an integer of 1 to 30. [

Examples of the compound represented by the formula (1) include compounds represented by the following formula (2)

(2)

In the formula,

Wherein n is an integer of 1 to 20;

Examples of the compound of formula (2) include a compound of formula (3), a compound of formula (4), and a compound of formula (5).

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

The unit of Formula 1 is induced by self-assembly and forms an electrochromic material by a photopolymerization process.

An example of a photopolymerization process according to such self-assembly is shown in the following reaction formula (1).

In the formula, R represents an alkyl chain.

In the above reaction scheme 1, self-assembly is induced by the mutual attractive force between the alkyl chains bonded to the nitrogen atom in each of the units, so that the units have a regularly ordered structure. Then, by the photopolymerization process Thereby forming an electrochromic material, which is the result of photopolymerization of these monomers.

The electrochromic material according to one embodiment has a high operating voltage (E1) due to the novel polymerization structure and has a high operating voltage (E1) of about 0.2 to about 3 V, for example about 0.4 to about 2 V, about 0.8 to about 1.5 V, Lt; RTI ID = 0.0 > V. &Lt; / RTI >

The electrochromic material according to one embodiment may have a wide range of potential windows of about 1 to about 3V, for example about 1.2 to about 2V, or about 1 to 1.5V. Here, the potential window means a voltage range in which the color can be maintained.

The electrochromic material may be changed from a bleached state (substantially or totally colorless state) to a color state upon application of a voltage. In addition, when the voltage is not applied or when a reverse voltage is applied, the electrochromic material may change from a color state to a decolorized state.

The electrochromic material may change from a decolorized state to a colored state when a voltage of about 0.5 V, for example, about 1 V, or about 1.2 V is applied to the graphene electrode.

In another embodiment, the electrochromic material may be changed from a decolorized state to a colored state when a voltage of about 0.5 to 6 V, for example about 0.8 to 4 V, or about 1 to 2 V, is applied to the graphene electrode have.

Further, when the electrochromic material in a color state is applied to the graphene electrode at a voltage of about 0.5 V or less, for example, about 0 V or about -0.5 V or less, the electrochromic material may be changed to a decolorized state.

In one embodiment, the electrochromic material in a chromogenic state has a color change of about 0.5 to -6 V, for example about 0 to -4 V, or about -0.5 to -2 V, State.

The electrochromic material in a chromogenic state can have an average reflectance of about 10% or less, for example, 8% or less, or 6% or less at about 400 to 700 nm.

In addition, the electrochromic material in the chromogenic state can have an average reflectance of about 0.1 to 10%, for example, about 0.2 to 8%, or about 0.4 to 6% at about 400 to 700 nm.

In other embodiments, the electrochromic material in the chromogenic state can have an average reflectivity of about 5% or less, e.g., 2.5% or less, or 1% or less at about 500 to 700 nm.

The electrochromic material in the chromogenic state may have an average reflectivity of about 0.01 to 5%, for example, about 0.02 to 2.5%, or about 0.04 to 1% at about 500 to 700 nm.

In another embodiment, the electrochromic material in the chromogenic state can have an average reflectivity of less than or equal to 5%, for example less than or equal to 2.5%, or less than or equal to 1% at about 425 to 475 nm.

The electrochromic material in the chromogenic state may have an average reflectivity of about 0.01 to 5%, for example, about 0.02 to 2.5%, or about 0.04 to 1% at about 425 to 475 nm.

Also, when oxidized at a voltage greater than 1 V with respect to the graphene electrode, the electrochromic material may exhibit a maximum reflectivity at about 400 to 500 nm, e.g., about 425 to 475 nm, or 450 nm.

As described above, the electrochromic materials according to the above embodiments enable a multicolor electrochromic material exhibiting two or more colors by controlling the reduction state of electrons.

The compound of Formula 1, which is a precursor of the electrochromic material, can be prepared according to the following Reaction Scheme 2:

In the formula,

N is an integer of 1 to 30,

X is a halogen atom.

As shown in Reaction Scheme 2, the compound of Formula 8 can be obtained by substituting the alkyl chain for the nitrogen atom of the compound of Formula 6, which is the starting material, to obtain the compound of Formula 7, followed by halogenation of the hydrogen at the 3-position. Subsequently, the halogen atom is substituted with an ethynyl group protected with a trimethylsilyl group to obtain a compound of the formula (9), followed by deprotection of the trimethylsilyl group to obtain the compound of the formula (9). The compound of formula (1) can be obtained by dimerizing two compounds of formula (9).

