A method for preparing an electrochromic device

Abstract

This disclosure provides an electrochromic composition comprising a first compound having the following formula I, an organic solvent, a composite catalyst, and an electrochromic compound; furthermore, the electrochromic composition may also comprise at least one of an electrolyte salt, a chain extender, a crosslinking agent, an ultraviolet stabilizer, and an additive.

Description

Technical Field

[0001] This disclosure relates to the field of electrochromic technology, and more particularly to a method for preparing an electrochromic device. Background Technology

[0002] Electrochromism refers to the phenomenon where the optical properties of an active material, such as its color or transmittance, are altered by the material's electrochemical oxidation-reduction reaction. Electrochromic devices utilizing this phenomenon can be manufactured at low cost, producing large-area devices with low energy consumption, making them suitable for various applications such as smart windows, smart mirrors, and electronic paper.

[0003] Compared to inorganic / organic polymer electrochromic products, organic small-molecule electrochromic products offer advantages such as deeper coloring / shallower fading and faster response speeds. However, the application range of traditional organic small-molecule electrochromic products is limited by factors such as the instability of organic small molecules in the excited state and the irregularity of the movement of organic small-molecule solution systems under an electric field. By introducing gels into the organic small-molecule system, the irregularity of the movement of organic small molecules under an electric field can be effectively reduced, the stability of organic small molecules in the excited state can be improved, the operating voltage can be reduced, and thus the lifespan of the device can be extended.

[0004] Polyurethane formation reaction has proven to be a feasible method for preparing gels in the field of electrochromic products. However, due to the characteristics of the functional groups involved in the polyurethane synthesis reaction, the reaction rate is slow at room temperature, and gel formation often takes several days. While commonly used catalysts (such as organotin compounds) can improve the curing speed, their high toxicity causes many adverse effects on subsequent product applications, severely restricting their large-scale promotion and use. Summary of the Invention

[0005] This disclosure provides an electrochromic composition, an electrochromic device comprising the composition, and a method for preparing the composition, in order to address the shortcomings of related technologies.

[0006] According to a first aspect of the present disclosure, an electrochromic composition is provided, the electrochromic composition comprising a first compound having the following formula I, an organic solvent, and the electrochromic compound:

[0007]

[0008] Formula I

[0009] Where n1 and n2 are selected from any integers from 1 to 10000;

[0010] R1 and R2 are each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heterocyclic, substituted or unsubstituted 5-30 membered heteroaryl, or substituted or unsubstituted 3-30 membered rings formed by bonding with adjacent substituents;

[0011] R3 is selected from substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C1-C30 alkoxy groups, substituted or unsubstituted C3-30 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted 3-30 membered heterocyclic groups, substituted or unsubstituted 5-30 membered heteroaryl groups, or substituted or unsubstituted 3-30 membered rings formed by bonding with adjacent substituents.

[0012] In one aspect of this disclosure, R1 and R2 are each independently selected from C1-C10 alkyl, C2-C10 alkenyl, C3-12 cycloalkyl, or C6-C12 aryl; wherein the C1-C10 alkyl, C2-C10 alkenyl, C3-12 cycloalkyl, or C6-C12 aryl group is optionally replaced by one or more C1-C5 alkyl, amino, or -R 11 -C(O)-R 12 Replaced; R 11 Selected from direct bonds or C1-C5 alkyl groups; R 12 Selected from C1-C5 alkyl, amino, or hydroxyl groups.

[0013] In one aspect of the embodiments of this disclosure, R3 is selected from C1-C10 alkyl, C3-12 cycloalkyl, C6-C12 aryl, 3-12 heterocyclic, or 5-12 heteroaryl; wherein the C1-C10 alkyl, C3-12 cycloalkyl, C6-C12 aryl, 3-12 heterocyclic, or 5-12 heteroaryl is optionally substituted by one or more C1-C5 alkyl, amino, hydroxyl, or nitro groups.

[0014] In one aspect of the embodiments of this disclosure, R1 and R2 are the same group.

[0015] In one aspect of the embodiments of this disclosure, R1 and R2 are the same group, and R1 and R2 are both selected from phenyl, methyl or ethyl.

