Electrochromic block copolymers and devices made therewith

Abstract

The medium for the electro-optical device comprises a first block copolymer unit comprising at least one of a first diblock copolymer and a first triblock copolymer, and at least one of a first donor compound and a first acceptor compound conjugated with at least one of the first diblock copolymer and the first triblock copolymer, thereby forming a first block copolymer unit. The medium further comprises a second block copolymer unit comprising at least one of a second diblock copolymer and a second triblock copolymer, and at least one of a second donor compound and a second acceptor compound conjugated with at least one of the second diblock copolymer and the second triblock copolymer, thereby forming a second block copolymer unit. The first block copolymer unit is polymerized with the second block copolymer unit.

Description

[Technical field]

[0001] The present disclosure relates generally to conductive polymers, and more specifically, to block copolymers for electro-optical devices and media. Summary of the Invention

[0002] In one embodiment of the present disclosure, a medium for an electro-optical device includes a first electrochromic block copolymer unit comprising at least one selected from the group of a first diblock copolymer and a first triblock copolymer, and at least one of a first donor compound and a first acceptor compound conjugated with at least one of the first diblock copolymer and the first triblock copolymer, where at least one of the first donor compound and the first acceptor compound is electrochromic, thereby forming a first electrochromic block copolymer unit. The medium further includes a second electrochromic block copolymer unit comprising at least one selected from the group of a second diblock copolymer and a second triblock copolymer, and at least one of a second donor compound and a second acceptor compound conjugated with at least one of the second diblock copolymer and the second triblock copolymer, where at least one of the second donor compound and the second acceptor compound is electrochromic, thereby forming a second electrochromic block copolymer unit. The first electrochromic block copolymer unit is polymerized with the second electrochromic block copolymer unit, thereby forming a repeating polymer.

[0003] In another aspect of the present disclosure, an electro-optical element includes a first substrate defining a first surface and a second surface, a first conductive layer disposed on the second surface, and a second substrate defining a third surface and a fourth surface, a second conductive layer disposed on the third surface. A medium is disposed between the second surface and the third surface. The medium includes a first block copolymer unit including (i) at least one selected from the group of a first diblock copolymer and a first triblock copolymer, and (ii) at least one of a first donor compound and a first acceptor compound conjugated with at least one of the first diblock copolymer and the first triblock copolymer, thereby forming a first block copolymer unit. The medium further comprises a second block copolymer unit comprising (i) at least one selected from the group of a second diblock copolymer and a second triblock copolymer, and (ii) at least one of a second donor compound and a second acceptor compound conjugated with the at least one of the second diblock copolymer and the second triblock copolymer, thereby forming a second block copolymer unit. The first block copolymer unit is polymerized with the second block copolymer unit.

[0004] In yet another aspect of the present disclosure, a medium for an electro-optical device comprises a chemical compound of formula (I): [ka]

[0005] These and other features, advantages, and objects of the present device will be further understood and appreciated by those skilled in the art upon study of the following specification, claims, and accompanying drawings.

[0006] The invention will now be described with reference to the following drawings. [Brief description of the drawings]

