WO2019066553A2 - Electrochromic composite, electrochromic element comprising same, and manufacturing method for electrochromic element - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic composite, an electrochromic device including the electrochromic composite, and a method of manufacturing the electrochromic device.

Description

Electrochromic composite, electrochromic device comprising same, and method of manufacturing electrochromic device

This application claims the benefit of Korean Patent Application No. 10-2017-0126180 filed on September 28, 2017, and Korean Patent Application No. 10-2018-0035643 filed on March 28, 2018, , The entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic composite, an electrochromic device including the electrochromic composite, and a method of manufacturing the electrochromic device.

Electrochromism is a technique for changing the color of a material through an electrochemical reaction. Electrochromism is a phenomenon in which the insertion of a cation in the electrode structure by an electrochemical oxidation / reduction reaction, which is caused by a change in applied voltage, It is a characteristic that the color of a substance changes reversibly while electron density changes with desorption.

An electrochromic device is a device that changes color by an electrochemical reaction. In the electrochromic device, when a potential difference is generated by an external electrical stimulus, ions or electrons contained in the electrolyte migrate into the electrochromic layer and an oxidation / reduction reaction occurs. The color of the electrochromic device is changed by the redox reaction of the electrochromic layer. Reduced coloring materials are substances that are colored when a cathodic reaction occurs and are discolored when an anodic reaction occurs. The oxidative discoloring substance means a substance which is colored when it is oxidized and decolorized when it is a reducing reaction.

The electrochromic device exhibits a high contrast ratio and can be used for optical shutters, displays, smart windows, or automotive electrochromic mirrors due to its ease of transmission control, low driving voltage, bistability, It has been actively studied in application fields.

The present invention is to provide an electrochromic composite, an electrochromic device including the electrochromic composite, and a method of manufacturing the electrochromic device.

One embodiment of the present application relates to an organic compound having electrochromic properties; And a carbon nanotube in which at least a part of the surface is covered with a polymer.

An embodiment of the present application also includes a first electrode; A second electrode facing the first electrode; An electrolyte layer provided between the first electrode and the second electrode; And an electrochromic layer provided between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to an embodiment of the present application.

Finally, one embodiment of the present application is a method comprising: preparing a first electrode; Forming a second electrode facing the first electrode; Forming an electrolyte layer between the first electrode and the second electrode; And forming an electrochromic layer between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to one embodiment of the present application. to provide.

The electrochromic device according to one embodiment of the present application uses an electrochromic composite comprising an organic compound having excellent electrochromic properties and a carbon nanotube having high charge mobility as an electrochromic layer, Color contrast), and at the same time, provides an electrochromic device improved in electric conductivity and process conditions.

In addition, the organic compound having an electrochromic property according to one embodiment of the present application is excellent in oxidation stability and has a long life when applied to an electrochromic device.

1 is a side view of an electrochromic device according to one embodiment of the present application.

FIG. 2 is a view showing a form of a carbon nanotube containing a polymer according to an embodiment of the present application. FIG.

3 is a graph showing the MS spectrum of Compound A-2.

4 shows the MS spectrum of Compound 1. Fig.

5 shows MS spectrum of compound B-2.

6 is a graph showing the MS spectrum of Compound B-3.

7 is a graph showing the MS spectrum of Compound 2. Fig.

8 is a diagram showing the UV spectrum of Compound 3. Fig.

9 is a graph showing the MS spectrum of Compound 3. Fig.

10 is a graph showing the MS spectrum of Compound 4. Fig.

11 is a graph showing the MS spectrum of Compound 5. Fig.

12 shows MS spectrum of Compound 6. Fig.

13 is a graph showing the MS spectrum of Compound 7. Fig.

14 is a graph showing the MS spectrum of Compound 8-2.

15 is a graph showing the MS spectrum of Compound 8. Fig.

16 is a graph showing the MS spectrum of Compound 9;

17 is a graph showing the MS spectrum of Compound 10. Fig.

18 is a graph showing an absorption wavelength according to a voltage change applied to the electrochromic device according to Comparative Example 1. Fig.

Fig. 19 is a graph showing an absorption wavelength according to a voltage change applied to the electrochromic device according to the first embodiment. Fig.

20 is a graph showing CV results of the electrochromic device according to Example 1 and Comparative Example 1. Fig.

FIGS. 21 to 25 are diagrams showing the difference in transmission between the coloration state and the bleaching state of Comparative Example 2 and Examples 2 to 5. FIG.

26 is a graph showing the change in absorbance of the electrochromic device according to Example 5 according to a voltage change applied thereto.

<Explanation of Symbols>

10: Electrochromic device

20: first electrode

30: electrolyte layer

40: electrochromic layer

50: second electrode

Hereinafter, the present application will be described in more detail.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

One embodiment of the present application relates to an organic compound having electrochromic properties; And a carbon nanotube in which at least a part of the surface is covered with a polymer.

The organic compound having an electrochromic property may include a polymer having an electrochromic property or a compound having an electrochromic property, but the present invention is not limited thereto.

When a carbon material such as carbon nanotubes is used to form an electrochromic layer, the thin film is uniform, and it is difficult to produce a thick film. Even if the diaphragm can be made thick, the transmittance may be low. As a result, electrochromic contrast using only carbon nanotubes is poor, and carbon nanotubes themselves have poor solubility in organic solvents, so that it is difficult to control the thickness of the thin film.

In addition, when an electrochromic layer is formed using an electrochromic organic compound alone, it has an advantage of excellent electrochromic contrast. However, since it has poor thermal stability and low charge mobility compared to other electrochromic materials such as an oxide semiconductor, Is slow.

That is, in order for the electrochromic characteristics to be well realized, the redox reaction of the electrochromic organic compound should be performed stably and rapidly. Carbon nanotubes may have excellent electrical conduction properties, but have limitations in their use in solution processes. Carbon nanotubes can be applied to electrochromic films by other methods than solution processes. However, when the film is formed thick, the degree of bleaching of the carbon nanotubes is unclear due to their low transparency. Therefore, when a polymer-wound carbon nanotube is used, it is possible to form a thin film with good dispersibility, but the electrochromic phenomenon itself is hardly observed. Therefore, according to the embodiments of the present application, it is possible to improve the electrochromic characteristics of the electrochromic organic compound by introducing the electroconductive property, which is an excellent characteristic of the carbon nanotube, by mixing the electrochromic organic compound and the carbon nanotube wound with the polymer .