[0016] In one aspect of this disclosure, R3 is selected from... , , , , , , , , , , or .

[0017] In one aspect of this disclosure, the mass percentage of the first compound is selected from 1% to 65% based on the total mass of the electrochromic composition; preferably, the mass percentage of the first compound is selected from 5% to 35% based on the total mass of the electrochromic composition.

[0018] In one aspect of the embodiments of this disclosure, specifically, based on the total mass of the electrochromic composition, the mass percentage of the first compound can be 5%, 10%, 15%, 20%, 25%, 28%, 30%, 32%, or 35%; but is not limited thereto.

[0019] In one aspect of the embodiments of this disclosure, the organic solvent is selected from at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, propylene carbonate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, ethyl butyrate, dimethyl sulfoxide, sulfolane, dimethyl sulfone, methyl ethyl sulfone, or diethyl sulfone.

[0020] In one aspect of this disclosure, the organic solvent is specifically selected from dimethylformamide or N-methylpyrrolidone.

[0021] In one aspect of this disclosure, the mass percentage of the organic solvent is selected from 10% to 98% based on the total mass of the electrochromic composition; preferably, the mass percentage of the organic solvent is selected from 35% to 55% based on the total mass of the electrochromic composition.

[0022] In one aspect of this disclosure, the electrochromic compound is selected from anodic and / or cathodic materials.

[0023] In one aspect of the embodiments of this disclosure, the anodic color-changing material is selected from at least one of the following compounds: metallocene, ferrocene, substituted ferrocene, phenazine, phenothiazine, substituted phenazine, 5,10-dihydrophenazine, 5,10-dimethyl-5,10-dihydrophenazine, 5,10-dineopentyl-5,10-dihydro-2,7-diisobutylphenazine, etc., but is not limited thereto.

[0024] In one aspect of the embodiments of this disclosure, the cathodic color-changing material is selected from at least one of viologen compounds such as 1-(4-indolylphenyl)-4,4′-bipyridine hexafluorophosphate, 1,1′-bis-2-ethylhexyl-4,4′-bipyridine tetrafluoroborate, 1-(4-benzimidazolylphenyl)-4,4′-bipyridine hexafluorophosphate, 1,1′-bis-isobutyl-4,4′-bipyridine tetrafluoroborate, 1,1′-bis(2,4,6-trimethylphenyl)-[4,4′-bipyridine]-1,1′-bis((trifluoromethyl)sulfonyl)diimide, and 1,1′-bis-2-ethylbutyl-4,4′-bipyridine tetrafluoroborate, but is not limited thereto.

[0025] In one aspect of the embodiments of this disclosure, specifically, the electrochromic compound is selected from a combination of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide and 5,10-dihydrophenazine.

[0026] In one aspect of this disclosure, the mass percentage of the electrochromic compound is selected from 0.1% to 20% based on the total mass of the electrochromic composition; preferably, the mass percentage of the electrochromic compound is selected from 0.25% to 5% based on the total mass of the electrochromic composition.

[0027] In one aspect of the embodiments of this disclosure, specifically, based on the total mass of the electrochromic composition, the mass percentage of the electrochromic compound can be 0.25%, 0.5%, 0.75%, 0.85%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 2.75%, 3%, 3.25%, 3.5%, 3.75%, or 4%; but is not limited thereto.

[0028] In one aspect of this disclosure, the electrochromic composition further comprises a composite catalyst, the composite catalyst comprising at least one selected from triethylenediamine, tin-based catalysts, titanium-based catalysts, germanium-based catalysts, antimony-based catalysts, metallocene catalysts, alkali metals, and their hydroxides. Preferably, the composite catalyst comprises triethylenediamine and a metallocene catalyst.

[0029] In one aspect of the embodiments of this disclosure, specifically, the composite catalyst comprises triethylenediamine and ferrocene catalyst; wherein the mass ratio of the triethylenediamine and ferrocene catalyst is selected from (2-5):1.