[0007] [Figure 1A]FIG. 1A shows a cross-sectional schematic diagram of an electro-optical element according to an embodiment of the present disclosure. [Figure 1B] FIG. 1B shows a cross-sectional schematic diagram of an electro-optical element according to an embodiment of the present disclosure. [Figure 2A] FIG. 2A shows a schematic diagram of the chemical structure of an exemplary diblock compound according to an embodiment of the present disclosure. [Figure 2B] FIG. 2B shows a schematic diagram of the chemical structure of an exemplary triblock compound according to an embodiment of the present disclosure. [Figure 3A] FIG. 3A shows a schematic chemical structure of an exemplary electrochromic compound conjugated with a diblock compound according to an embodiment of the present disclosure. [Figure 3B] FIG. 3B shows a schematic chemical structure of an exemplary electrochromic compound conjugated with a triblock compound according to an embodiment of the present disclosure. [Figure 4A] FIG. 4A shows a schematic chemical structure of an exemplary electrochromic compound conjugated with a diblock compound according to an embodiment of the present disclosure. [Figure 4B] FIG. 4B shows a schematic chemical structure of an exemplary electrochromic compound conjugated with a triblock compound according to an embodiment of the present disclosure. [Figure 5A] FIG. 5A shows schematic chemical structures of exemplary electrochromic compounds and auxiliary materials conjugated with triblock compounds according to embodiments of the present disclosure. [Figure 5B] FIG. 5B shows schematic chemical structures of exemplary conductive compounds and auxiliary materials conjugated with triblock compounds according to embodiments of the present disclosure. [Figure 6] FIG. 6 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 7] FIG. 7 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 8] FIG. 8 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 9] FIG. 9 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 10]FIG. 10 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 11] FIG. 11 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 12] FIG. 12 shows an exemplary synthesis scheme according to an embodiment of the present disclosure. [Figure 13] FIG. 13 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 14] FIG. 14 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 15] FIG. 15 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 16] FIG. 16 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 17] FIG. 17 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 18] FIG. 18 shows an exemplary synthetic scheme according to an embodiment of the present disclosure. [Figure 19] FIG. 19 is an infrared spectroscopy plot of absorbance intensity as a function of wavenumber for monomers utilized to produce block copolymers according to embodiments of the present disclosure. [Figure 20] FIG. 20 is an infrared spectroscopy plot of absorbance intensity as a function of wavenumber for an exemplary diblock copolymer according to an embodiment of the present disclosure. [Figure 21A] FIG. 21A is an image showing the morphology of a polymer according to an embodiment of the present disclosure. [Figure 21B] FIG. 21B is an image showing the morphology of the polymer of FIG. 21A according to an embodiment of the present disclosure. [Figure 22A] FIG. 22A is a plot of current (left axis) and absorbance (right axis) as a function of time for an exemplary electrochromic device including the polymer of FIG. 21A according to an embodiment of the present disclosure. [Figure 22B] FIG. 22B is a plot of absorbance as a function of wavelength for the exemplary electrochromic device of FIG. 22A according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The illustrated embodiment resides primarily in the combination of materials, method steps, and device components related to block copolymers as components of electro-optical elements and electro-optical media, as discussed below. Accordingly, device components and method steps are described, and, where necessary, conventional numerals in the drawings are used to indicate only those specific details that are relevant to an understanding of the embodiments of the present disclosure, so as not to obscure the detailed disclosure that one of ordinary skill in the art will readily appreciate and have the benefit of the description herein. Additionally, like numerals in the description and drawings represent like elements.

[0009] As used herein, the term "and / or" when used with a list of two or more items means that any one of the listed items may be used by itself or any combination of two or more of the listed items may be used. For example, if a composition is described as containing components A, B, and / or C, the composition may contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0010] In this specification, related terms such as first and second, above and below, etc., are used singly to distinguish one component or operation from another and do not necessarily require or imply an actual such interrelationship or order among such components or operations. The terms "comprises", "comprising" or other variations of these terms are intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus that includes recited elements does not include only those elements, but may include other elements not expressly recited or inherent to such process, method, article, or apparatus. An element preceded by "comprising a..." does not, without further constraints, exclude the presence of additional identical elements in the process, method, article, or apparatus that includes the element.

[0011] Aspects of the present disclosure relate to conductive polymers, and more specifically to block copolymers as components of electro-optical elements and electro-optical media. The block copolymers of the present disclosure can be used in electro-optical elements and electrochromic devices incorporating such electro-optical elements. By way of preamble, an electrochromic device generally includes an electrochromic medium that transitions between an inactivated state in which the electrochromic medium is relatively transparent to light having wavelengths within a predetermined wavelength range, and an activated state in which the electrochromic medium exhibits reduced transmission to light within a predetermined wavelength range when an electrical potential is applied to the electrochromic device. The electrochromic medium includes anodic and cathodic components (also referred to as electroactive components), at least one of which is also electrochromic. The electrochromic electroactive component can provide the perceived color of the electrochromic device when the electrochromic device is in an activated state and / or when the device transitions between the inactivated and activated states.

[0012] Although embodiments of the present disclosure are described in the context of electro-optical elements 20, embodiments of the present disclosure may also be utilized in the context of other electrochromic or electro-optical devices, non-limiting examples of which include interior and exterior mirror assemblies, bi-stable devices, interior and exterior windows, display screens, head-up displays, vehicle window assemblies, architectural window assemblies, filter assemblies, eyewear, cameras, and display boards. Additionally, the block copolymers described herein may be applicable to other devices, including, but not limited to, substrates such as organic light emitting diodes ("OLEDs"), organic field effect transistors ("OFETs"), and the like.

