High transparency electrochromic polymers

Abstract

To provide a new type of electrochromic polymers comprising meta-conjugated linkers and aromatic moieties, which present high transparency in the visible light region in a neutral state.SOLUTION: An electrochromic polymer comprises a repeat unit comprising one or more meta-conjugated linkers (MCLs) and one or more aromatic moieties (Ars). Each of the one or more MCLs is partially conjugated with the one or more Ars at meta positions of the MCLs to form a polymer main chain of the electrochromic polymer. The electrochromic polymer undergoes optical switching and color change in an electrochromic device, where the electrochromic device shows high transparency and high optical contrast.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and benefit of U.S. Patent Application No. 18 / 093,287 filed on 4 January 2023, U.S. Patent Application No. 17 / 748,383 filed on 19 May 2022, and U.S. Patent Application No. 17 / 668,300 filed on 9 February 2022. The entire contents of all of the above applications are incorporated herein by reference.

[0002] This disclosure relates to a novel type of electrochromic polymer comprising a meta-conjugated linker and an aromatic moiety, which exhibits high transparency in the visible light region in a neutral state. When the film of this polymer is oxidized, it becomes highly absorbent in the visible and near-infrared regions and thus colored. Devices incorporating such conjugated electrochromic polymer films having high optical contrast and high transmittance are also disclosed. [Background technology]

[0003] Electrochromic elements allow for the adjustment of light transmittance and control of solar thermal gain. Compared to inorganic electrochromic elements manufactured through vacuum sputtering processes, polymer-based electrochromic windows can be manufactured through roll-to-roll coating and lamination. Therefore, this results in low-cost production and manufacturing flexibility.

[0004] Polymer-based electrochromic elements are typically sp 2It is composed of conjugated electrochromic polymers (ECPs) characterized by a fully conjugated polymer backbone made of hybrid carbon. Conventionally, ECPs typically have strong absorbance in the visible light region and are therefore colored in their neutral state. When they are oxidized, their absorption shifts to the near-infrared (near-infrared) region and they become transparent in the visible light region. However, oxidized polymers have weak absorption in the visible light region, resulting in residual color. The problem becomes more serious with thicker polymer films. As a result, it negatively affects the optical contrast of the polymer. Furthermore, it limits the highest light transmittance that conjugated electrochromic polymers can achieve. In addition, conventional ECPs in the neutral state block visible light and transmit near-infrared light through the film, while in the transparent state, they transmit visible light and block near-infrared light. This combination is inefficient for heat management and control of solar heat gain (SHG). SHG represents the way in which radiation from the sun is converted into heat through the window product. [Overview of the Initiative] [Means for solving the problem]

[0005] This disclosure relates to a novel type of electrochromic polymer. The electrochromic polymers disclosed herein consist of a polymer backbone comprising one or more meta-conjugated linkers (MCLs) and one or more aromatic moieties (Ar). Each of the one or more MCLs is partially conjugated with one or more Ar at the meta position of the one or more MCLs to form the polymer backbone of the electrochromic polymer. In some embodiments, the electrochromic polymers disclosed herein are anodically-coloring electrochromic polymers (AC-ECPs) that become colored upon oxidation.

[0006] In some embodiments, the electrochromic polymers of this disclosure have an absorption onset of 420 nm or less in a neutral state. In some embodiments, the absorption maximum (λ maxThe wavelength at which the polymer has its strongest photon absorption is less than 410 nm in the neutral state. In some embodiments, the electrochromic polymers of this disclosure are colorless in the neutral state, while in the oxidized state they are colored, visible, and near-infrared absorbent. Oxidized electrochromic polymers are 10 in the visible and / or near-IR region. 4 cm -1 It has a higher absorption coefficient and therefore is colored in the oxidized state.

[0007] Despite the high band gap, the electrochromic polymers of this disclosure still have relatively low oxidation potentials in the range of 0.1 to 1.5 V, including both ends, with respect to Ag / AgCl electrodes in some embodiments.

[0008] MCL comprises at least one aromatic structure or condensed aromatic structure, or a combination thereof. The aromatic structure comprises a benzene structure or a heterocyclic structure. The condensed aromatic structure comprises a condensed benzene structure, or a condensed heterocyclic structure, or a condensed benzene and heterocyclic structure.

[0009] In some embodiments, one or more MCLs and one or more Ars are added to the electrochromic polymer of the Disclosure.

[0010] [ka]

[0011] The general formula is arranged in an alternating or random pattern.

[0012] In this structure, n is an integer greater than 0, and m1, m2, ..., m n Each of them is a non-negative integer, where m1, m2, ..., m n At least one of them is greater than 0. One or more MCLs (or one or more Ars) can be the same as or different from each other.