[0030] In one aspect of the embodiments of this disclosure, preferably, the mass percentage of the ferrocene catalyst is selected from 0.2% to 0.7% based on the total mass of the electrochromic composition; specifically, the mass percentage of the ferrocene catalyst can be 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, or 0.6%; but is not limited thereto.

[0031] In one aspect of the embodiments of this disclosure, the tin catalyst is optionally selected from one or more of stannous octoate, di(dodecyl sulfide)dibutyltin, butyltin trichloride, monobutyltin oxide, dibutyltin oxide, or dibutyltin diacetate.

[0032] In one aspect of the embodiments of this disclosure, the electrochromic composition further comprises an electrolyte salt selected from at least one of lithium tetrafluoroborate, lithium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tributylmethylammonium bis(trifluoromethanesulfonyl)imide salt, tetrabutylammonium bis(trifluoromethanesulfonyl)imide salt, or bislithium(trifluoromethanesulfonyl)imide salt, but is not limited thereto.

[0033] In one aspect of this disclosure, specifically, the electrolyte salt is selected from lithium tetrafluoroborate.

[0034] In one aspect of this disclosure, the mass percentage of the electrolyte salt is selected from 0.5% to 20% based on the total mass of the electrochromic composition; preferably, the mass percentage of the electrolyte salt is selected from 1% to 5% based on the total mass of the electrochromic composition.

[0035] In one aspect of the embodiments of this disclosure, specifically, based on the total mass of the electrochromic composition, the mass percentage of the electrolyte salt can be 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, or 4%; but is not limited thereto.

[0036] In one aspect of the embodiments of this disclosure, the electrochromic composition may further include a chain extender for improving the mechanical properties of the electrochromic composition. The chain extender may be selected from at least one of dihydroxy compounds with different chain lengths, such as ethylene glycol, diethylene glycol butyl ether, polyethylene glycol with a molecular weight between 200 and 20000, polycaprolactone diol with a molecular weight between 200 and 20000, and polytetrahydrofuran with a molecular weight between 200 and 20000, but is not limited thereto.

[0037] In one aspect of this disclosure, the chain extender is selected from 0.5% to 30% by mass based on the total mass of the electrochromic composition; preferably, the chain extender is selected from 1% to 10% by mass based on the total mass of the electrochromic composition.

[0038] In one aspect of this disclosure, the electrochromic composition may further comprise a crosslinking agent for further curing the electrochromic composition. The crosslinking agent may be selected from at least one of polyhydroxy- and polyamino compounds with three or more functional groups, such as glycerol, 2-10 polyglycerol, pentaerythritol, melamine, phloroglucinol, and polyacrylamide, but is not limited thereto.

[0039] In one aspect of this disclosure, the mass percentage of the crosslinking agent is selected from 0.2% to 20% based on the total mass of the electrochromic composition; preferably, the mass percentage of the crosslinking agent is selected from 0.5% to 10% based on the total mass of the electrochromic composition.

[0040] In one aspect of this disclosure, the electrochromic composition may further comprise a UV stabilizer for improving the internal stability of the electrochromic composition, thereby extending its service life; the UV stabilizer is selected from at least one of 2-ethyl-2-cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate, 2-(2′-hydroxy-4′-methylphenyl)benzotriazole, or 3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]pentyl propionate, but is not limited thereto.

[0041] In one aspect of this disclosure, the mass percentage of the UV stabilizer is selected from 0.2% to 20% based on the total mass of the electrochromic composition; preferably, the mass percentage of the UV stabilizer is selected from 0.5% to 8% based on the total mass of the electrochromic composition.

[0042] In one aspect of the embodiments of this disclosure, the electrochromic composition may further comprise an additive; the mass percentage of the additive is selected from 0.1% to 15% based on the total mass of the electrochromic composition; the additive comprises one or more of defoamers, dispersants, leveling agents, substrate wetting agents, surface tension additives, anti-settling agents, and antioxidants.

[0043] In one aspect of the embodiments of this disclosure, the defoamer is selected from one or more of tributyl phosphate, defoamer Deqian 3100, and defoamer BYK088; but is not limited thereto.

[0044] In one aspect of this disclosure, the dispersant is selected from polycarboxylate dispersant 5040 or sodium hexametaphosphate; however, it is not limited thereto.