In the above production process, any process known in the art of organic synthesis can be used without limitation, for example, alkyl group substitution reaction, halogenation reaction, deprotection reaction, dimerization reaction and the like.

The compound of formula (1) prepared as described above is used as a unit and forms a polymer by a photopolymerization process to form an electrochromic material.

The compound of the formula (1) can be used in one kind of polymer to form a polymer, and it is of course possible to use two or more kinds thereof to form a polymer.

The electrochromic device using the electrochromic material will now be described with reference to FIG.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

1 is a cross-sectional view schematically showing an electrochromic device according to one embodiment.

1, an electrochromic device according to an embodiment includes a pair of insulating substrates 10 and 20 facing each other, a first electrode 12 and a second electrode 12 formed on the insulating substrates 10 and 20, Two electrodes 22 are formed.

The insulating substrates 10 and 20 may be made of transparent glass or plastic, and the plastic may be made of, for example, polyacrylate, polyethylene ether phthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyetherimide, Meade. &Lt; / RTI >

The first electrode 12 may be made of a transparent conductive material such as indium tin oxide (ITO), fluorine tin oxide (FTO), carbon nanotube, carbon Nanofibers, inorganic conductive substances such as fullerene, graphene and graphite, and organic conductive substances such as polyacetylene or polythiophene. These can be used in combination with each other. That is, a double layered electrode structure can be used by combining indium tin oxide and graphene.

The second electrode 22 may be made of a transparent or opaque conductive material such as a metal such as Al, indium tin oxide (ITO), fluorine containing tin oxide (FTO), antimony doped tin oxide , ATO), carbon nanotubes, carbon nanofibers, fullerene, graphene, graphite, or combinations thereof.

Graphene, which is a material used for the first electrode 12 and the second electrode 22, has a structure in which a plurality of carbon atoms are covalently linked to each other to form a polycyclic aromatic molecule in a sheet form, And is distinguished from carbon nanotubes. The carbon atoms linked by the covalent bond may form a 6-membered ring as a basic repeating unit, but may further include a 5-membered ring and / or a 7-membered ring. The graphene thus appears as a single layer of covalently bonded carbon atoms (usually sp2 bonds). The graphene may be formed of a single layer of graphene as described above, but they may be stacked to form a plurality of layers, and a thickness of up to 300 layers may be formed. Typically, the side ends of the graphene are saturated with hydrogen atoms.

Such graphene can be produced by a physical process such as a mechanical peeling process or a chemical peeling process, or can be produced by a growth process such as a chemical vapor deposition process.

The graphene sheet can be a large sheet or a graphene sheet in which graphene flakes obtained by a chemical stripping method form a thin film on each other can be used.

The graphene may have a single crystal structure or a polycrystal structure, and the graphene of the polycrystalline structure may include a plurality of grains separated by a grain boundary.

Since such graphene has excellent transparency and conductivity, it can be usefully used as an electrode or an auxiliary layer of the electrochromic device. In addition, since it exhibits excellent conductivity even at a very thin thickness, it has a flexible ductility characteristic. Therefore, it can be usefully used for constructing a flexible display device.

When such graphene is used as an electrode structure, the compound of Formula 1 may be laminated and then photopolymerized to form a discoloring material layer on the graphene surface by a simple process without the aid of a material such as TiO ₂ . That is, in order to bond a conventional color-change material to indium tin oxide or the like, an auxiliary material such as TiO ₂ is required and a high temperature process of 450 ° C or more is required. However, the polymer obtained by photopolymerization of the compound of the above- Layer can be formed and can be formed in a low-temperature process of 150 DEG C or less, or 100 DEG C or less, thereby reducing the cost and simplifying the process.

According to one embodiment, as a method of applying the compound of Formula 1 onto the graphene, a method of spray-coating, dip-coating, spin-coating, flow-coating or the like may be used in which a solution of the compound of Formula 1 is dissolved in an organic solvent .

Then, the organic solvent is dried through a drying process, and then photopolymerization is performed by irradiating light such as ultraviolet rays to form a photopolymer composed of the unit of Formula 1 on the graphene.

The drying process may be performed at a high temperature, for example, at a temperature of 50 to 150 ° C. for 1 minute to 1 hour.