The present application is based on the finding that the use of carbon nanotubes in which at least a part of the surface of the carbon nanotubes is covered with a polymer makes it possible to obtain an electrochromic device having an excellent dispersibility in an organic solvent, The present invention provides an electrochromic device having improved electrochromic characteristics (color contrast) and improved electrical conductivity and process conditions by being used in an electrochromic layer.

In the present application, when a component is referred to as " comprising ", it means that it can include other components as well, without excluding other components unless specifically stated otherwise.

In the present application, when a member is located on another member, this includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

According to an embodiment of the present invention, a carbon nanotube having a polymer covered at least a part of the surface thereof has a structure in which the polymer is surrounded by carbon nanotubes.

In one embodiment of the present application, the shape of the carbon nanotubes containing the polymer is such that the polymer has a structure spirally surrounded by the carbon nanotubes.

The production of carbon nanotubes in which at least a part of the surface according to one embodiment of the present application is covered with a polymer is disclosed in ACS Appl. Mater. Interfaces, 2016, 8 (47), pp 32421-32431.

FIG. 2 is a view showing a form of a carbon nanotube in which a polymer is covered at least a part of the surface according to an embodiment of the present application. FIG. Specifically, the carbon nanotube has a structure in which a polymer is spirally surrounded by a carbon nanotube.

In one embodiment of the present application, the polymer comprises at least one selected from the group consisting of a thiophene-based polymer and a fluorene-based polymer.

Examples of the thiophene-based polymer include, but are not limited to, P3HT (poly (3-hexylthiophene)) and P3DDT (poly (3-dodecylthiophene-2,5-diyl).

The fluorene-based polymer includes, but is not limited to, poly (9,9-di-n-octylfluorenyl-2,7-diyl).

In one embodiment of the present application, the polymer may be P3HT (Poly (3-hexylthiophene)).

Conventional carbon nanotubes are not well dispersed in a solvent because of their strong aggregation. However, the carbon nanotubes containing the polymer may be more dispersed than general carbon nanotubes due to solubility of the polymer.

In one embodiment of the present application, the weight ratio of the organic compound and the carbon nanotubes covered with the polymer may be 10: 1 to 400: 1, preferably 35: 1 to 150: 1.

In one embodiment of the present application. Wherein the weight ratio of the organic compound to the carbon nanotubes covered with the polymer is 10: 1 to 400: 1.

When the mixing ratio of the carbon nanotubes is within the above range, it is possible to improve the electrochromic response speed and the driving voltage by securing adequate permeability and improving charge mobility.

As the solvent, a commonly used solvent may be used, and it is not particularly limited as long as it is capable of dissolving an organic compound having an electrochromic property, specifically, an organic solvent.

Examples of the organic solvent include chlorobenzene, toluene, chloroform, 1,2-dichlorobenzene, xylene, and the like, and are not limited as long as they can dissolve an organic compound having an electrochromic property.

According to one embodiment of the present application, the polymer is used in an amount of 30 parts by weight to 200 parts by weight, preferably 35 parts by weight to 190 parts by weight, and more preferably 40 parts by weight, based on 100 parts by weight of the carbon nanotubes, Parts by weight to 180 parts by weight.

When the content of the polymer is in the above range, it is possible to drive the electrochromism even at a low voltage due to an increase in charge mobility and the like, and the coloration and bleaching speed can be accelerated.

The electrochromic composite according to one embodiment of the present application can form an electrochromic composite in which an organic compound having excellent electrochromic properties is mixed with the carbon nanotube because the carbon nanotube contains a polymer, Thus, it can be used as an electrochromic layer of an electrochromic device.

In one embodiment of the present application, the weight average molecular weight of the polymer may be from 3,000 g / mol to 1,000,000 g / mol, preferably from 5,000 g / mol to 1,000,000 g / mol.

When the polymer has a weight average molecular weight in the above range, the thermal stability of the polymer itself increases, and when used as an electrochromic layer of the electrochromic device, the thermal stability of the electrochromic device may increase.

In one embodiment of the present application, the organic compound having an electrochromic property may be represented by any one of the following formulas (1) to (7).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the general formulas (1) to (7)

X, X1 to X4 and Z1 to Z5 are the same or different from each other, and each independently C = CRR '; SiRR '; O; S; Or NR,

Ar1 and Ar2 are the same or different and are each a group independently acting as an electron acceptor,

Ar 3 to Ar 6 are the same or different from each other, and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted alkoxy group; Or SiRR'R "

A is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

T1 and T2 are the same or different and are each independently a direct bond; O; Or S,

R1 to R18 are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

A halogen atom, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, A substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

p and q are each an integer of 0 to 5,

a and b are each an integer of 0 to 3,

n is an integer of 1 to 1000,

a1 is a number of 0 < a1 < 1, a2 is a number of 0 < a2 < 1,

b1 is a number of 0 < b1 < 1, b2 is a number of 0 < b2 <

a1 + a2 and b1 + b2 are integers of 1,

m1, m2, m3, n1 and n2 are integers of 0 to 4, respectively.

In the present application, the weight average molecular weight of the organic compound of Formulas 4 to 7 may be 1000 g / mol or more and 100000 g / mol or less, preferably 10000 g / mol or more and 70000 g / mol or less.

및

는 다른 치환기에 연결되는 부분을 의미한다.In the present specification,

And

Quot; means a moiety connected to another substituent.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; And a heterocyclic group, or a substituted or unsubstituted one in which at least two of the above-exemplified substituents are connected to each other. For example, &quot; a substituent to which at least two substituents are connected &quot; may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an ester group oxygen by a straight-chain, branched or cyclic alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRaRbRc, wherein Ra, Rb and Rc are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl and phenylsilyl groups. Do not.