[0045] In one aspect of this disclosure, the leveling agent is selected from leveling agent BYK-333 or silicone leveling agent HY-5030; however, it is not limited thereto.

[0046] In one aspect of the embodiments of this disclosure, the substrate wetting agent is selected from one or more of sodium alkylnaphthalene sulfonate, castor oil sulfate, sodium dodecyl sulfonate, lauryl sulfate, alkylphenol polyoxyethylene ether, alkyl alcohol polyoxyethylene ether, ethylene glycol polyoxyethylene alkyl ester, ethylene glycol polyoxyethylene alkyl aryl ether, and ethylene glycol acetylene; but is not limited thereto.

[0047] In one aspect of this disclosure, the surface tension aid is selected from polysiloxane-polyalkoxy polyether copolymers; however, it is not limited thereto.

[0048] In one aspect of this disclosure, the anti-settling agent is selected from modified polyurea compounds; however, it is not limited thereto.

[0049] In one aspect of the embodiments of this disclosure, the antioxidant is selected from one or more of antioxidant 1010, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; but is not limited thereto.

[0050] According to a second aspect of the present disclosure, an electrochromic device is provided, the electrochromic device comprising at least one electrochromic unit, the electrochromic unit comprising a pair of substrates facing each other and forming a gap, and the gap being filled by the aforementioned electrochromic composition.

[0051] In one aspect of the embodiments of this disclosure, the electrochromic unit may be transparent or reflective / opaque, and the choice may be made adaptively as needed.

[0052] In one aspect of the embodiments of this disclosure, the substrate is selected from one or more of ITO conductive glass, FTO conductive glass, silver nanowire conductive glass, graphene-coated conductive glass, conductive polymer-based conductive glass, silver mirror conductive glass, and aluminum mirror conductive glass; but is not limited thereto.

[0053] According to a third aspect of the present disclosure, a method for preparing the aforementioned electrochromic device is provided, the method comprising the following steps:

[0054] Step 1: Dissolve at least one polymer containing a secondary amine group in an organic solvent to obtain a solution;

[0055] Step 2: Add the composite catalyst and at least one electrochromic compound to the solution obtained in Step 1. After stirring and mixing evenly, add an isocyanate compound to obtain the electrochromic composition.

[0056] Step 3: Provide at least one electrochromic unit, the electrochromic unit comprising a pair of substrates facing each other and forming a gap, fill the gap of the substrates with the electrochromic composition obtained in Step 2, and obtain the electrochromic device after the electrochromic composition has cured.

[0057] In one aspect of this disclosure, the polymer containing secondary amine groups is selected from polyethyleneimine and / or polyaniline.

[0058] In one aspect of the embodiments of this disclosure, the isocyanate compound is selected from toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl isophthalimethylene diisocyanate, or 1,4-cyclohexane diisocyanate, etc.

[0059] In one aspect of this disclosure, the polymer containing secondary amine groups has an average degree of polymerization of 5-200.

[0060] In one aspect of this disclosure, the polymer containing secondary amine groups is selected in a mass ratio of (0.15-1):1 to the isocyanate compound.

[0061] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects:

[0062] As can be seen from the above embodiments, this disclosure provides a method for reacting isocyanate compounds with polymers containing secondary amine groups to obtain a gel composition, while including an electrochromic compound therein, which not only results in a fast gel formation rate but also avoids the introduction of highly toxic catalysts.

[0063] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Detailed Implementation

[0064] Exemplary embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings. When the following description relates to the drawings, unless otherwise indicated, the same numerals in different drawings denote the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.

[0065] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0066] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0067] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0068] In this description, unless otherwise stated, "above" and "below" include the stated number.

[0069] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values ​​of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).

[0070] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, quantities, ratios, and other numerical values ​​are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values ​​explicitly specified as range limits but also all individual numerical values ​​or subranges covered within the range, as if each numerical value and subrange were explicitly specified.

[0071] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0072] In this disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, that link a linear alkyl chain. "Lower alkyl" refers to a group containing about 1 to about 6 carbon atoms in the chain, which can be straight-chain or branched.