[0013] In some embodiments, one or more MCLs and corresponding meta-positions are given by the following formula:

[0014]

Chemical Formula

[0015]

Chemical Formula

[0016]

Chemical Formula

[0017]

Chemical Formula

[0018]

Chemical Formula

[0019] (where each wavy line represents a meta-position adjacent to and connected to one or more Ars; X is S, Se, N, C, or O; R1 to R 12 include, but are not limited to, the following: hydrogen, C1 - C 30 alkyl, C2 - C 30 alkenyl, C2 - C 30 alkynyl, C2 - C 30 alkylcarbonyl, C1 - C 30 alkoxy, C3 - C 30 alkoxyalkyl, C2 - C 30 alkoxycarbonyl, C4 - C 30 alkoxycarbonylalkyl, C1 - C 30 alkylthio, C1 - C 30 aminylcarbonyl, C4 - C 30 aminylalkyl, C1 - C 30 alkylaminyl, C1 - C 30 alkylsulfonyl, C3 - C 30Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, or C3~C 30 (Selected independently from substituents including heteroarylalkyl groups) It includes one of the following.

[0020] In some embodiments, one or more Ars are given by the following formula:

[0021] [ka]

[0022] (In the formula, R 13 , R 14 and R 15 Each of these, but not limited to, includes the following: hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, or C3~C 30 (Selected independently from substituents including heteroarylalkyl groups) It includes one of the following: a thiophene unit, a furan unit, a selenophene unit, or a pyrrole unit, or any combination thereof.

[0023] In some embodiments, the thiophene unit is given by the following formula:

[0024] [ka]

[0025] (wherein X is S, Se, N, C or O; R 15 ~R 18 Each of these is, but is not limited to, the following hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Alkylthio, C1-C 30 Aminylcarbonyl, C4-C 30 Aminylalkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkylalkyloxy, C1-C 12 Heterocyclyl, C1-C 12 Heterocyclyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, or C3-C 30 selected independently from substituents including heteroarylalkyl); Y is any one or more of Ar, an aromatic structure, or a fused aromatic structure, or a combination thereof) or a combination thereof.

[0026] In some embodiments, X of the thiophene-based unit is O.

[0027] In some embodiments, the electrochromic polymer of the present disclosure has the following formula:

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] (In the formula, n and m are integers greater than 0, and a and b are integers greater than or equal to 0, with at least one of a and b being greater than 0.) Includes.

[0033] Features of various embodiments of this technology are described in detail in the appended claims. A better understanding of the features and advantages of this technology will be obtained by referring to the following detailed description illustrating exemplary embodiments in which the principles of the present invention are utilized, and to the accompanying drawings below. For the purpose of illustrating the present invention, the drawings illustrate aspects of one or more embodiments of the present invention. However, it should be understood that the present invention is not limited to the exact apparatus and means shown in the drawings. [Brief explanation of the drawing]

[0034] [Figure 1(A)] This figure illustrates a different color change mechanism of the ECP of this disclosure compared to a conventional ECP (Figure 1(B)). [Figure 1(B)] This diagram illustrates the color change mechanism of conventional ECP. [Figure 2] This figure shows the CV data of an exemplary solid-state device using Example ECP-1 according to one embodiment. [Figure 3] This is a diagram illustrating the switching kinetics of a typical solid-state device using Example ECP-1 at 545 nm according to one embodiment. [Figure 4] This figure shows the absorbance spectra of an exemplary ECP-1 thin film at different voltages according to one embodiment. [Figure 5] This figure shows the CV data of an exemplary solid-state element using another embodiment, ECP-2, according to one of the embodiments. [Figure 6] This is a diagram illustrating the switching kinetics of an exemplary solid-state device using Example ECP-2 at 550 nm according to one embodiment. [Figure 7] This figure shows the absorbance spectra of an exemplary ECP-2 thin film at different voltages according to one embodiment. [Figure 8] This figure shows the absorbance spectra of an exemplary ECP-6 solution at 0.1 mg / mL in dichloromethane at different voltages according to one embodiment. [Figure 9] This figure shows the absorbance spectra of an exemplary ECP-7 solution in dichloromethane at a concentration of 0.1 mg / mL at different voltages according to one embodiment. [Modes for carrying out the invention]

[0035] The following description includes certain details in order to provide a complete understanding of the various embodiments of the present invention. However, those skilled in the art will understand that the present invention can be carried out without these details. Furthermore, although various embodiments of the present invention are disclosed herein, many modifications and alterations can be made within the scope of the invention in accordance with the general knowledge common to those skilled in the art. Such modifications include the substitution of known equivalents for any aspect of the present invention in order to achieve substantially the same results in substantially the same manner.