In the present specification, the boron group may be represented by the formula of -BRaRbRc, wherein Ra, Rb and Rc are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, a n-butyl group, an isobutyl group, Hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-tert-butylpentyl group, 1-methylbutyl group, Methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, ethylhexyl group, 1-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, Propyl group, isohexyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited thereto.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

Substituents comprising the alkyl groups, alkoxy groups and other alkyl moieties described herein include both straight chain and branched forms.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the number of carbon atoms of the alkylamine group is not particularly limited, but is preferably 1 to 40. Specific examples of the alkylamine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, Group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group containing at least two heterocyclic groups may contain a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.

In the present specification, examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group. The aryl group in the arylphosphine group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a triphenyl group, a klycenyl group and a fluorenyl group.

In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

, A spirofluorenyl group

(9,9-dimethylfluorenyl group), and

(9,9-diphenylfluorenyl group), and the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group and is a heterocyclic group containing at least one of N, O, P, S, Si and Se, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60 carbon atoms. According to one embodiment, the number of carbon atoms of the heterocyclic group is from 1 to 30. [ Examples of the heterocyclic group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophenyl group, an imidazole group, a pyrazole group, an oxazole group, an isoxazole group, a thiazole group, A thiadiazole group, a thiadiazole group, a tetrazolyl group, a pyranyl group, a thiopyranyl group, a pyrazinyl group, an oxazinyl group, a thiazinyl group, a dioxinyl group, a triazinyl group, a tetrazinyl group, A phenanthridinyl group, a diazanaphthalenyl group, a triazinylidene group, an indole group, a thiazolidinyl group, a thiomorpholinyl group, a thiomorpholinyl group, a thiomorpholinyl group, an isothiazolyl group, , Indolinyl group, indolizinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, benzothiazole group, benzoxazole group, benzimidazole group, benzothiophene group , Benzofuranyl group, dibenzothiophenyl group, dibenzofuranyl , A carbazole group, a benzocarbazole group, a dibenzocarbazole group, an indolocarbazole group, an indenocarbazole group, a phenazinyl group, an imidazopyridine group, a phenoxazinyl group, a phenanthroline group, a phenanthroline group, Phenothiazine group, imidazopyridine group, imidazophenanthridine group. A benzoimidazoquinazolinyl group, a benzoimidazophenanthridin group, and the like, but are not limited thereto.

In the present specification, the description of the aforementioned heterocyclic group can be applied, except that the heteroaryl group is aromatic.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the arylphosphine group, the aralkyl group, the aralkylamine group, the aralkenyl group, the alkylaryl group, the arylamine group and the arylheteroarylamine group, The description of one aryl group may be applied.

In the present specification, the alkyl group in the alkylthio group, the alkylsulfoxy group, the aralkyl group, the aralkylamine group, the alkylaryl group and the alkylamine group can be applied to the alkyl group described above.

In the present specification, the heteroaryl group in the heteroaryl group, the heteroarylamine group and the arylheteroarylamine group can be applied to the description of the above-mentioned heterocyclic group.

In the present specification, the alkenyl group in the aralkenyl group can be applied to the description of the alkenyl group described above.

In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group.

In one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other and each is any one of the following structures.

In the above structure,

c and d are integers of 1 to 4,

When c and d are two or more, structures in parentheses of two or more are the same or different from each other,

R15 to R20 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; A halogen group; A nitrile group; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present application, R15 to R20 are the same or different and each independently hydrogen; Or an alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present application, R18 and R20 are hydrogen.

이고, R18 및 c는 전술한 바와 같다.In one embodiment of the present application, Arl and Ar2 are each

Lt; 18 &gt; and c are as described above.

이고, R18은 수소이다.In one embodiment of the present application, Arl and Ar2 are each

And R18 is hydrogen.

이고, R15는 전술한 바와 같다.In one embodiment of the present application, Arl and Ar2 are each

And R &lt; 15 &gt; is as described above.

이고, R15는 탄소수 1 내지 10의 알킬기이다.In one embodiment of the present application, Arl and Ar2 are each

And R15 is an alkyl group having 1 to 10 carbon atoms.

이고, R19는 전술한 바와 같다.In one embodiment of the present application, Arl and Ar2 are each

And R19 is as described above.

이고, R20 및 d는 전술한 바와 같다.In one embodiment of the present application, Arl and Ar2 are each

, R &lt; 20 &gt; and d are as described above.

In one embodiment of the present application, Ar3 to Ar6 are the same or different and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted alkoxy group; Or SiRR'R ".

In another embodiment, Ar 3 to Ar 6 are the same or different and each independently is a substituted or unsubstituted alkyl group; Or SiRR'R ".

In another embodiment, Ar 3 to Ar 6 are the same or different and each independently is a substituted or unsubstituted branched alkyl group; Or SiRR'R ".

In another embodiment, Ar 3 to Ar 6 are the same or different and are each independently a substituted or unsubstituted, branched alkyl group having 3 to 30 carbon atoms; Or SiRR'R ".

In another embodiment, Ar 3 to Ar 6 are the same or different and are each independently a substituted or unsubstituted, branched alkyl group having 3 to 20 carbon atoms; Or SiRR'R ".

In one embodiment of the present application, Ar6 may be a substituted or unsubstituted, branched alkyl group having 3 to 20 carbon atoms.

In one embodiment of the present application, A is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

In yet another embodiment, A provides an electrochromic composite comprising one of the following structures:

In the above structure,

R21 is hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group,

R22 to R24 are the same or different and each independently represents a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

e is an integer of 1 or 2, and when e is an integer of 2, R ₂₁ are the same or different from each other.

In one embodiment of the present application, R21 is selected from the group consisting of hydrogen; Or a halogen group.

In another embodiment, R21 is selected from the group consisting of hydrogen; Or fluorine.

In one embodiment of the present application, R22 and R23 may be the same or different and each independently a substituted or unsubstituted alkyl group.

In another embodiment, R22 and R23 may be the same or different and each independently an alkyl group substituted or unsubstituted with SiRR'R ".

In one embodiment of the present application, R24 may be a substituted or unsubstituted aryl group.

In another embodiment, R24 may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In another embodiment, R24 may be an aryl group having 6 to 40 carbon atoms substituted or unsubstituted with an alkoxy group having 1 to 15 carbon atoms.

In another embodiment, R24 may be an aryl group having 6 to 40 carbon atoms substituted or unsubstituted with an octyloxy group.