[0073] In this disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon double bond, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkenyl chain. "Lower alkenyl" refers to a group containing about 2 to about 6 carbon atoms in the chain, which can be straight-chain or branched.

[0074] In this disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond, which can be straight-chain or branched. Branching refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkynyl chain. "Lower alkynyl" refers to a chain containing about 2 to about 6 carbon atoms, which can be straight-chain or branched. Non-limiting examples of alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl, and decynyl.

[0075] In this disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. An aryl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0076] In this disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system, wherein one or more ring atoms are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination, and preferably a heteroaryl contains about 5 to about 6 ring atoms. A "heteroaryl" may optionally be substituted by one or more "cyclic substituents," which may be the same or different, as defined herein. The prefixes azido, oxa, or thiado preceding the name of a heteroaryl root indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The nitrogen atom of a heteroaryl may optionally be oxidized to the corresponding N-oxide. Suitable, non-limiting examples of heteroaryl groups include pyridyl, pyrazinyl, furanyl, phenylthio, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrroleyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-diazanaphthyl, imidazo[1,2-a]pyridyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indoleyl, azaindoleyl, benzimidazolyl, benzothiopheneyl, quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindoleyl, 1,2,4-triazinyl, benzothiazolyl, etc.

[0077] In this disclosure, the term "amino" refers to the -NR′R′′ group. The amino group may optionally be substituted. In an unsubstituted amino group, R′ and R′′ are hydrogen. In a substituted amino group, R′ and R′′ may each independently be, but not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkanoyl, aryl, arylalkyl, or heteroaryl, provided that R′ and R′′ are not both hydrogen. In a substituted amino group, R′ and R′′ may cyclize to form a cyclic amino group, such as pyrrolidinyl or piperidinyl. Such cyclic amino groups may incorporate other heteroatoms, for example, to form piperazine or morpholine groups. Such cyclic amino groups may optionally be substituted, for example, by an amino, hydroxyl, or oxo group.

[0078] In this disclosure, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to a straight-chain, branched, or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, and pentoxy. Alkoxy may optionally be substituted by one or more alkoxy substituents ("substituted alkoxy").

[0079] In this disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system, preferably containing about 5 to about 7 ring atoms. The cycloalkyl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined above. Suitable monocyclic cycloalkyl groups, without limitation, include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Suitable polycyclic cycloalkyl groups, without limitation, include 1-decahydronaphthyl, norcamphenyl, adamantyl, etc. In this disclosure, the term "cycloalkoxy" refers to a group in which one or more carbon atoms in the mono- or polycyclic ring system of the "cycloalkyl" group are substituted with oxygen atoms.

[0080] In this disclosure, the term "heterocyclic group" refers to a non-aromatic saturated monocyclic or polycyclic ring system, wherein one or more ring atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination. Adjacent oxygen and / or sulfur atoms are absent in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefixes aza, oxa, or thioa preceding the name of the heterocyclic group indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The heterocyclic group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. The nitrogen or sulfur atom of the heterocyclic group may optionally be oxidized to the corresponding N-oxide, S-oxide, or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclic rings include piperidinyl, pyrrolyl, piperazine, morpholinyl, thiomorpholinyl, thiazolyl, 1,3-dioxolanecycloyl, 1,4-dioxacyclohexyl, tetrahydrofuranyl, tetrahydrophenylthio, tetrahydrothiopyranyl, etc.

[0081] The present disclosure will be further described below by way of specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of the present disclosure are obtained through conventional commercial means. Unless otherwise specified, all contents mentioned below are mass contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0082] Example

[0083] Example 1:

[0084] At 25°C and 40% humidity, 30 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added. After stirring until homogeneous, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixture. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0085] Example 2:

[0086] At 25°C and 40% humidity, 30 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 1 part by weight of ferrocene catalyst was added and stirred until homogeneous. Next, 100 parts by weight of toluene diisocyanate (TDI) was added to the mixture. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and timer t0 was started. When the system viscosity exceeded the maximum range, timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0087] Example 3:

[0088] At 25°C and 40% humidity, 30 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine were added and stirred until homogeneous. Next, 100 parts by weight of toluene diisocyanate (TDI) was added to the mixture. After mixing for 1 minute, the viscosity change was observed using a rotational viscometer (maximum range 10000 cp), and timing was started at t0. When the viscosity exceeded the maximum range, timing was started at t1. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0089] Example 4:

[0090] At 25°C and 40% humidity, 30 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of stannous octoate catalyst were added. After stirring until homogeneous, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the system viscosity exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0091] Comparative Example 1:

[0092] At 25°C and 40% humidity, 30 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added. After stirring until homogeneous, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0093] Comparative Example 2:

[0094] At 25°C and 40% humidity, 30 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of stannous octoate catalyst were added. After stirring until homogeneous, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0095] Example 5:

[0096] At 25°C and 40% humidity, 20 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added and stirred until homogeneous. Then, 100 parts by weight of hexamethylene diisocyanate (HDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times plus the mixing time of 1 minute is the gel time of the system.

[0097] Example 6:

[0098] At 25°C and 40% humidity, 20 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of stannous octoate catalyst were added and stirred until homogeneous. Then, 100 parts by weight of hexamethylene diisocyanate (HDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times plus the mixing time of 1 minute is the gel time of the system.

[0099] Comparative Example 3:

[0100] At 25°C and 40% humidity, 20 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added. After stirring until homogeneous, 100 parts by weight of hexamethylene diisocyanate (HDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and timer t0 was started. When the viscosity of the system exceeded the maximum range, timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0101] Comparative Example 4:

[0102] At 25°C and 40% humidity, 20 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of stannous octoate catalyst were added. After stirring until homogeneous, 100 parts by weight of hexamethylene diisocyanate (HDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and timer t0 was started. When the viscosity of the system exceeded the maximum range, timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0103] Example 7:

[0104] At 25°C and 40% humidity, 25 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added. After stirring until homogeneous, 100 parts by weight of isophorone diisocyanate (IPDI) was added to the above mixture. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and timer t0 was started. When the viscosity of the system exceeded the maximum range, timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0105] Example 8:

[0106] At 25°C and 40% humidity, 25 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of butyltin trichloride catalyst were added and stirred until homogeneous. Then, 100 parts by weight of isophorone diisocyanate (IPDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times plus the mixing time of 1 minute is the gel time of the system.

[0107] Comparative Example 5:

[0108] At 25°C and 40% humidity, 25 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of butyltin trichloride catalyst were added. After stirring until homogeneous, 100 parts by weight of isophorone diisocyanate (IPDI) was added to the above mixture. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0109] Example 9:

[0110] At 25°C and 40% humidity, 30 parts by weight of polyethyleneimine with an average degree of polymerization of 100 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added and stirred until homogeneous. Next, 100 parts by weight of toluene diisocyanate (TDI) was added to the mixture. After mixing for 1 minute, the viscosity change was observed using a rotational viscometer (maximum range 10000 cp), and timing was started at t0. When the viscosity exceeded the maximum range, timing was started at t1. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0111] Comparative Example 6:

[0112] At 25°C and 40% humidity, 30 parts by weight of polyvinyl alcohol with an average degree of polymerization of 100 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of stannous octoate were added and stirred until homogeneous. Then, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer was started at t0. When the viscosity of the system exceeded the maximum range, the timer was started at t1. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0113] Example 10:

[0114] At 25°C and 40% humidity, 20 parts by weight of polyethyleneimine with an average degree of polymerization of 100 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added and stirred until homogeneous. Next, 100 parts by weight of hexamethylene diisocyanate (HDI) was added to the above mixed solution. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0115] Example 11:

[0116] At 25°C and 40% humidity, 20 parts by weight of polyethyleneimine with an average degree of polymerization of 100 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 3 parts by weight of triethylenediamine and 1 part by weight of ferrocene catalyst were added. After stirring until homogeneous, 100 parts by weight of isophorone diisocyanate were added to the above mixture. After mixing for 1 minute, the viscosity change of the system was observed using a rotational viscometer (maximum range 10000 cp), and the timer t0 was started. When the viscosity of the system exceeded the maximum range, the timer t1 was started. The difference between the two times, plus the mixing time of 1 minute, is the gel time of the system.