[0036] Unless otherwise specified in the context, the word “comprise,” and its variations such as “comprises” and “comprising,” throughout this specification and the claims should be interpreted as having an open and inclusive meaning, i.e., “includes, but is not limited to.” Numerical range descriptions throughout the specification are intended to function as abbreviations for each individual value within the range that includes the value defining the range, and each individual value is incorporated into the specification as it is individually described herein. Furthermore, the singular forms “a,” “an,” and “the” include multiple referents unless explicitly indicated in the context.

[0037] Throughout this specification, any reference to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in relation to an embodiment is included in at least one embodiment of the present invention. Therefore, the occurrence of the phrase “in one embodiment” or “in one embodiment” in various places throughout this specification does not necessarily refer to the same embodiment, but could be several examples. Furthermore, particular features, structures, or characteristics may be combined in any preferred manner in one or more embodiments.

[0038] This disclosure relates to a novel type of electrochromic polymer. The electrochromic polymers disclosed herein consist of a polymer backbone comprising one or more metaconjugated linkers (MCLs) and one or more aromatic moieties (Ars). Each of the one or more MCLs is partially conjugated with one or more Ars at the meta position of the one or more MCLs to form the polymer backbone of the electrochromic polymer. In some embodiments, the electrochromic polymers disclosed herein consist of repeating units comprising one or more MCLs and one or more Ars, and the metaconjugation is introduced along the polymer backbone through the use of MCLs. In some embodiments, the electrochromic polymer is an anodic colored electrochromic polymer (AC-ECP), which becomes colored upon oxidation.

[0039] As shown in Figure 1, conventional conjugated ECP (Figure 1(B)) is fully conjugated and has strong absorbance in the visible light region, and therefore is colored in its neutral state, while when oxidized (oxidized state), its absorption shifts towards the near-infrared region and becomes transmissive. However, the oxidized polymer still has weak absorption in the visible light region, leading to residual color. On the other hand, as illustrated in one example disclosed in the ECP of Figure 1(A), the ECP shows virtually no absorption after 450 nm in the neutral state, and in the oxidized state, it has several absorption peaks in the visible light and near-infrared ranges, showing coloration in the visible light range and near-infrared absorption.

[0040] The electrochromic polymers of this disclosure can synchronize the passage or blocking of visible light and near-irradiance light, which is very useful in one embodiment for an electrochromic window for managing solar thermal gain. The electrochromic polymers of this disclosure are transparent in a neutral state and colored and IR absorbent in an oxidized state, and this property is highly desirable for achieving high optical contrast, high transmittance, and synergistic solar thermal gain.

[0041] The electrochromic polymers of this disclosure are transparent in the visible light region in a neutral state and colored in an oxidized state. For example, the electrochromic polymers of this disclosure may have a transmittance of at least 60% in the visible light region (e.g., 450–750 nm) in a neutral state. In some embodiments, the electrochromic polymers of this disclosure may have a transmittance of at least 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 98%, or higher in the 450–750 nm range in a neutral state. In some embodiments, the electrochromic polymers of this disclosure are transparent in the visible light region in a neutral state. In an oxidized state, the electrochromic polymers of this disclosure have absorption in the visible light region (e.g., about 360–750 nm) and the near-infrared region (e.g., about 750–1600 nanometers), thereby coloring and being near-infrared absorbent.

[0042] The electrochromic polymers of this disclosure have UV absorption and an energy band gap. The energy band gap is the energy difference between the valence band and the conduction band of an electron. It is the minimum change in energy required to excite an electron to a state in the conduction band that can participate in conduction. Absorption onset (λ c ) is a wavelength higher than the wavelength at which the polymer does not exhibit photon absorption. The energy band gap can be calculated as 1240 / absorption onset wavelength. In some embodiments, the electrochromic polymers disclosed herein have absorption onset at 450 nm or less in a neutral state. In some embodiments, the electrochromic polymers disclosed herein have absorption onset at 440 nm, 430 nm, 420 nm, 410 nm, 405 nm, or 400 nm or less in a neutral state. In some embodiments, the absorption maximum (λ max The wavelength at which the polymer has its strongest photon absorption is less than 420 nm in a neutral state. In some embodiments, the absorption maximum is less than 410 nm, 405 nm, or 400 nm in a neutral state. In some embodiments, the electrochromic polymer of the Disclosure has an energy band gap of 2.8 eV or greater and less than 4.0 eV in a neutral state. In some embodiments, the electrochromic polymer of the Disclosure has an energy band gap of 2.9, 3.0, or 3.1 eV or greater and less than 4.0 eV in a neutral state. In some embodiments, the electrochromic polymers of the present disclosure are colorless in a neutral state (e.g., no absorbance at 400-750 nm, 410-750 nm, or 420-750 nm) or yellow (e.g., tailing absorption at 400-500 nm, 410-500 nm, 420-500 nm, 400-480 nm, 410-480 nm, 420-480 nm, 400-450 nm, 410-450 nm, or 420-450 nm), colored in an oxidized state, visible, and near-IR absorbent. The oxidized electrochromic polymers are 10 in the visible and / or near-IR region. 4 cm -1 It has a higher absorption coefficient and therefore discolors in an oxidized state.