[0013] The term "electroactive" as used herein means a material that can undergo modification in its oxidation state when exposed to a specific potential difference. The term "electrochromic" as used herein means a material that can exhibit a change in its extinction coefficient at one or more wavelengths when exposed to a specific potential difference. Electrochromic components, as described herein, include materials whose color and opacity are affected by an electric current, so that when an electric field is applied to the material, the color or opacity changes from a first state to a second state (e.g., an inactivated state and an activated state). Thus, an electrochromic device can exhibit a change in transparency as a result of an electrochemical redox reaction that occurs between electroactive components (e.g., an anodic component and a cathodic component), at least one of which is also electrochromic. In other words, when a sufficient potential difference is applied between the electrodes of an electrochromic device, the electrochromic medium can shift from a substantially transparent state (e.g., a high transmission state, e.g., an inactivated state) to a substantially dark or darkened state (e.g., a low transmission state, e.g., an activated state), as well as intermediate states therebetween, when one or more of the anodic and cathodic components are oxidized and reduced, respectively. Specifically, an anode component is oxidized by donating electrons to an anode, and a cathode component is reduced by receiving electrons from a cathode. Thus, as used herein, the term "acceptor compound" refers to an electron-deficient compound, and as used herein, the term "donor compound" refers to an electron-rich compound. Examples of acceptor compounds include, but are not limited to, benzothiadiazole (BDT), benzoselenadiazole, quinoxaline, pyrazino(2,3-g)quinoxaline, isoindigo, pyrrolopyrrole-1,4-dione, and the like. Examples of donor compounds include, but are not limited to, carbazole, fluorene, silafluorene, benzodithiophene, thiophene, cyclopentadithiophene, and the like.

[0014] 1A and 1B, reference numeral 10 generally indicates an electro-optical element that may be included in the aforementioned electrochromic device 14. The electro-optical element 10 may include a first substrate 18 having a first surface 22 and a second surface 26. A first conductive layer 30 is disposed on the second surface 26. A second substrate 34 is provided opposite the first substrate 18 and includes a third surface 38 and a fourth surface 42. A second conductive layer 46 is disposed on the third surface 38. The first substrate 18 and the second substrate 34, together with a sealing member 50, define a chamber 54 for containing an electrochromic medium 58.

[0015] The electro-optic element 10 allows the electrochromic device 14 to be operable between a first state of the electro-optic element 10 that allows passage of electromagnetic radiation having a wavelength within a predetermined wavelength range, and a second state in which a portion of, or no, electromagnetic radiation having a wavelength within the predetermined wavelength range is transmitted through the electro-optic element 10 (e.g., the electro-optic element 10 is generally opaque or partially opaque to electromagnetic radiation having a wavelength within the predetermined wavelength range). The second state of the electro-optic element 10 may be defined relative to the transmittance of the first state. According to aspects of the present disclosure, the transmittance of electromagnetic radiation of a predetermined wavelength or range of wavelengths through the electro-optic element 10 in the first state may be greater than about 25%, greater than about 50%, greater than about 55%, or greater than about 85%. Typically, the reflectance, transmittance, and absorbance percentages of the electro-optic element 10 add up to 100%. In some embodiments, the transmittance of electromagnetic radiation of a given wavelength or range of wavelengths through electro-optical element 10 substantially in the second state may be less than about 10%, less than about 1%, less than about 0.1%, less than about 0.01%, or less than about 0.001%.

[0016] The first substrate 18 and / or the second substrate 34 can be made of glass, plastic, or other optically transparent or translucent materials, non-limiting examples of which include borosilicate glass, soda lime glass, or polymeric materials, such as natural and synthetic polymeric resins, plastics, and / or composites. Non-limiting examples of such materials include polyesters (e.g., PET), polyimides (PI), polycarbonates, polysulfones, polyethylene naphthalates (PEN), ethylene vinyl acetate (EVA), acrylate polymers, and cyclic olefin copolymers (COC), such as those commercially available from TOPAS® Advanced Polymers. In some embodiments, both the first substrate 18 and the second substrate 34 are made of optically transparent or translucent materials, while in other embodiments, only a single substrate, such as the first substrate 18, is made of an optically transparent or translucent material. The first substrate 18 and the second substrate 34 can be made of the same or different materials and may have the same or different dimensions.