[0117] The numerical values ​​for Examples 1-11 and Comparative Examples 1-6 are shown in Table 1:

[0118] Table 1

[0119]

[0120] Example 12:

[0121] Example 12: Using the gel system of Example 1, the device of Example 12 was prepared.

[0122] At 25°C and 40% humidity, 30 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 5 parts by weight of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide, 3 parts by weight of lithium tetrafluoroborate, 3 parts by weight of 5,10-dihydrophenazine, 3 parts by weight of triethylenediamine, and 1 part by weight of ferrocene catalyst were added. After stirring until homogeneous, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution. After mixing, the mixture was allowed to stand for 10 minutes to obtain the gel of Example 12. The obtained gel was added to a container made of two pieces of ITO conductive glass. In the device housing, the slit width is 100 micrometers. After the gel has solidified, it is sealed with sealing glue to obtain the device of Example 12.

[0123] Comparative Example 7:

[0124] Comparative Example 7 uses the gel system of Comparative Example 2 to fabricate the device of Comparative Example 7:

[0125] At 25°C and 40% humidity, 30 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 5 parts by weight of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide, 3 parts by weight of lithium tetrafluoroborate, 3 parts by weight of 5,10-dihydrophenazine, 3 parts by weight of triethylenediamine, and 1 part by weight of stannous octoate catalyst were added. After stirring until homogeneous, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution. After mixing, the mixture was allowed to stand for 24 hours to obtain the gel of Comparative Example 7. The obtained gel was added to a container made of two pieces of ITO conductive glass. In the device housing, the slit width is 100 micrometers. After the gel has solidified, it is sealed with sealing glue to obtain the device of Comparative Example 7.

[0126] Example 13:

[0127] Example 13: The device of Example 13 was prepared using the gel system of Example 8.

[0128] At 25°C and 40% humidity, 25 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 5 parts by weight of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide, 3 parts by weight of lithium tetrafluoroborate, 3 parts by weight of 5,10-dihydrophenazine, 3 parts by weight of triethylenediamine, and 1 part by weight of butyltin trichloride catalyst were added. After stirring until homogeneous, 100 parts by weight of isophorone diisocyanate (IPDI) was added to the above mixed solution. After mixing, the mixture was allowed to stand for 20 minutes to obtain the gel of Example 13. The obtained gel was added to a container made of two pieces of ITO conductive glass. In the device housing, the slit width is 100 micrometers. After the gel has solidified, it is sealed with sealing glue to obtain the device of Example 13.

[0129] Comparative Example 8:

[0130] Comparative Example 8 uses the gel system of Comparative Example 5 to fabricate the device of Comparative Example 8:

[0131] At 25°C and 40% humidity, 25 parts by weight of polyvinyl alcohol with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 5 parts by weight of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide, 3 parts by weight of lithium tetrafluoroborate, 3 parts by weight of 5,10-dihydrophenazine, 3 parts by weight of triethylenediamine, and 1 part by weight of butyltin trichloride catalyst were added. After stirring until homogeneous, 100 parts by weight of isophorone diisocyanate (IPDI) was added to the above mixed solution. After mixing, the mixture was allowed to stand for 72 minutes to obtain the gel of Comparative Example 8. The obtained gel was then added to a container made of two pieces of ITO conductive glass. In the device housing, the slit width is 100 micrometers. After the gel has solidified, it is sealed with sealing glue to obtain the device of Comparative Example 8.