[0043] Due to substantial absorbance in the visible light range in the neutral state and high absorbance in the visible light range in the oxidized state, the electrochromic polymers of this disclosure exhibit higher optical contrast and higher light transmittance compared to conventional ECPs. Despite the high band gap, the electrochromic polymers of this disclosure have a relatively low oxidation potential in the range of 0.1 to 1.5 V (inclusive) with respect to the Ag / AgCl electrode in some embodiments. In some embodiments, the electrochromic polymers of this disclosure have a low oxidation potential in the range of 0.1 to 1 V (inclusive) with respect to the Ag / AgCl electrode. The relatively low oxidation potential can be beneficial to the cycling durability of the ECP. Therefore, the electrochromic polymers of this disclosure can be successfully incorporated into devices with good cycling stability / reliability and high optical contrast.

[0044] MCL comprises at least one aromatic structure or condensed aromatic structure, or a combination thereof. The aromatic structure comprises a benzene structure or a heterocyclic structure. The condensed aromatic structure comprises a condensed benzene structure, or a condensed heterocyclic structure, or a condensed benzene and heterocyclic structure. In some embodiments, MCL comprises at least one benzene, or naphthalene, or a 5-membered heterocyclic, or a benzene-condensed 5-membered heterocyclic, or a combination thereof. Side chains or aromatic side chains may also be introduced onto the MCL to modify the performance of the MCL, for example, its solubility, processability, or stability.

[0045] In some embodiments, one or more MCLs and one or more Ars are given by the following general formula:

[0046] [ka]

[0047] They are arranged in an alternating or random pattern.

[0048] In this structure, n is an integer greater than 0, and m1, m2, ..., m n Each of them is a non-negative integer, where m1, m2, ..., m n At least one of these is greater than 0. One or more Ars are aromatic moieties, and an aromatic moiety may contain one or more aromatic structures. Each of the one or more MCLs (or Ars) may be the same as or different from one another.

[0049] Metaconjugation is introduced into the polymer backbone through the use of one or more MCLs. Each of the one or more MCLs is partially conjugated in the polymer backbone by linking with one or more Ar atoms through their meta positions. For example, the meta positions are two positions in the aromatic or condensed aromatic structure of the MCL. When meta positions are linked, the π electrons from the aromatic or condensed aromatic structure cannot be completely delocalized to another adjacent linked unit through the p orbitals.

[0050] In some embodiments, the aromatic structure of MCL comprises a benzene structure or a five-membered heterocyclic structure, and the aromatic structure of MCL is substituted at the meta position, with the meta positions being the 1- and 3-positions of the aromatic structure. In some embodiments, the condensed aromatic structure of MCL comprises naphthalene, and the condensed aromatic structure is substituted at the meta position, with the meta positions being the 1- and 3-positions, or the 1- and 4-positions, or the 1- and 6-positions on the naphthalene. In some embodiments, the condensed aromatic structure of MCL comprises benzene fused with a five-membered heterocyclic ring, and the condensed aromatic structure is substituted at the meta position, with the meta positions being the 1- and 3-positions, or the 1- and 5-positions, on the benzene condensed heterocyclic ring.

[0051] The following are example structures of one or more MCLs and their corresponding meta-positions:

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] (In the formula, X is S, Se, N, C or O; R1~R 12 This includes, but is not limited to, the following: hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, or C3~C 30 It may include one of the substituents independently selected from heteroarylalkyl groups (the tilde indicates the meta position).

[0058] One or more Ars may include, but are not limited to:

[0059] [ka]

[0060] It may contain one of the following units having the formula: a thiophene unit, a furan unit, a selenophene unit, or a pyrrole unit, or any combination thereof.

[0061] With the above structure, R 13 , R 14 and R 15 Each of these is, but is not limited to, the following hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, or C3~C 30 The substituents are independently selected from those containing heteroarylalkyl groups.

[0062] Thiophene units are not limited to the following, but include:

[0063] [ka]

[0064] This may include the formulas or combinations thereof.

[0065] In the above structure, X is S, Se, N, C, or O; R 15 ~R 18 Each of these is not limited to, but includes the following: hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, or C3~C 30 A substituent is independently selected from heteroarylalkyl groups; Y is one or more of Ar, an aromatic structure, or a condensed aromatic structure, or a combination thereof.