Examples of the organic solvent used for applying the compound of Formula 1 include methanol, ethanol, toluene, chlorobenzene, xylene, methanesulfonic acid, benzenesulfonic acid, ethylene dichloride, tetrahydrofuran, tetrachloroethane, Can be used.

On the first electrode 12, an electrochromic layer 14 including the electrochromic material is formed. A reflection plate (not shown) may be formed under the second electrode 22.

The first substrate 10 and the second substrate 20 are fixed by a gap 15 and an electrolyte 30 may be present between the first substrate 10 and the second substrate 20.

The electrolyte 30 supplies an oxidation / reduction material that reacts with an electrochromic compound, and may be a liquid electrolyte or a solid polymer electrolyte. As the liquid electrolyte, a solution in which a lithium salt such as LiOH or LiClO ₄ , a potassium salt such as KOH and a sodium salt such as NaOH are dissolved in a solvent may be used, but the present invention is not limited thereto. As the solid electrolyte, for example, poly (2-acrylamino-2-methylpropane sulfonic acid) or polyethylene oxide (poly (ethylene oxide) It is not.

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example 1

Was prepared as shown in the following Reaction Scheme 3 to prepare an electrochromic unit of Formula (3).

(1) A condenser was connected to a 50 ml two-neck Schlenk, and then flame dry Phenothiazine (5 mmol), DMF 5 ml, NaH (15 mmol) Lt; / RTI > 1-Bromobutane (6 mmol) was added dropwise, and the mixture was stirred at 160 캜 (reflux) for 2 hours.

Cool the temperature to room temperature and slowly add it to distilled water. Extraction (ether / H ₂ O) followed by separation by column (hexane) chromatography yields the compound of formula (12).

Compound ^{_{12: 1 H NMR (CDCl 3}} ): δ 7.15-7.12 (m, 4H), 6.94-6.84 (m, 4H), 3.86 (t, J = 6.9 Hz, 2H), 1.80 (t, J = 6.9 Hz , 2H), 1.27 (m, 2H), 0.94 (m, 3H)

(2) A condenser is connected to a 50 ml two-neck shunnel, followed by addition of a flame-dried compound of formula (12) (5.05 mmol) and DMF (10 ml). 0 ℃ Dipping in ice water bath. NBS (5.05 mmol) is dissolved in 5 ml of DMF and slowly added to RM. Stir at 0 ° C for 30 minutes. After the temperature is raised to room temperature, distilled water is added. After extraction (EA / H ₂ O), the product is separated by column (hexane) chromatography to obtain the compound of formula (13).

Compound ^{_{13: 1 H NMR (CDCl 3}} ): δ 7.26-7.12 (m, 4H), 6.94 (t, J = 7.5 Hz, 1H), 6.87 (d, J = 8.1 Hz, 1H), 6.71 (d, J = 9.9 Hz, 1H), 3.83 (t, J = 6.8 Hz, 2H), 1.78 (t, J = 6.3 Hz, 2H), 1.28 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H)

(3) 50 ml two-neck, connect the capacitor to the shoe Lenk, flames compounds of the dry formula 13 (5.17 mmol), THF 5 ml, Et 3 N 8 ml, PdCl 2 (PPh 3) 2 (0.20 mmol, 3.8 mol%), PPh ₃ (0.20 mmol, 3.8 mol%), CuI (0.20 mmol, 3.8 mol%), ethynyltrimethylsilane (5.17 mmol). Stir at 80 < 0 > C (reflux) overnight. After the temperature is cooled to room temperature, distilled water is added. Extraction (EA / H ₂ O) followed by separation by column (hexane / EA) chromatography gave the compound of formula 14.

Compound ^{_{14: 1 H NMR (CDCl 3}} ): δ 7.22-7.11 (m, 4H), 6.96 (t, J = 6.9 Hz, 1H), 6.86 (d, J = 8.1 Hz, 1H), 6.75 (d, J = 8.1 Hz, 1H), 3.83 (t, J = 7.0 Hz, 2H), 1.78 (m, 2H), 1.47 (m, 2H), 0.96 (t, J = 7.3 Hz, 3H), 0.3 (m, 9H )

(4) To a 50 ml one-neck Schlenk is added a dry compound of formula 14 (1.5 mmol), THF 5 ml, TBAF (2.25 mmol, 1.5 eq). Stir at room temperature for 6 hours. Extraction (EA / H ₂ O) followed by separation by column (hexane / EA) chromatography gave the compound of formula (15).