In one embodiment of the present application, R 1 to R 18 are the same or different and each independently hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In another embodiment, R 1 to R 18 are the same or different and are each independently selected from the group consisting of hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; Or a substituted or unsubstituted C2-C30 heteroaryl group.

In another embodiment, R 1 to R 18 are the same or different and are each independently selected from the group consisting of hydrogen; A halogen group; An alkoxy group substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms; Or a linear or branched alkyl group having 3 to 30 carbon atoms.

In one embodiment of the present application, R, R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, halogen, nitrile, nitro, imide, amide, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, A substituted or unsubstituted alkylamine group, an unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

In another embodiment, R, R 'and R "are the same or different from each other and each independently hydrogen, a substituted or unsubstituted alkyl group, an alkylsilyloxy group, or an alkylthioxy group.

In another embodiment, R, R 'and R " are the same or different from each other and each independently hydrogen, a linear or branched alkyl group, an alkylsilyloxy group, or an alkylthioxy group.

In another embodiment, R, R 'and R "are the same or different from each other and each independently represents hydrogen, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, an alkylsilyloxy group Or an alkylthio group.

In one embodiment of the present application, a1 is a number of 0 <a1 <1, a2 is a number of 0 <a2 <1, b1 is a number of 0 <b1 <1, and b2 is 0 <a2 <1 And a1 + a2 and b1 + b2 may be integers of 1.

In one embodiment of the present application, a1 may be a number of 0 < a1 < 0.8, and a2 may be a number of 0 < a2 <

In another embodiment, a1 may be a number of 0.5 < a1 < 0.8, and a2 may be a number of 0 < a2 < 0.29.

In yet another embodiment, a1 may be 0.75 and a2 may be 0.25.

A1 and a2 mean the molar ratio of the monomers contained in the repeating unit, and a1 may have a number larger than a2.

In one embodiment of the present application, b1 may be a number of 0 < b1 < 0.6 and b2 may be a number of 0 < b2 < 0.6.

In yet another embodiment, b1 may be a number 0.1 < b1 < 0.55, and b2 may be a number 0.1 < b2 < 0.55.

In yet another embodiment, b1 may be 0.5 and b2 may be 0.5.

B1 and b2 mean the molar ratio of the monomers contained in the repeating unit, and b1 and b2 may have the same number.

In one embodiment of the present application, the organic compound having an electrochromic property may be represented by any one of the following compounds.

In the above formula,

n is an integer of 1 to 1000;

One embodiment of the present application includes a first electrode; A second electrode facing the first electrode; An electrolyte layer provided between the first electrode and the second electrode; And an electrochromic layer provided between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to an embodiment of the present application.

In one embodiment of the present application, the first electrode and the second electrode are not particularly limited as long as they are well known in the art. In one embodiment, the first electrode and the second electrode may be formed of indium doped tin oxide (ITO), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), indium doped zinc oxide (IZO) , Platinum, and the like, but is not limited thereto.

In one embodiment of the present application, the first electrode and the second electrode may each be a transparent electrode. Specifically, ITO having a transmittance of 80% or more can be used.

In one embodiment of the present application, the thicknesses of the first electrode and the second electrode are each independently 10 to 500 nm.

The first electrode or the second electrode may refer to a substrate coated with an anode active material commonly used in an electrochromic device. In addition, one embodiment of the substrate may be a current collector, and a copper, nickel, or SUS current collector may be used depending on a voltage region. Specifically, a copper current collector may be used.

The anode may be coated with a conventional anode active material used in an electrochromic device, and may include lithium, a metal material that can be alloyed with lithium, a transition metal oxide, a material capable of doping and dedoping lithium , A material capable of reversibly inserting and removing lithium ions, and the like can be used.

More specifically, according to one embodiment of the present application, the first electrode and the second electrode are each independently composed of lithium (Li), potassium (K), calcium (Ca), sodium (Na), magnesium (Mg) Aluminum, aluminum, zinc, iron, nickel, tin, lead, copper, indium, titanium, vanadium, And zirconium (Zr), or an alloy thereof.

Specific examples of the transition metal oxide include vanadium oxide and lithium vanadium oxide. Examples of the material capable of doping and dedoping lithium include Si, SiOx (0 <x <2), Si-Y alloy ( (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element or a combination element thereof and is not Si), Sn, SnO ₂ , Sn- Earth metals, Group 13 elements, Group 14 elements, transition metals, rare earth elements, or combinations thereof, but not Sn), and at least one of them may be mixed with SiO ₂ .

Specific examples of the element Y include, but are not limited to, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, Pd, Ru, Os, Hs, Rh, Ir, Pd, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.

As the material capable of reversibly intercalating and deintercalating lithium ions, any of carbonaceous anode active materials generally used in electrochromic devices can be used as the carbonaceous material, and typical examples thereof include crystalline carbon, amorphous carbon, Can be used. Examples of the crystalline carbon include graphite such as natural graphite or artificial graphite of amorphous, flake, flake, spherical or fiber type. Examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.

In one embodiment of the present application, the method of forming the electrochromic layer may employ any method known in the art, and is not particularly limited. For example, electroplating, sputtering, e-beam evaporation, chemical vapor deposition, or sol-gel coating may be used.

In one embodiment of the present application, the production of the electrolyte layer may utilize materials and methods known in the art. Specifically, pentaerythritol triacrylate (PETA) monomer, 1M or more LiClO ₄ , polycarbonate (PC), or the like can be used, but is not limited thereto.

In one embodiment of the present application, a solid electrolyte or a liquid electrolyte may be used for the electrolyte layer and is not particularly limited as long as it can act to transfer ions and electrons.

In one embodiment of the present application, the electrolyte layer may include a lithium salt, a plasticizer, an oligomer, a monomer, an additive, a radical initiator, and the like. Oligomers used in the present invention should be compatible with plasticizers.

In one embodiment of the present application, the thickness of the electrochromic layer may be 10 nm or more and 1.5 μm or less, preferably 20 nm or more and 1 μm or less.

The degree of discoloration and coloring can be controlled by varying the thickness of the electrochromic layer. Thinness can be controlled when transparency is required, and thickness can be adjusted when opacity is required rather than transparency.