[0066] In some embodiments, the thiophene unit X is O.

[0067] By introducing metaconjugation to the electrochromic polymer backbone, electron conjugation along the polymer backbone is disrupted, leading to a high band gap (>2.0 eV). Consequently, the electrochromic polymers of this disclosure appear highly transmissive (or even transparent) in a neutral state. Oxidation of the ECP results in a lower band gap (<1.5 eV), and the polymer's absorption redshifts from the UV region to the visible and near-IR regions. Consequently, the polymer becomes highly colored.

[0068] One or more Ar groups may comprise one or more aromatic or condensed aromatic structures. By controlling the type and amount of Ar, the redox potential of the electrochromic polymers of this disclosure can be easily adjusted while maintaining high transparency in the visible light range at neutral conditions. For example, by introducing electron-rich units (e.g., dioxythiophene) onto the main chain, the polymer can be made more easily oxidized, thereby lowering its onset potential and improving its electrochemical and electrochromic cycling stability. The redox potential of the electrochromic polymers of this disclosure can also be adjusted by changing substituents on the MCL (e.g., introducing alkoxy side chains).

[0069] The electrochromic polymers of this disclosure can be dissolved in a solvent, such as toluene or p-xylene, and used in a solution-processable film casting process. By controlling the concentration of the polymer solution, polymer thin films with controllable thickness can be obtained. Furthermore, the excellent solubility makes the electrochromic polymers of this disclosure compatible with various casting methods, such as spin coating, spray coating, and drop casting. The manufacturing-friendly process enables a wider range of applications.

[0070] Examples are shown below.

[0071] Embodiment [Examples]

[0072] ECP-1 In some embodiments, the ECP-1 of this disclosure is as follows:

[0073] [ka]

[0074] It has the formula.

[0075] ECP-1 is synthesized by preparing a carbazole-containing reaction unit and then polymerizing it with a dimer unit. The detailed method includes the following steps:

[0076] Step 1-1: Preparation of the carbazole-containing reaction unit (compound 2).

[0077] [ka]

[0078] 3,6-Dibromocarbazole is dissolved in DMF. Then, 1.2 equivalents of NaH are added and the mixture is stirred for 2 hours. Next, 1.2 equivalents of compound 1 are added to the reaction and the mixture is stirred overnight. Then water is added to the reaction and the solid is precipitated. The suspension is filtered to obtain the desired product, compound 2, as a white solid.

[0079] Step 1-2: Polymerization: Polymerization of carbazole-containing reaction units with dimer units.

[0080] [ka]

[0081] Compound 2 (1 equivalent), Compound 3 (1 equivalent), K2CO3 (2.6 equivalents), PivOH (0.3 equivalents), and Pd(OAc)2 (0.02 equivalents) were added to a Schenk tube. The tube was then aspirated (for 3-5 minutes) and refilled with nitrogen. This procedure was repeated three times. Subsequently, the nitrogen degassing solvent dimethylacetamide (DMAc) was added, and the mixture was heated to 120°C and maintained for 14 hours. The mixture was then poured into methanol to precipitate the crude polymer solid. The solid was filtered, redissolved in chloroform, and washed three times with water. The chloroform solution was added to a large amount of methanol to precipitate the polymer. The suspension was filtered to obtain the desired product, polymer ECP-1.

[0082] The resulting ECP-1 has an oxidation potential of approximately 0.75 V (vs. Ag / AgCl) and an energy band gap higher than 3.0 eV. ECP-1 is assembled into a solid-state ECD using ECP-1 as the electrochromic layer, 0.2 M LiTFSI in PEGDA as the electrolyte, and VOx as the ion storage layer. The solid-state ECD can be stably switched between -0.5 V and 1.5 V (Figure 2). The absorbance spectra of ECP-1 in the neutral and oxidized states are shown in Figure 4, along with λc at 405 nm and λmax at 320 nm. The solid-state ECD exhibits high transparency with a high transmittance of 93% in the neutral state (Figure 3), and when ECP-1 is oxidized, it switches to a vivid blue color with one absorption peak at approximately 614 nm and another broader absorption band in the near-IR region at approximately 900–1100 nm (Figure 4). The optical contrast of solid-state ECDs is approximately 75% (Figure 3). [Examples]

[0083] ECP-2 In some embodiments, the ECP-2 of this disclosure is expressed as follows:

[0084] [ka]

[0085] It has.

[0086] ECP-2 is synthesized by first preparing substituted benzene reaction units and then polymerizing them with acyclic dioxythiophene (AcDOT) units. The detailed method includes the following steps:

[0087] Step 2-1: A step in which a benzene-containing reaction unit (compound 4) is prepared by two steps.