Compound ^{_{15: 1 H NMR (CDCl 3}} ): δ 7.25-7.21 (m, 2H), 7.12 (t, J = 8.1 Hz, 2H), 6.93 (t, J = 7.5 Hz, 1H), 6.87 (d, J = 8.1 Hz, 1H), 6.78 (d, J = 8.4 Hz, 1H), 3.85 (t, J = 7.2 Hz, 2H), 3.18 ), 0.95 (t, J = 7.3 Hz, 3H)

(5) To a 50 ml one-neck Schlenk solution of compound of formula 15 (0.66 mmol), DMF (5 ml) and Cu (I) I (5 mmol, 5 mol%). The mixture is stirred at 90 DEG C for 5 hours in an open state. After the temperature is cooled to room temperature, it is filtered with ethanol. Column (hexane / EA) chromatography gave the compound of formula (3).

Compound ^{_{3: 1 H NMR (CDCl 3}} ): δ 7.22-7.16 (m, 2H), 7.23 (d, J = 1.8 Hz, 2H), 7.04 (t, J = 8.1 Hz, 4H), 6.85 (t, J = 7.2 Hz, 2H), 6.78 (d, J = 8.1 Hz, 2H), 6.68 (d, J = 8.4 Hz, 2H), 3.76 (t, J = 7.1 Hz, 4H), 1.68 (m, 4H), 1.38 (m, 4H), 0.87 (t, J = 7.3 Hz, 6H)

Example 2

Was prepared in accordance with the following Reaction Scheme 4 to prepare an electrochromic unit of Formula 4 below.

(1) A 50 ml two-neck Schlenk condenser was connected, followed by addition of flame-dried phenothiazine (5 mmol), DMF (5 ml) and NaH (15 mmol). 1-Bromo octane (6 mmol) was added dropwise, and the mixture was stirred at 160 占 폚 (reflux) for 2 hours. After the temperature is cooled to room temperature, it is slowly added to distilled water. Extraction (ether / H ₂ O) followed by separation by column chromatography (hexane) gave the compound of formula 22.

Compound ^{_{22: 1 H NMR (CDCl 3}} ): δ 7.17-7.11 (m, 4H), 6.93-6.84 (m, 4H), 3.83 (t, J = 7.2 Hz, 2H), 1.80 (t, J = 7.0 Hz , 2H), 1.27 (m, 2H), 0.94 (m, 3H)

(2) Condenser is connected to a 50 ml two-neck shunnel, followed by adding flame-dried compound of formula 22 (4.72 mmol) and DMF 10 ml. 0 ℃ Dipping in ice water bath. NBS (4.72 mmol) is dissolved in DMF (5 ml), and then slowly added to RM. Stir at 0 ° C for 30 minutes. After the temperature is raised to room temperature, distilled water is added. After extraction (EA / H ₂ O), the product was separated by column chromatography (hexane) to obtain the compound of Formula 23.

Compound ^{_{23: 1 H NMR (CDCl 3}} ): δ 7.25-7.12 (m, 4H), 6.93 (t, J = 7.5 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.70 (d, J = 9.6 Hz, 1H), 3.80 (t, J = 7.2 Hz, 2H), 1.78 (t, J = 6.6 Hz, 2H), 1.27 (m, 10H), 0.88 (t, J = 6.6 Hz, 3H)

(3) A 50 ml two-neck Schlenk condenser was connected and a flame dried compound of formula 23 (4.23 mmol), THF 5 ml, Et ₃ N 8 ml, PdCl ₂ (PPh ₃ ) ₂ (0.163 mmol, 3.8 mol), PPh ₃ (0.163 mmol, 3.8 mol%), CuI (0.163 mmol, 3.8 mol%) and ethynyltrimethylsilane (4.23 mmol). Stir at 80 < 0 > C (reflux) overnight. After the temperature is cooled to room temperature, distilled water is added. Extraction (EA / H ₂ O) followed by separation by column (hexane / EA) chromatography gave the compound of formula 24.