One embodiment of the present application is a method of manufacturing a semiconductor device, comprising: preparing a first electrode; Forming a second electrode facing the first electrode; Forming an electrolyte layer between the first electrode and the second electrode; And forming an electrochromic layer between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to one embodiment of the present application. to provide.

In one embodiment of the present application, the method of forming the electrochromic layer may be a solution process.

As the solution process, spin coating, bar coating, slot die coating, and ink jet coating may be used.

In the present application, the production method of the organic compound and the production of the electrochromic device will be specifically described in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Manufacturing example  1. Preparation of compound 1

(1) Preparation of Compound A-2

1.39 mL phosphorus oxychloride (POCl ₃ ) (16 mmol) was added to 1.55 mL of N, N-dimethylformamide (DMF) (20 mmol), and the mixture was stirred at 0 ° C for 60 minutes A mixed solution was prepared. A solution of Compound A-1 (1.53 mmol) dissolved in 20 mL of dichloroethane (DCE) was added to the prepared mixed solution, and the mixture was stirred at 100 캜 for 48 hours. After stirring, 1 M sodium hydroxide (NaOH) was added and stirred for 1 hour for neutralization. Thereafter, the mixture was extracted with dichloromethane, and the extract was dried over anhydrous MgSO ₄ and evaporated. After removing the solvent under reduced pressure, the residue was purified by flash chromatography (hexane: chloroform = 4: 1) using hexane and chloroform as an eluent to obtain 1.066 g of Compound A-2 was obtained. (Yield: 67.3%).

3 is a graph showing the MS spectrum of Compound A-2.

(2) Preparation of compound 1

To a solution of Compound A-2 (0.725 g, 0.7 mmol) and Compound C-1 (0.68 g, 3.5 mmol) in 40 mL of chloroform (CHCl ₃ ) under nitrogen (N ₂ ) atmosphere, 2 mL of pyridine . The mixed solution was refluxed in a nitrogen atmosphere for 24 hours, extracted with dichloromethane (CH ₂ Cl ₂ ), and washed with water. After removal of the solvent, recrystallization was performed with methyl chloride (MC) / methanol, and the product was purified by using hexane, acetone, ethyl acetate, and chloroform (CHCl ₃ ) And purified by chromatography using a silica gel column. The resulting solid was recrystallized through chloroform. Thereafter, it was washed with methanol and dried under vacuum to obtain 905 mg of Compound 1. (Yield: 93%).

4 shows the MS spectrum of Compound 1. Fig.

Manufacturing example  2. Preparation of compound 2

(1) Preparation of compound B-2

Compound B-1 (2.5g, 9.4mmol) is NaOC (CH ₃₎ in 100mL of tetrahydrofuran (THF) is dissolved ₃ 4.13 g (43 mmol) of sodium-t-butoxide were added and a total of 2.58 mL of carbon disulfide (CS ₂ ) (43 mmol) was added over 1 hour. Then, 8.89 mL (50 mmol) of 2-ethylhexyl bromide was added, and the mixture was stirred for 24 hours. After the reaction, ammonium hydroxide (NH ₄ OH) was added to terminate the reaction, extracted with dichloromethane (DCM), and washed three times with water. The product was purified by chromatography on a silica gel column using hexane as eluent to give 3.63 g of compound B-2 in the form of a red oil. (Yield: 45%).

5 shows MS spectrum of compound B-2.

(2) Preparation of compound B-3

4 ml of phosphorus oxychloride (POCl ₃ ) (43 mmol) was added to N, N-dimethylformamide (DMF) (55 mmol) and stirred at 0 ° C for 60 minutes to prepare a mixed solution Respectively. A solution of Compound B-2 (4.19 mmol) in 40 mL of dichloroethane (DCE) was added to the prepared mixed solution, and the mixture was stirred at 100 ° C for 48 hours. After stirring, 1 M sodium hydroxide (NaOH) was added and stirred for 1 hour for neutralization. Thereafter, the mixture was extracted with dichloromethane, and the extract was dried over anhydrous MgSO ₄ and evaporated. After removal of the solvent under reduced pressure, the residue was purified by flash chromatography (hexane: chloroform = 4: 1) using hexane and chloroform as the eluent to obtain 2.47 g of Compound B-3 was obtained. (Yield: 64%).

6 is a graph showing the MS spectrum of Compound B-3.

(3) Preparation of Compound 2

To a solution of Compound B-3 (0.44 g, 0.48 mmol) and Compound C-1 (0.93 g, 4.8 mmol) in 30 mL of chloroform (CHCl ₃ ) under nitrogen (N ₂ ) atmosphere, 2 mL of pyridine . The mixed solution was refluxed in a nitrogen atmosphere for 24 hours, extracted with dichloromethane (CH ₂ Cl ₂ ), and washed with water. After removal of the solvent, recrystallization was carried out through methyl chloride (MC) / methanol and the product was purified by silica gel column chromatography using hexane, ethyl acetate and chloroform (CHCl ₃ ) gel column). The resulting solid was recrystallized through chloroform. It was then washed with methanol and dried under vacuum to give 550 mg of compound 2. [ (Yield: 90%).

7 is a graph showing the MS spectrum of Compound 2. Fig.

Manufacturing example  3. Preparation of Compound 3

To a solution of Compound B-3 (0.83 g, 0.9 mmol) and Compound C-2 (1.45 g, 9 mmol) in 15 mL of chloroform (CHCl ₃ ) under nitrogen (N ₂ ) atmosphere, three drops of piperidine ). The mixed solution was refluxed in a nitrogen atmosphere for 24 hours, extracted with dichloromethane (CH ₂ Cl ₂ ), and washed with water. After removal of the solvent, recrystallization was carried out through methyl chloride (MC) / methanol and the product was purified by silica gel column chromatography using hexane, ethyl acetate and chloroform (CHCl ₃ ) gel column). The resulting solid was recrystallized through chloroform. It was then washed with methanol and dried under vacuum to give 918 mg of compound 3. (Yield: 84.3%) (MALDI-TOF MS: 1208.3 g / mol)

8 is a diagram showing the UV spectrum of Compound 3. Fig.

8 (a) is the UV data in the solution state of the compound 3, (b) shows the compound 3 in the film state, (c) shows the compound 3 after the heat treatment at 110 캜 for 10 minutes in the film state UV data.