[0017] The first conductive layer 30 and the second conductive layer 46 may comprise one or more layers of conductive material disposed on the first substrate 18 and the second substrate 34, respectively. These layers function as electrodes (e.g., cathode and anode) of the electro-optical element 10. The conductive material of the first conductive layer 30 and / or the second conductive layer 46 may be any suitable material that includes one or more of the following characteristics: (a) is substantially transparent to electromagnetic radiation in the visible and / or infrared wavelength ranges; (b) bonds reasonably well to the first substrate 18 and the second substrate 34; (c) maintains a bond with the first substrate 18 and the second substrate 34 when associated with a sealing member 50; (d) is generally resistant to corrosion by materials contained within the electrochromic device 14 or the atmosphere; and / or (e) exhibits minimal diffuse or specular reflectance and sufficient electrical conductance. Depending on the application, only one of the first conductive layer 30 and the second conductive layer 46 may be required to be transparent, while the other conductive layer 30, 46 may be opaque. In some applications, both the first conductive layer 30 and the second conductive layer 46 may be transparent. According to some embodiments, one of the first conductive layer 30 and the second conductive layer 46, such as the second conductive layer 46, may include one or more coatings configured as a metallic reflector or a partially reflective and partially transmissive ("semi-transmissive") coating. The inclusion of a metallic reflector or a semi-transmissive coating may at least partially reflect the electrochromic device. Thus, the conductive materials forming the first conductive layer 30 and the second conductive layer 46 may be the same or different. Non-limiting examples of conductive materials that may be used to form the first conductive layer 30 and / or the second conductive layer 46 can include transparent conductive oxides (TCOs), such as fluorine doped tin oxide (FTO), such as TEC™ glass, indium tin oxide (ITO), doped zinc oxide, indium zinc oxide (IZO), aluminum doped zinc oxide (AZO), and metal oxides / metal / metal oxides (wherein the metal oxides can be substituted with metal carbides, metal nitrides, metal sulfides, etc.).

[0018] 1A and 1B, the sealing member 50 can extend across or along substantially the periphery of the first substrate 18 and the second substrate 34 and cooperate therewith to define the chamber 54 as substantially sealed. The sealing member 50 can be disposed about the periphery of the electrochromic material 58 (e.g., extending from the second surface 26 to the third surface 38). The sealing member 50 can be in the form of any suitable sealing type and material. For example, the sealing member 50 can include a thermoplastic polyurethane (TPU).

[0019] In some embodiments, the first 62 and second 64 annular bands of highly conductive material are optionally deposited around the periphery of the first and second substrates 18 and 34, respectively, and conductive structures 68 (e.g., conductive tape, clips, traces, or wires) are affixed to the highly conductive material and spatially separated from one another. The conductive structures 68 may provide a voltage to the first 62 and second 64 annular bands of highly conductive material to generate a voltage across the electro-optic element 10, thereby reversibly driving the electro-optic element 10 between states, such as a substantially dark state and a substantially transparent state. The first 62 and second 64 annular bands of highly conductive material may include silver, gold, copper, or aluminum (e.g., in the form of metal flakes or particles dispersed in a host material).

[0020] The electro-optical element 10 includes an electrochromic medium 58. The electrochromic medium 58 includes at least one cathodic component and at least one anodic component. The anodic and cathodic components may alternatively be referred to as chromophores, electrochromic molecules, or electrochromic polymers. According to some embodiments of the present disclosure, the anodic and / or cathodic components may be polymeric. In some embodiments, both the cathodic and anodic components are electroactive, and at least the anodic component is electrochromic. Furthermore, the components of the electrochromic medium 58 may be utilized in solution form, gel form, or film form (e.g., solid or gel polymer) within the electro-optical element 10. Thus, the electrochromic medium 58 may include one or more layers of material attached directly to or trapped adjacent to the conductive layers (e.g., 30, 46) that remain attached or trapped when the components are oxidized and / or reduced.