Compound ^{_{24: 1 H NMR (CDCl 3}} ): δ 7.29-7.12 (m, 4H), 6.94 (t, J = 7.2 Hz, 1H), 6.87 (d, J = 7.2 Hz, 1H), 6.76 (d, J = 9.6 Hz, 1H), 3.84 (t, J = 7.2 Hz, 2H), 1.81 (m, 2H), 1.30 (m, 10H), 0.92 (t, J = 6.6 Hz, 3H), 0.29 (m, 9H )

(4) Add 50 mg of the compound of formula 24 (1.5 mmol), THF 5 ml, TBAF (2.25 mmol, 1.5 eq), which is flame-dried to a 50 ml one-neck shunnel. Stir at room temperature for 6 hours. Extraction (EA / H ₂ O) followed by separation by column (hexane / EA) chromatography gave the compound of formula 25.

Compound ^{_{25: 1 H NMR (CDCl 3}} ): δ 7.28-7.24 (m, 2H), 7.12 (t, J = 8.1 Hz, 2H), 6.93 (t, J = 7.5 Hz, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.77 (d, J = 8.4 Hz, 1H), 3.83 (t, J = 7.2 Hz, 2H), 3.04 (s, ), 0.88 (t, J = 7.1 Hz, 3 H)

(5) To a 50 ml one-necked schlenk were added the compound of formula 25 (0.66 mmol), DMF 5 ml and Cu (I) I (5 mmol, 5 mol%). The mixture is stirred at 90 DEG C for 5 hours in an open state. After the temperature is cooled to room temperature, it is filtered with ethanol. Column chromatography (hexane / EA) gave the compound of formula (4).

Compound ^{_{4: 1 H NMR (CDCl 3}} ): δ 7.29-7.25 (m, 2H), 7.23 (d, J = 1.8 Hz, 2H), 7.13 (t, J = 8.1 Hz, 4H), 6.94 (t, J = 7.2 Hz, 2H), 6.85 (d, J = 8.1 Hz, 2H), 6.75 (d, J = 8.4 Hz, 2H), 3.84 (t, J = 7.2 Hz, 4H), 1.80 (m, 4H), 1.28 (m, 20H), 0.88 (t, J = 6.9 Hz, 6H)

Example 3

Was prepared in accordance with the following Reaction Scheme 5 to prepare an electrochromic unit of Formula 5 below.

(1) A condenser is connected to a 50 ml two-neck Schlenk, followed by addition of flame-dried phenothiazine (5 mmol), DMF (5 ml) and NaH (15 mmol). 1-Bromododecane (5.6 mmol) was added dropwise, and the mixture was stirred at 160 캜 (reflux) for 2 hours. After the temperature is cooled to room temperature, it is slowly added to distilled water. Extraction (Ether / H ₂ O) followed by separation by column (hexane) chromatography gave the compound of formula 32.

Compound ^{_{32: 1 H NMR (CDCl 3}} ): δ 7.17-7.16 (m, 4H), 6.93-6.84 (m, 4H), 3.83 (t, J = 6.9 Hz, 2H), 1.80 (t, J = 6.9 Hz , 2H), 1.24 (m, 18H), 0.88 (m, 3H)

(2) A condenser is connected to a 50 ml two-neck Schlenk, and then a flame-dried compound of Formula 32 (2.7 mmol) and DMF 10 ml are added. Dip into an ice bath at 0 ° C. NBS (2.7 mmol) is dissolved in 5 ml of DMF and slowly added to RM. Stir at 0 ° C for 30 minutes. After the temperature is raised to room temperature, distilled water is added. Extraction (EA / H ₂ O) followed by separation by column (hexane) chromatography gave the compound of formula 33.

Compound ^{_{33: 1 H NMR (CDCl 3}} ): δ 7.23-7.10 (m, 4H), 6.92 (t, J = 6.0 Hz, 1H), 6.85 (d, J = 9.0 Hz, 1H), 6.69 (d, J = 9.0 Hz, 1H), 3.79 (t, J = 6.0 Hz, 2H), 1.76 (t, J = 6.0 Hz, 2H), 1.24 (m, 18H), 0.88 (t, J = 6.0 Hz, 3H)

(3) A condenser was connected to a 50 ml two-neck Schlenk, followed by heating and drying the compound of Formula 33 (1.86 mmol), THF 5 ml, Et ₃ N 8 ml, PdCl ₂ (PPh ₃ ) ₂ (0.07 mmol, mol%), PPh ₃ (0.07 mmol, 3.8 mol%), CuI (0.07 mmol, 3.8 mol%), ethynyltrimethylsilane (1.86 mmol). Stir at 80 < 0 > C (reflux) overnight. After the temperature is cooled to room temperature, distilled water is added. Extraction (ether / H ₂ O) followed by separation by column (hexane / ether) chromatography gave the compound of formula 34.