At this time, in the solution state, the compound 3 was dissolved in the chlorobenzene solution, and the film 3 was formed through the spin coating method in the solution state.

In FIG. 8, it can be seen that the vibration peak of (c) after heat treatment of the film is higher than the vibration peak of the film before heat treatment. As a result, it can be confirmed that the crystallinity is excellent after the heat treatment.

9 is a graph showing the MS spectrum of Compound 3. Fig.

Manufacturing example  4. Preparation of Compound 4

(1) Preparation of compound 4-1

(Pph ₃ ) ₄ catalyst (0.014 g, 0.012 mmol) was dissolved by dissolving the compound (0.268 g, 0.23 mmol) in which Sn was introduced in 20 mL of toluene: DMF = 3: 1 and the compound (0.557 g, And the mixture was stirred at 110 ° C for 48 hours. After the reaction, the reaction mixture was extracted with DCM, MgSO ₄ After removing the residue with magnesium sulfate, the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: Hex to CH: EA = 495: 5) to obtain a purple powder (Compound 4-1).

(2) Preparation of Compound 4

The precursor and 3-octylrhodanine were dissolved in CHCl ₃ , and three drops of piperidine were added at room temperature and refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CHCl ₃ to CHCl ₃ with EA) to give a dark green solid. The resulting solid (Compound 4) was recrystallized from CHCl ₃ and hexane.

10 is a graph showing the MS spectrum of Compound 4. Fig.

Manufacturing example  5. Preparation of Compound 5

The precursor and 3-ethylrhodanine were dissolved in CHCl ₃ , and three drops of piperidine were added at room temperature and refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CHCl ₃ to CHCl ₃ with EA) to give a dark green solid. The resulting solid (Compound 5) was recrystallized from CHCl ₃ and hexane.

11 is a graph showing the MS spectrum of Compound 5. Fig.

Manufacturing example  6. Preparation of Compound 6

(1) Preparation of Compound 6-3

60 mL of toluene and the compound of 6 mL DMF 6-1 (1.18 g, 1.1 mmol) and compound 6-2 (2.62 g, 2.45 mmol) was dissolved, Pd ₂ dba ₃ catalyst (0.0504 g, 0.055 mmol) and PPh ₃ (0.058 g, 0.22 mmol) was added thereto, and the mixture was stirred at 110 占 폚 for 48 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified through silica column (eluent: DCM to Cf) to give a dark purple solid (Compound 6-3) (59%).

(2) Preparation of Compound 6

The precursor and terminal group were dissolved in CHCl ₃ , and three drops of piperidine were added at room temperature and refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CHCl ₃ to CHCl ₃ with EA) to give a dark green solid (Compound 6). The resulting solid was recrystallized from CHCl ₃ and hexane.

12 shows MS spectrum of Compound 6. Fig.

Manufacturing example  7. Preparation of Compound 7

The precursor (1.17 g, 0.7 mmol) and 3-octylrhodanine (1.72 g, 7.0 mmol) were dissolved in 70 mL of CHCl ₃ and three drops of piperidine were added at room temperature and refluxed for 24 hours . After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CHCl ₃ to CHCl ₃ with EA) to give a dark green solid. The obtained solid (Compound 7) was recrystallized from CHCl ₃ and hexane. (96%)

13 is a graph showing the MS spectrum of Compound 7. Fig.

Manufacturing example  8. Preparation of Compound 8

(1) Preparation of Compound 8-2

A solution of Pd ₂ dba ₃ catalyst (0.0385 g, 0.042 mmol) and PPh ₃ ligand (0.38 g, 1.9 mmol) was dissolved in 40 mL of toluene and 4 mL of DMF and the compound 8-1 (0.99 g, 0.85 mmol) (0.0441 g, 0.168 mmol), which was stirred for 48 hours at 110 deg. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue is purified through silica column (eluent: DCM to Cf) to give a dark purple solid (Compound 8-2).

14 is a graph showing the MS spectrum of Compound 8-2.

(2) Preparation of Compound 8

(0.153 g, 0.1 mmol) and 3-octylrhodanine (0.245 g, 1.0 mmol) were dissolved in 10 mL of CHCl ₃ , and three drops of piperidine were added at room temperature. Lt; / RTI &gt; After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residual product was purified through silica column (eluent: CH ₂ Cl ₂ to CHCl ₃ ) to give a dark purple solid (Compound 8).

15 is a graph showing the MS spectrum of Compound 8. Fig.

Manufacturing example  9. Preparation of Compound 9

The precursor and the terminal group were dissolved in 10 mL of CHCl _{3, and} 5 mL of pyridine was added thereto at room temperature, followed by refluxing for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residual product was purified through silica column (eluent: CH ₂ Cl ₂ to CHCl ₃ ) to give a dark purple solid (Compound 9).

16 is a graph showing the MS spectrum of Compound 9;

Manufacturing example  10. Preparation of Compound 10

The precursor and the terminal group were dissolved in 10 mL of CHCl ₃ , 1 mL of piperidine was added at room temperature, and the mixture was refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO ₄ (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CH ₂ Cl ₂ to CHCl ₃ ) to give a dark purple solid (Compound 10).

17 is a graph showing the MS spectrum of Compound 10. Fig.

Manufacturing example  11. Preparation of compound 11

A microwave reaction vessel was charged with M1 (215 mg, 0.525 mmol), M2 (106 mg, 0.175 mmol), M3 (712 mg, 0.7 mmol), tris (dibenzylideneacetone) dipalladium (0 mol%) (2 mol%) and tri (o-tolyl) phosphine (8 mol%) were dissolved in 6 mL of chlorobenzene. 20 minutes at 170 ° C, 30 minutes at 170 ° C, and 10 minutes at 180 ° C. After the polymerization, 2,5-bis (trimethylstannyl) thiophene and 4-bromobenzotrifluoride were added and further reacted at 150 ° C. for 30 minutes . The reaction product was precipitated in methanol, and then purified by Soxhlet in the order of methanol, hexane, dichloromethane and chloroform. The polymer dissolved in chloroform was precipitated in methanol and filtered to obtain a final polymer. (yield = 82.4%; Mn = 44.6 kDa, and polydispersity index (PDI) = 1.44)