[0088] [ka]

[0089] Compound 5 and p-toluenesulfonic acid are dissolved in acetonitrile. Then, N-bromosuccinimide is added, and the mixture is stirred overnight. The suspension is filtered to obtain the desired product. The product, compound 6, is a white solid.

[0090] [ka]

[0091] Compound 6 is dissolved in DMF under N2 conditions. K2CO3 is added to the solution, and the reaction mixture is stirred for 15 minutes, after which 2-ethylhexyl bromide is added. The reaction mixture is stirred overnight at 100°C. The reaction is stopped and allowed to cool to room temperature. The solvent is removed under vacuum, and the residue is dissolved in diethyl ether. The organic phase is washed with water, and the aqueous phase is extracted with ethyl acetate. The combined organic phase is dried, and volatile substances are removed under vacuum. The stock solution is passed through a small silica column, and the solvent is dried under vacuum to obtain compound 4 as a yellow oily substance.

[0092] Step 2-2: Polymerization: The polymerization method is similar to that of Step 1-2, and the substituted benzene reaction unit (compound 4) and

[0093] [ka]

[0094] The reaction unit used is AcDOT (compound 8), which has the following structure.

[0095] The resulting ECP-2 has an oxidation potential of approximately 0.95 V (against Ag / AgCl) and an energy band gap higher than 3.1 eV. ECP-2 consists of ECP-2 used as the electrochromic layer, 1 M LiPF6 in PEGMEA as the electrolyte, and VO2 as the ion storage layer. xIt is assembled into a solid-state ECD using [a specific method]. The solid-state ECD can be stably switched between -0.6V and 1.7V (Figure 5). The absorbance spectra of the neutral and oxidized states of ECP-2 are obtained at 410 nm λ c and λ of 350nm max This is shown in Figure 7. The solid-state ECD exhibits high transparency, with a high transmittance of 94% at 550 nm in the neutral state (Figure 6). When ECP-2 is oxidized, it switches to a vivid red color, exhibiting one absorption peak at approximately 546 nm and another broader absorption band at wavelengths of approximately 800-1100 nm (Figure 7). The optical contrast of the solid-state ECD is 87% (Figure 6). [Examples]

[0096] ECP-3 In some embodiments, the ECP-3 of this disclosure is expressed as follows:

[0097] [ka]

[0098] It has.

[0099] ECP-3 is synthesized by preparing benzene-containing reaction units and polymerizing them together with ProDot units. The detailed method includes the following steps:

[0100] Step 3-1: Same as Step 2-1.

[0101] Step 3-2: Polymerization: The polymerization method is similar to that of Step 1-2, and includes a benzene-containing reaction unit (compound 4), and

[0102] [ka]

[0103] Different reaction units of 3,4-ethylenedioxythiophene (EDOT, compound 9) having the structure shown are used. [Examples]

[0104] ECP-4 In some embodiments, the ECP-4 of this disclosure is expressed as follows:

[0105] [ka]

[0106] It has.

[0107] ECP-4 is synthesized by preparing naphthalene-containing reaction units and then polymerizing them with AcDOT units. The detailed method includes the following steps:

[0108] Step 4-1: A naphthalene-containing reaction unit (compound 10) is prepared through two steps.

[0109] [ka]

[0110] A solution of bromine in dichloromethane was added dropwise to a solution of compound 11 in dichloromethane over 15 minutes at -78°C. The reaction mixture was stirred at -78°C for 2 hours, then gradually warmed to room temperature and left at room temperature for another 2 hours. The excess bromine was rapidly cooled with saturated sodium sulfite aqueous solution and stirred at room temperature for 2 hours. After extraction with dichloromethane, the combined organic phase was washed with brine, dried on sodium sulfate, and concentrated under vacuum.

[0111] [ka]

[0112] Compound 12 is dissolved in DMF under N2 conditions, K2CO3 is added to the solution, the reaction mixture is stirred for 15 minutes, and then 2-ethylhexyl bromide is added. The reaction mixture is stirred overnight at 100°C. The reaction is stopped and allowed to cool to room temperature. The solvent is removed under vacuum, and the residue is dissolved in diethyl ether. The organic phase is washed with water, and the aqueous phase is extracted with ethyl acetate. The combined organic phase is dried under vacuum.

[0113] Step 4-2: Polymerization: The polymerization method is similar to that of Step 1-2, but uses different reaction units: a naphthalene-containing reaction unit (compound 10) and AcDOT (compound 8). [Examples]

[0114] ECP-5 In some embodiments, the ECP-5 of this disclosure is expressed as follows:

[0115] [ka]

[0116] It has.