Compound ^{_{34: 1 H NMR (CDCl 3}} ): δ 7.24-7.09 (m, 4H), 6.92 (t, J = 6.0 Hz, 1H), 6.85 (d, J = 9.0 Hz, 1H), 6.76 (d, J = 9.0 Hz, 1H), 3.82 (t, J = 6.0 Hz, 2H), 1.80 (m, 2H), 1.24 (m, 18H), 0.88 (t, J = 6.0 Hz, 3H), 0.04 (m, 9H )

(4) Add 50 mg of the compound of Formula 34 (3.85 mmol), 10 ml of THF and 5.78 mmol (1.5 eq) of TBAF, which is flame-dried in a one-neck shunnel. Stir at room temperature for 6 hours. Extraction (EA / H ₂ O) followed by separation by column (hexane / ether) chromatography gave the compound of formula 35.

Compound ^{_{35: 1 H NMR (CDCl 3}} ): δ 7.24-7.21 (m, 2H), 7.12 (t, J = 6.0 Hz, 2H), 6.84 (d, J = 8.1 Hz, 1H), 6.75 (d, J = 8.4 Hz, 1H), 3.82 (t, J = 6.9 Hz, 2H), 3.03 (s, 1H), 1.78 (m, 2H), 1.24 (m, 18H), 0.88 (t, J = 6.6 Hz, 3H )

(5) To 20 ml of bayer are added the compound of formula 35 (1.5 mmol), DMSO 5 ml and Cu (I) Cl (0.075 mmol, 5 mol%). The mixture is stirred at 90 DEG C for 5 hours in an open state. After the temperature is cooled to room temperature, it is filtered with ethanol. Column (hexane / ether) chromatography afforded the compound of formula (5).

Compound ^{_{5: 1 H NMR (CDCl 3}} ): δ 7.3 (d, J = 1.8 Hz, 2H), 7.23 (d, J = 1.8 Hz, 2H), 7.17-7.08 (m, 4H), 6.92 (t, J = 7.5Hz, 2H), 6.84 ( d, J = 8.4 Hz, 2H), 6.75 (d, J = 8.1 Hz, 2H), 3.82 (t, J = 7.2 Hz, 4H), 1.78 (m, 4H), 1.24 (m, 36H), 0.88 (t, J = 6.3 Hz, 6H)

Example 4

The compound of Formula 3 obtained in Example 1 was dissolved in toluene at a concentration of 1 wt%, and then spin-coated on ITO (thickness 200 nm) having a width of 1 cm and a length of 5 cm at 500 rpm for 5 seconds. And then dried in an oven at 80 DEG C for 20 minutes to remove the toluene. The compound of Formula 1 was photopolymerized by irradiating ultraviolet rays for 10 minutes using a xenon lamp of 250 nm to form a layer of electrochromic material formed of the polymer of the following Formula 41 on the ITO.

&Lt; EMI ID =

Wherein R is a butyl group.

Example 5

The compound of Formula 4 obtained in Example 2 was dissolved in toluene at a concentration of 1 wt%, and then spin-coated on ITO (thickness 200 nm) having a width of 1 cm and a length of 1 cm at 1,000 rpm for 25 seconds. And then dried in an oven at 80 DEG C for 20 minutes to remove the toluene. The compound of Formula 1 was photopolymerized by irradiation with ultraviolet rays for 20 minutes using a xenon lamp of 250 nm to form a layer of electrochromic material formed of the polymer represented by the following Chemical Formula 42 on the ITO.

(42)

Wherein R is an octyl group.

Example 6

The compound of Chemical Formula 5 obtained in Example 3 was dissolved in toluene at a concentration of 1 wt%, and then spin-coated on ITO (thickness 200 nm) having a width of 1 cm and a length of 5 cm at 500 rpm for 5 seconds. And then dried in an oven at 80 DEG C for 20 minutes to remove the toluene. The compound of Formula 1 was photopolymerized by irradiating with ultraviolet rays for 30 minutes using a 250 nm xenon lamp to form a layer of electrochromic material formed of the polymer of Formula 43 on the ITO.