[0021] The electrochromic medium 58 can include one or more anodic components. Non-limiting examples of anodic components include tri-phenylamine (TPA), vanadium-titanium oxide (VTiO X ), metallocenes, 5,10-dihydrophenazine, phenothiazine, phenoxazine, carbazole, triphenothiazine, triphendioxazine, ferrocene, substituted ferrocenyl salts, phenazine, substituted phenazines, phenothiazines, substituted phenothiazines (including substituted dithiazines, thianthrenes, and substituted thianthrenes), di-tert-butyl-diethylferrocene, 5,10-dimethyl-5,10-dihydrophenazine (DMP), 3,7,10-trimethylphenothiazine, 2,3,7,8-Tetramethoxy-thianthrene, 10-methylphenothiazine, tetramethylphenazine (TMP), Bis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT), 3,10-dimethoxy-7,14-(triethylammonium butyl)-triphenodithiazine bis(tetrafluoroborate), and combinations thereof.

[0022] The electrochromic medium 58 can include one or more cathodic components that can include a reducible compound. Non-limiting examples of cathodic components include dioxythiophenes, viologens, low dimerized viologens, or non-dimerized viologens. Exemplary viologens include, but are not limited to, methyl viologen, octyl viologen, benzyl viologen, polymeric viologens, and viologens described in U.S. Patent Nos. 4,902,108, 6,188,505, 5,998,617, 9,964,828, and 6,710,906, which are incorporated herein by reference in their entireties. In one embodiment, the cathodic component is selected from viologen, low dimerized viologen, non-dimerized viologen, substituted viologen, diacrylate viologen, cathodic divinyl viologen, cathodic divinyl ether viologen, cathodic diepoxy viologen, cathodic dioxetane viologen, cathodic dihydroxy viologen, or combinations thereof. In some embodiments, the electrochromic medium may include a combination of two or more cathodic components to provide an electrochromic medium 58 having a desired color when activated. Examples of suitable combinations of anodic and cathodic components can be found in U.S. Patent No. 6,020,987, issued Feb. 1, 2000, entitled "Electrochromic Medium Capable of Producing a Pre-Selected Color," the contents of which are incorporated herein by reference in their entirety.

[0023] The electrochromic medium 58 may also include one or more electrolytes, which may be in the form of a solvent and a salt. The salt may be a metal salt or an ammonium salt. Non-limiting examples of suitable solvents for use in the electrolyte include 3-methylsulfolane, dimethylsulfoxide, dimethylformamide, tetraglyme, and other polyethers, alcohols such as ethoxyethanol, nitriles such as acetonitrile, glutaronitrile, 3-hydroxypropionitrile, and 2-methylglutaronitrile, ketones including 2-acetylbutyrolactone and cyclopentanone, cyclic esters including β-propiolactone, γ-butyrolactone, and γ-valerolactone, propylene carbonate (PC), ethylene carbonate, and homogeneous mixtures thereof. Non-limiting examples of suitable salts include metal or ammonium salts (e.g., lithium triflate, lithium perchlorate, sodium triflate, sodium perchlorate, etc., Li + , Na + , K + , NR'4 + where each R′ is independently H, alkyl, or cycloalkyl, or an anion (F - , Cl - , Br - , I - , BF4 - , PF6 - , SbF6 - , AsF6 - , ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5) - , Al(OC(CF3)3)4 - , or BAr4 - where Ar is an aryl or fluorinated aryl group, such as, but not limited to, C6H5, 3,5-(CF3)2C6H3, or C6F5.

[0024] The electrochromic medium 58 may optionally include additional materials, such as thermal initiators, light absorbers, light stabilizers, heat stabilizers, antioxidants, oxygen scavengers, thickeners, viscosity modifiers, tinting agents, redox buffers, and mixtures of any two or more of such materials. According to aspects of the present disclosure, the additional materials may provide solution enhancing properties. Non-limiting examples of UV stabilizers for use in electrochromic medium 58 may include 2-ethyl-2-cyano-3,3-diphenylacrylate, (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate, 2-(2'-hydroxy-4'-methylphenyl)benzotriazole (such as that sold under the trademark Tinuvin® P by Ciba-Geigy Corp.), 3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionic acid pentyl ester (hereinafter "Tinuvin® PE") prepared from Tinuvin® 213 sold by Ciba-Geigy Corp. by conventional hydrolysis followed by conventional esterification, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-ethyl-2'-ethoxyalanilide.