[0117] ECP-5 is synthesized by a polymerization method similar to that of steps 1-2, using different reaction units: 1,5-dibromo-2,4-bis(hexyloxy)benzene and 3,4-dimethylthiophene.

[0118] In some embodiments, the ECP of this disclosure is expressed as follows:

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] (In the formula, n and m are integers greater than 0, and a and b are integers greater than or equal to 0, provided that at least one of a and b is greater than 0.) It has.

[0123] In some embodiments, the ECP of this disclosure has an absorption onset of less than 400 nm. In one embodiment,

[0124] [ka]

[0125] The ECP-6 solution having the formula has a λc of 376 nm, as shown in Figure 8. In one embodiment,

[0126] [ka]

[0127] The ECP-7 solution, having the formula shown, has a λc of 391 nm, as shown in Figure 9. Both ECP-6 and ECP-7 were fabricated as thin films and showed absorption spectra similar to those in solution.

[0128] In another embodiment, the polymers of the present disclosure may have fluorescent emission and may be applied to fluorescent products.

[0129] The preceding descriptions of this disclosure are provided for illustrative and explanatory purposes only. They are not intended to be exhaustive or to limit the disclosure to any specific form of disclosure. The scope and breadth of this disclosure should not be limited by any of the exemplary embodiments described above. Many modifications and changes will be obvious to those skilled in the art. These modifications and changes include any appropriate combination of the features of this disclosure. The embodiments have been selected and described in such a way that they best illustrate the principles and practical applications of this disclosure, and that the disclosure can be understood by others skilled in the art for various embodiments, along with various modifications suitable for specific intended uses. The scope of this disclosure is intended to be defined by the following claims and their equivalents.

Claims

1. An electrochromic polymer comprising a polymer main chain containing one or more meta-conjugated linkers (MCLs) and one or more aromatic moieties (Ar), Each of the one or more MCLs is partially conjugated with one or more Ars at the meta position of that one or more MCLs. In a neutral state, it has an energy band gap of 2.9 eV or more and less than 4.0 eV. Electrochromic polymer.

2. The electrochromic polymer according to claim 1, having an absorption maximum (λ max) of less than 410 nm in a neutral state.

3. The electrochromic polymer according to claim 1, which is colorless in a neutral state.

4. The electrochromic polymer according to claim 1, which has visible and / or near-infrared wavelength absorption in an oxidized state.

5. 10 in oxidized state 4 cm -1 The electrochromic polymer according to claim 4, having a larger absorption coefficient.

6. The electrochromic polymer according to claim 1, having an oxidation potential in the range of 0.1 to 1.5 V (including both ends) with respect to an Ag / AgCl electrode.

7. The electrochromic polymer according to claim 1, wherein one or more MCLs comprise at least one aromatic structure or condensed aromatic structure.

8. The electrochromic polymer according to claim 7, wherein one or more MCLs include an aromatic structure, and the aromatic structure includes a benzene structure or a heterocyclic structure.

9. The electrochromic polymer according to claim 7, wherein one or more MCLs include a condensed aromatic structure, and the condensed aromatic structure includes a condensed benzene structure, or a condensed heterocyclic structure, or a condensed benzene and a heterocyclic structure.

10. One or more MCLs and one or more Ars are given by the following formula: 【Chemistry 1】 (In the formula, n is an integer greater than 0, and m 1 , m 2 , , m n Each of them is a non-negative integer, except m 1 , m 2 , , m n (At least one of them is greater than 0) The electrochromic polymer according to claim 1, arranged in an alternating pattern.

11. Each of one or more MCLs and their corresponding meta positions is given by the following formula: 【Chemistry 2A】 【Chemistry 2B】 【Chem.2C】 [Transformation into 2D] (wherein X is S, Se, N, C or O; R 1 to R 12 each is hydrogen, C 1 to C 30 alkyl, C 2 to C 30 alkenyl, C 2 to C 30 alkynyl, C 2 to C 30 alkylcarbonyl, C 1 to C 30 alkoxy, C 3 to C 30 alkoxyalkyl, C 2 to C 30 alkoxycarbonyl, C 4 to C 30 alkoxycarbonylalkyl, C 1 to C 30 alkylthio, C 1 to C 30 aminylcarbonyl, C 4 to C 30 aminylalkyl, C 1 to C 30 alkylaminyl, C 1 to C 30 alkylsulfonyl, C 3 to C 30 alkylsulfonylalkyl, C 6 to C 18 aryl, C 3 to C 15 cycloalkyl, C 3 to C 30 cycloalkylaminyl, C 5 to C 30 cycloalkylalkylaminyl, C 5 to C 30 cycloalkylalkyl, C 5 to C 30 cycloalkylalkyloxy, C 1 to C 12 heterocyclyl, C 1 [[ID=9`0]]to C 12 heterocyclyloxy, C 1 to C 30 heterocyclylalkyloxy, C 1 to C 30 heterocyclylaminyl, C 5 ~C 30 Heterocyclylalkylaminyl, C 2 ~C 12 Heterocyclylcarbonyl, C 3 ~C 30 Heterocyclylalkyl, C 1 ~C 13 Heteroaryl, or C 3 ~C 30 (Independently selected from one of the heteroarylalkyl groups; each tilde represents one of the meta positions) The electrochromic polymer according to claim 1, comprising one of the above.