(42)

Wherein R is a dodecyl group.

(The main feature of the present invention is the layer of electrochromic material self-assembled on the graphene.) It is known that the above example uses only the ITO electrode material after the assignment is completed.

Example 7

An electrochromic device was prepared using the electrode material obtained in Example 4 above. The electrolyte used was 0.10 M tetrabutylammonium hexafluorophosphate in AcCN, and the counter electrode was ITO (thickness 200 nm), which is located on the glass and has a width of 1 cm and a length of 1 cm, respectively.

Example 8

An electrochromic device was produced using the electrode material obtained in Example 6 above. The electrolyte used was 0.10 M tetrabutylammonium hexafluorophosphate in AcCN, and the counter electrode was ITO (thickness 200 nm), which is located on the glass and has a width of 1 cm and a length of 1 cm, respectively.

Experimental Example 1

The electrochemical characteristics of the electrochromic device prepared in Example 7 were measured using cyclic voltammetry and shown in FIG. The reversible CV peak was confirmed along with the color change at +0.8 V (vs Ag / Ag +) due to oxidation. As shown in FIG. 3, the discoloration property was changed from an oxidized state to a dark red color and exhibited excellent reversibility.

Experimental Example 2

The electrochemical characteristics of the electrochromic device prepared in Example 8 were measured using cyclic voltammetry and shown in FIG. The reversible CV peak was confirmed along with the color change at +0.8 V (vs Ag / Ag +) due to oxidation. As shown in FIG. 5, the discoloration property was changed from an oxidized state to a dark red color and exhibited excellent reversibility.

Claims

An electrochromic material comprising a photopolymerization product of a compound of the formula
&Lt; Formula 1 >

In the formula,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same or different and each represents a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 A substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 hetero A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 oxyaryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a phosphonic acid group, a carboxyl group, A sulfonic acid group, a hydroxyl group, a thiol group, or a combination thereof,
And n is an integer of 1 to 30. [

The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by Formula 2:
(2)

In the formula,
Wherein n is an integer of 1 to 20;

The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by Formula 3, a compound represented by Formula 4, or a compound represented by Formula 5 below.
(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

The method according to claim 1,
Wherein the electrochromic material exhibits a color close to black or black.

The method according to claim 1,
Wherein the electrochromic material has an average reflectivity of less than 10% at 400 to 700 nm in a chromogenic state when the electrochromic material is oxidized at a voltage of 0.5 V or more.

The method according to claim 1,
Wherein the electrochromic material has a maximum reflectance at 425 to 475 nm in a chromogenic state when the electrochromic material is oxidized at a voltage of 0.5 V or more.

Using a phenothiazine-based compound to prepare a compound of the formula 1 below; And
And photopolymerizing the compound of Formula 1 to form a polymer.
&Lt; Formula 1 >

8. The method of claim 7,
Wherein the step of preparing a compound represented by the following formula (1) using the phenothiazine-
Substituting an alkyl chain at the nitrogen atom of the starting compound of formula (6) to obtain a compound of formula (7);
Halogenating the hydrogen at the 3-position of the compound of formula (7) to obtain a compound of formula (8);
To obtain a compound of the following general formula (9) by substituting the halogen atom of the compound of the general formula (8) with an ethynyl group protected with trimethylsilyl group;
Deprotecting a trimethylsilyl group of the following formula (8) to obtain a compound of the formula (9); And
A process for producing a electrochromic material, comprising: dimerizing a compound represented by the following formula (9) to prepare a compound represented by the following formula

In the formula,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same or different and each represents a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 A substituted or unsubstituted C1 to C30 fluoroalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 hetero A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 oxyaryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a phosphonic acid group, a carboxyl group, A sulfonic acid group, a hydroxyl group, a thiol group, or a combination thereof,
N is an integer of 1 to 30,
X is a halogen atom.

A first electrode and a second electrode facing each other;
An electrochromic material disposed on one of the first electrode and the second electrode; And
And an electrolyte layer disposed between the first electrode and the second electrode,
Wherein the electrochromic material is the electrochromic material according to any one of claims 1 to 6.

10. The method of claim 9,
Wherein the first electrode or the second electrode is graphene.

11. The method of claim 10,
Wherein the electrochromic material is self-assembled to the graphene.