[0132] Comparative Example 9:

[0133] Comparative Example 9 provides an organic gel system for fabricating the device of Comparative Example 9:

[0134] At 25°C and 40% humidity, 12.5 parts by weight of thiol-terminated tetra-arm polyethylene glycol 2000, 12.5 parts by weight of alkynyl-terminated bi-arm polyethylene glycol 2000, and 0.05 parts by weight of α,α-dimethoxy-α-phenylacetophenone were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 5 parts by weight of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide, 3 parts by weight of lithium tetrafluoroborate, and 3 parts by weight of 5,10-dihydrophenazine were added, and the mixture was stirred until homogeneous. The resulting solution was then added to a container made of two pieces of ITO conductive glass. In the device housing, the slit width is 100 micrometers. After sealing with adhesive, it is cured by irradiation with a 365nm wavelength ultraviolet lamp for 20 minutes to obtain the device of Comparative Example 9.

[0135] Comparative Example 10:

[0136] At 25°C and 40% humidity, 25 parts by weight of polyaniline with an average degree of polymerization of 10 were dissolved in 75 parts by weight of N-methylpyrrolidone. Then, 5 parts by weight of 1,1'-bis(2,4,6-trimethylphenyl)-[4,4'-bipyridine]-1,1'-bis((trifluoromethyl)sulfonyl)diimide, 3 parts by weight of lithium tetrafluoroborate, and 3 parts by weight of 5,10-dihydrophenazine were added. After stirring until homogeneous, 100 parts by weight of isophorone diisocyanate (IPDI) were added to the above mixed solution. After mixing, the solution was allowed to stand for 20 minutes to obtain the solution of Comparative Example 10. The obtained solution was then added to a container made of two pieces of ITO conductive glass. In the device housing, the slit width is 100 micrometers. After the gel has solidified, it is sealed with sealing glue to obtain the device of Comparative Example 10.

[0137] Comparative Example 10, due to the absence of a catalyst, could not yield a gel and could only produce a solution.

[0138] The self-fading time and coloring time of Examples 12-13 and Comparative Examples 7-9 were tested respectively, and the results are shown in Table 2 below:

[0139] Table 2

[0140]

[0141] As can be seen, the self-fading time after power-off in Examples 12-13 is longer. This is because the gel system prepared by the examples of this application contains abundant -NH- and -C(O)-. The H of -NH- on one chain segment can form hydrogen bonds with the O of -C(O)- on another chain segment. The cross-linked network structure formed by the gel system increases the density of the formed hydrogen bonds. Therefore, the cross-linked network structure formed by the gel system and the formed hydrogen bonds increase the shuttle resistance of concentration diffusion of the anode and cathode materials, thereby reducing the self-fading speed of the electrochromic unit after power-off, that is, increasing the color retention ability of the colored state, which is manifested as a reduction in the overall working energy consumption of the electrochromic unit. Therefore, the working energy consumption of Examples 12-13 is lower than that of Comparative Example 10, which does not use a gel system. Furthermore, in the organic gel system of Comparative Example 9, the formation of numerous covalent bonds within the gel not only increases the concentration diffusion shuttle resistance of the anode and cathode materials but also significantly increases the charge-driven shuttle resistance during the coloring process. Therefore, compared to Examples 12-13, while reducing the self-fading speed of the electrochromic unit upon power-off, it also significantly affects the coloring speed. The gel network-hydrogen bond system provided in this application neither affects the coloring speed of the electrochromic unit nor hinders its energy consumption.

[0142] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A method of preparing an electrochromic device, characterized by, The method comprises the following steps: Step 1: dissolving at least one polymer containing a secondary amine group in an organic solvent to obtain a solution; Step 2: adding a composite catalyst and at least one electrochromic compound to the solution obtained in step 1, stirring to mix uniformly, then adding an isocyanate compound to obtain an electrochromic composition; The electrochromic composition comprises a first compound having the following formula I, an organic solvent, and an electrochromic compound: wherein n1 and n2 are selected from 10-100; R1 and R2 are simultaneously selected from phenyl, methyl or ethyl; R3is selected from , , , , , , , , , , or ; The electrochromic composition further comprises an electrolyte salt; the composite catalyst comprises triethylenediamine, and a tin catalyst or a ferrocene catalyst; Step 3: providing an electrochromic device comprising at least one electrochromic unit, the electrochromic unit comprising a pair of substrates facing each other and forming a gap, filling the electrochromic composition obtained in step 2 into the gap of the substrate, and obtaining the electrochromic device after the electrochromic composition is cured.

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