Manufacturing example  12. Preparation of Compound 12

To the microwave reaction vessel was added N1 (506.4 mg, 0.3 mmol), N2 (365.7 mg, 0.3 mmol) and tetrakis (triphenylphosphine) palladium (6.9 mg, 0.006 mmol) And dissolved in toluene and 2 mL of DMF. The mixture was polymerized at 110 DEG C for 10 minutes, at 130 DEG C for 10 minutes, at 140 DEG C for 10 minutes, and at 150 DEG C for 60 minutes. After the polymerization, the reaction product was precipitated in methanol, and purified through a Soxhlet in the order of methanol, hexane, dichloromethane and chloroform. The polymer dissolved in chloroform was precipitated in methanol and filtered to obtain a final polymer. (Yield = 24%, Mn = 9.9 kDa, PDI = 1.508)

Manufacturing example  13. Preparation of Compound 13

(0.316 g, 0.35 mmol), S2 (0.211 g, 0.35 mmol), S3 (0.487 g, 0.7 mmol), tris (dibenzylideneacetone) (8 mol%) of tri (o-tolyl) phosphine and 7 mL of vacuum chlorobenzene were added to the reaction mixture at 120 ° C. for 10 minutes and at 150 ° C. 20 minutes, 170 占 폚 for 30 minutes, and 180 占 폚 for 10 minutes. After the polymerization, the polymer was reacted with 2,5-bis (trimethylstannyl) thiophene and 4-bromobenzotrifluoride at 150 ° C for 30 minutes And finally capped. After the polymerization, the reaction product was precipitated in methanol and then purified through a Soxhlet in the order of methanol, hexane and dichloromethane. The polymer dissolved in dichloromethane was precipitated in methanol and filtered to obtain a final polymer. (Yield = 24%, Mn = 3.2 kDa, PDI = 1.57)

Examples. One

Compound 5 according to Preparation Example 5 was dissolved in chlorobenzene solvent in a concentration of 7 wt% and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed with a chlorobenzene solution (concentration -100 袖 g / mL) And then the mixture was mixed in a volume ratio of 1: 1. Then, the mixture was spin-coated on an ITO (indium tin oxide) substrate as a working electrode and dried, and LiClO ₄ was dissolved in propylene carbonate as an electrolyte layer. And a silver electrode were used to fabricate an electrochromic device.

Comparative Example. One

In Example 1, an electrochromic device was fabricated in the same manner as in Example 1 except that P3HT (poly (3-hexylthiophene) -containing carbon nanotubes were not used.

The electrochromic device manufactured according to Example 1 and Comparative Example 1 was subjected to measurement of change in absorption wavelength according to a voltage change. The results are shown in FIGS. 18 and 19.

In the case of FIG. 18 of Comparative Example 1, a quenching phenomenon in which the absorption decreases from 0.6 V is observed, but it can be confirmed that the absorption starts to decrease from 0.4 V in the case of FIG. 19 of Example 1. As a result, it can be confirmed that the driving voltage of the electrochromic device is lowered, and it is confirmed that the device stability of the electrochromic device can be improved relatively because the device operates at a low voltage.

20 is a graph showing CV results of Example 1 and Comparative Example 1. Fig. As can be seen from FIG. 20, it was confirmed that the electrochromic device of Example 1 decreased the oxidation potential by about 0.2 V as compared with the electrochromic device of Comparative Example 1 on CV, which means that the electrochemical reaction activity was increased .

Example 2.

P3HT was dissolved in chlorobenzene solvent to a concentration of 7 wt%, and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed with chlorobenzene solution (concentration -100 μg / mL) at a volume ratio of 0.5: 1. After spin coating on an indium tin oxide (ITO) substrate as a working electrode, LiClO ₄ was dissolved in propylene carbonate as an electrolyte layer, which was used as an electrolyte, and a counter electrode and a reference electrode were electroplated A coloring element was prepared.

Example 3.

P3HT was dissolved in chlorobenzene solvent to a concentration of 7 wt%, and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed in a 1: 1 volume ratio with chlorobenzene solution (concentration -100 μg / mL) After spin coating on an indium tin oxide (ITO) substrate as a working electrode, LiClO ₄ was dissolved in propylene carbonate as an electrolyte layer, which was used as an electrolyte, and a counter electrode and a reference electrode were electroplated A coloring element was prepared.

Example 4.

P3HT was dissolved in a chlorobenzene solvent to a concentration of 7 wt%, and then carbon nanotubes surrounded by poly (3-hexylthiophene) were mixed with a chlorobenzene solution (concentration: -100 μg / mL) in a volume ratio of 2: 1. After spin coating on an indium tin oxide (ITO) substrate as a working electrode, LiClO ₄ was dissolved in propylene carbonate as an electrolyte layer, which was used as an electrolyte, and a counter electrode and a reference electrode were electroplated A coloring element was prepared.

Comparative Example 2

The electrochromic device was fabricated in the same manner as in Example 2 except that P3HT (poly (3-hexylthiophene) -containing carbon nanotubes were not used in Example 2.

Example 5.

Compound 13 according to Preparation Example 13 was dissolved in chlorobenzene solvent in a concentration of 7 wt%, and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed with chlorobenzene solution (concentration -100 μg / mL) And then the mixture was mixed in a volume ratio of 1: 1. Then, the mixture was spin-coated on an ITO (indium tin oxide) substrate as a working electrode and dried, and LiClO ₄ was dissolved in propylene carbonate as an electrolyte layer. And a silver electrode were used to fabricate an electrochromic device.

The electrochromic devices prepared according to Example 5 were subjected to measurement of spectroelectrochemical graphs according to the voltage change. The results are shown in FIG. 26.

As can be seen from FIG. 26, absorption peaks were observed at 400 nm and 620 nm before applying a voltage, but when a voltage of 0.6 V or higher was applied, the absorption peak gradually decreased. When 1.0 V was applied, the absorption peak decreased, Of the total number of patients.

FIGS. 21 to 25 are diagrams showing the difference in transmittance between the coloration state and the bleaching state of Comparative Example 2 and Examples 2 to 5. FIG.