12. Each of one or more Ars is given by the following formula: 【Transformation 3】 (wherein, R 13 , R 14 and R 15 each is hydrogen, C 1 - C 30 alkyl, C 2 - C 30 alkenyl, C 2 - C 30 alkynyl, C 2 - C 30 alkylcarbonyl, C 1 - C 30 alkoxy, C 3 - C 30 alkoxyalkyl, C 2 - C 30 alkoxycarbonyl, C 4 - C 30 alkoxycarbonylalkyl, C 1 - C 30 alkylthio, C 1 - C 30 aminylcarbonyl, C 4 - C 30 aminylalkyl, C 1 - C 30 alkylaminyl, C 1 - C 30 alkylsulfonyl, C 3 - C 30 alkylsulfonylalkyl, C 6 - C 18 aryl, C 3 - C 15 cycloalkyl, C 3 - C 30 cycloalkylaminyl, C 5 - C 30 cycloalkylalkylaminyl, C 5 - C 30 cycloalkylalkyl, C 5 - C 30 cycloalkylalkyloxy, C 1 - C 12 heterocyclyl, C 1 - C 12 heterocyclyloxy, C 1 - C 30 heterocyclylalkyloxy, C 1 - C 30 heterocyclylaminyl, C 5 ~C 30 Heterocyclylalkylaminyl, C 2 ~C 12 Heterocyclylcarbonyl, C 3 ~C 30 Heterocyclylalkyl, C 1 ~C 13 Heteroaryl, or C 3 ~C 30 (Independently selected from one of the heteroarylalkyl groups) The electrochromic polymer according to claim 1, comprising one of a thiophene unit, a furan unit, a selenofene unit, or a pyrrole unit having one of the above.

13. Each of the one or more Ar atoms contains a thiophene unit, which is given by the following formula: 【Chemistry 4】 (wherein X is S, Se, N, C or O; R 15 ~R 18 Each of them is hydrogen, C 1 ~C 30 Alkyl, C 2 ~C 30 Alkenil, C 2 ~C 30 Alkinyl, C 2 ~C 30 Alkylcarbonyl, C 1 ~C 30 Alkoxy, C 3 ~C 30 Alkoxyalkyl, C 2 ~C 30 Alkoxycarbonyl, C 4 ~C 30 Alkoxycarbonylalkyl, C 1 ~C 30 Alkylthio, C 1 ~C 30 Aminylcarbonyl, C 4 ~C 30 Aminylalkyl, C 1 ~C 30 Alkyl aminyl, C 1 ~C 30 Alkyl sulfonyl, C 3 ~C 30 Alkylsulfonylalkyl, C 6 ~C 18 Ariel, C 3 ~C 15 Cycloalkyl, C 3 ~C 30 Cycloalkylaminyl, C 5 ~C 30 Cycloalkylalkylaminyl, C 5 ~C 30 Cycloalkylalkyl, C 5 ~C 30 Cycloalkylalkyloxy, C 1 ~C 12 Heterocyclyl, C 1 ~C 12 Heterocyclyloxy, C 1 ~C 30 Heterocyclylalkyloxy, C 1 ~C 30 Heterocyclylaminyl, C 5 ~C 30 Heterocyclylalkylaminyl, C 2 ~C 12 Heterocyclylcarbonyl, C 3 ~C 30 Heterocyclylalkyl, C 1 ~C 13 Heteroaryl, or C 3 ~C 30 (Independently selected from one of the heteroarylalkyl groups; Y is one or more of Ar, an aromatic structure, or a condensed aromatic structure, or a combination thereof.) The electrochromic polymer according to claim 1, comprising one of the above.

14. The electrochromic polymer according to claim 13, wherein the thiophene unit X is O.

15. The following formula: [Chemistry 5A] 【Chem.5B】 【5C】 [5D Transformation] (In the formula, n and m are integers greater than 0, and a and b are integers greater than 0, provided that at least one of a and b is greater than 0.) The electrochromic polymer according to claim 1, comprising the formula.

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