FIG. 21 is a graph showing the difference in transmittance between the coloration state and the bleaching state of Comparative Example 2. FIG. As can be seen in FIG. 21, the difference in transmission between the coloration state and the bleaching state is 42.3%, the coloration speed is 1.1 seconds, and the bleaching speed is 1.5 seconds.

FIG. 22 is a graph showing the difference in transmission between the coloration state and the bleaching state of Example 2. FIG. The difference in transmittance between the coloration state and the bleaching state was 42.8%, which is not much different from that of Comparative Example 2 in which carbon nanotubes were not mixed. However, when the carbon nanotubes were introduced, the change in transmittance was not significant, the coloring speed was 0.4 seconds and the bleaching speed was 0.4 seconds. As a result, it was confirmed that the rate of electrochromatography was improved as compared with Comparative Example 2.

FIG. 23 is a graph showing the difference in transmittance between the coloration state and the bleaching state of Example 3. The difference in transmittance between the coloration state and the bleaching state is 43.5%, which means that the carbon nanotubes are not mixed The coloring speed was 0.5 seconds and the bleaching speed was 1.1 seconds as compared with Comparative Example 2, although there was no significant difference from Comparative Example 2 in which the carbon nanotubes were introduced , It was confirmed that the rate of electrochromatography was improved.

FIG. 24 is a graph showing the difference in transmittance between the coloration state and the bleaching state of the fourth embodiment. FIG. The difference in transmittance between the coloration state and the bleaching state was 33.6%, the coloration speed was 0.4 seconds, and the bleaching speed was 0.5 seconds. As compared with Comparative Example 2, Of the total population.

FIG. 25 is a graph showing the difference in transmittance between the coloration state and the bleaching state of the fifth embodiment. FIG. The difference in transmittance between the coloration state and the bleaching state was 19.5%, the coloration speed was 0.19 seconds, and the bleaching speed was 0.47 seconds. As compared with Comparative Example 2, Of the total population.

Comparing the above Examples 2 to 5 and Comparative Example 2, the carbon nanotube-based electrochromic coloring has a disadvantage in that the transmittance is poor in a coloration state, but the carbon nanotube-based carbon nanotube (P3HT) It can be seen that there is no great difference in the transmittance of the coloration state of the second to fourth embodiments relative to the second comparative example.

In addition, when carbon nanotubes surrounded by poly (3-hexylthiophene) are introduced, the time required to decolorize in a color state and the time to change a color in a decolorized state become faster, The introduction of nanotubes accelerates the rate of charge transfer, which leads to faster coloration and bleaching speeds, ie, improved switching speed.

The coloration rate refers to the time taken to have the color in the discolored state-the time taken to less than 5% of the final color (transmittance). For example, if the transmittance of a colored state is 0% and the transmittance of a decolored state is 100%, the time it takes to change from 100% to 5% is the coloration speed.

The bleaching speed means the time taken to decolorize in the state of having color - the time taken up to less than 5% of the final decoloring. For example, assuming that the transmittance of a colored state is 0% and the transmittance of a decolored state is 100%, the time it takes to change from 0% to 95% is the bleaching speed.

Claims (13)

Organic compounds having electrochromic properties; And A carbon nanotube whose surface is covered with a polymer at least in part; &Lt; / RTI &gt; The electrochromic composite according to claim 1, wherein the shape of the carbon nanotube in which the polymer is covered with at least a part of the surface has a structure in which the polymer is spirally surrounded by the carbon nanotube. The electrochromic composite according to claim 1, wherein the weight ratio of the organic compound to the carbon nanotubes covered with the polymer is 10: 1 to 400: 1. The electrochromic composite according to claim 1, wherein the polymer comprises at least one member selected from the group consisting of a thiophene-based polymer and a fluorene-based polymer. [2] The electrochromic composite according to claim 1, wherein the polymer comprises 30 to 200 parts by weight based on 100 parts by weight of the carbon nanotubes based on the solid content. The electrochromic composite according to claim 1, wherein the weight average molecular weight of the polymer is 3,000 g / mol to 1,000,000 g / mol. The electrochromic composite according to claim 1, wherein the organic compound having an electrochromic property is any one of the following formulas (1) to (7): [Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the general formulas (1) to (7) X, X1 to X4 and Z1 to Z5 are the same or different from each other, and each independently C = CRR '; SiRR '; O; S; Or NR, Ar1 and Ar2 are the same or different and are each a group independently acting as an electron acceptor, Ar 3 to Ar 6 are the same or different from each other, and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted alkoxy group; Or SiRR'R " A is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, T1 and T2 are the same or different and are each independently a direct bond; O; Or S, R1 to R18 are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, A halogen atom, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, A substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, p and q are each an integer of 0 to 5, a and b are each an integer of 0 to 3, a1 is a number of 0 < a1 < 1, a2 is a number of 0 < a2 < 1, b1 is a number of 0 < b1 < 1, b2 is a number of 0 < b2 < a1 + a2 and b1 + b2 are integers of 1, n is an integer of 1 to 1000, m1, m2, m3, n1 and n2 are integers of 0 to 4, respectively. The electrochromic composite according to claim 7, wherein Ar1 and Ar2 are the same or different and each is any one of the following structures:

In the above structure, c and d are integers of 1 to 4, When c and d are two or more, structures in parentheses of two or more are the same or different from each other, R15 to R20 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method of claim 7, Wherein the organic compound having an electrochromic property is represented by any one of the following compounds:

In the above formula, n is an integer of 1 to 1000; A first electrode; A second electrode facing the first electrode; An electrolyte layer provided between the first electrode and the second electrode; And An electrochromic layer provided between the electrolyte layer and the second electrode; / RTI &gt; Wherein the electrochromic layer comprises the electrochromic composite according to any one of claims 1 to 9. The electrochromic device according to claim 10, wherein the thickness of the electrochromic layer is 20 nm or more and 1 m or less. Preparing a first electrode; Forming a second electrode facing the first electrode; Forming an electrolyte layer between the first electrode and the second electrode; And And forming an electrochromic layer between the electrolyte layer and the second electrode, Wherein the electrochromic layer comprises the electrochromic composite according to any one of claims 1 to 9. The method of claim 12, Wherein the step of forming the electrochromic layer is a solution process.

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