[0025] Referring now to the example shown in FIG. 1A, the electrochromic medium 58 utilized with the electro-optic element 10 may include an electrochromic or electro-optic film 70 as previously described. Thus, the device 14 incorporating the electro-optic film 70 may be in the form of a full-film device. The electro-optic film 70 may be a polymeric material comprised of a plurality of mixed polymers or a single polymer. In such an embodiment, the electro-optic film 70 may contain both anodic and cathodic components on the backbone of the polymer chain and / or as pendant groups, as will be further discussed in connection with FIGS. 2A-5B. In an embodiment of the electro-optic film 70, the anodic and cathodic components are both located on the same polymer chain.

[0026] 1B, in this embodiment, the electrochromic medium 58 utilized with the electro-optical element 10 includes both a cathode film 74 and an anode film 78. An electrolyte layer 84 separates the cathode film 74 and the anode film 78. In this manner, the cathode film 74, the anode film 78, and the electrolyte layer 84 define the electrochromic medium 58. In such an embodiment, the cathode film 74 may contain cathode components on the backbone of the polymer chains and / or as pendant groups, and the anode film 78 may contain anodic components on the backbone of the polymer chains and / or as pendant groups, as will be further discussed in connection with FIGS. 2A-5B.

[0027] The electrolyte layer 84 may be a gel (e.g., a semi-liquid configured to permeate the cathode membrane 74 and the anode membrane 78) or a polymer electrolyte configured as a thin film electrolyte. In examples utilizing a polymer electrolyte as the electrolyte layer 84, the polymer electrolyte may include a polymer, such as, for example, polymethyl methacrylate ("PMMA"), poly(styrene-lan-ethylene), polystyrene-block-poly(ethylene-lan-butylene), poly(styrene-lan-ethylene), polystyrene-block-poly(ethylene / butylene)-block-polystyrene, poly(ethylene glycol), poly(methyl methacrylate), other polymer electrolytes and / or combinations thereof, as well as various plasticizers, such as propylene carbonate, ethylene carbonate, dimethyl carbonate, and the like. The electrolyte layer 84 may partially permeate the cathode membrane 74 and the anode membrane 78.

[0028] Recent synthetic research efforts towards conductive polymer design have led to the need to tailor such polymers to enhance processing. Conductive polymers can be formulated to contain specific properties that impart beneficial properties to processing, such as specific molecular weights and solvent compatibility factors. For example, properly formulated polymers can enhance solution quality for various coating techniques, including but not limited to slot-die, gravure, inkjet, spray coating, and the like. Utilizing polymer blends (e.g., polymers not formulated as a single bulk material) to impart desired properties to the material may provide some benefit. However, the chemical synthesis of each different blend must be controlled independently.

[0029] Currently, conductive polymers may be formulated using linear polymerization (e.g., aryl coupling), which may result in polymers with tuned absorbance ranging from UV-visible to near-infrared wavelengths. For example, conductive polymers derived from thiophene-based chemistries may utilize aryl coupling methods to combine various donor and acceptor compounds to vary the polymer band gap and the mobility of the associated electrochromic material. Electrochromic materials made in this way often require solubilizing units to make the polymer solution processable. A drawback of this approach is that only one polymer may be tuned to the desired color at a time. Furthermore, the incorporation of acceptor compounds is often limited by the compound, which may make further improvements difficult.

[0030] According to the present disclosure, it has been found that incorporating conjugates into the chemical composition of the polymer (e.g., side chain modifications) to produce a polymer with specific functionality in each block as a single bulk material benefits the overall prepolymerization processability and resulting morphology of the polymer. Block polymers, such as diblock and triblock copolymers, allow fine control over the individual blocks to tailor the molecular weight and / or incorporate various tailored colors in each unit. Furthermore, the incorporation of conjugation into the chemical composition (e.g., formulating the conductive polymer as a bulk material rather than a polymer blend) is beneficial to the electro-optical element 10 for improved electrochromic device speed, electrochromic response time, and device stability and durability. Furthermore, the block copolymers of the present disclosure reduce the susceptibility of the electro-optical element 10 to degradation, thereby providing a more durable device. Conventional conductive polymer blends can be prone to resistive losses due to the chemical structure and processing of the blend, which can result in slower absorbance switching (i.e., color / bleaching) response times.

[0031] 2A-5B, embodiments of the present disclosure relate to the formulation of block copolymers that may include blocks of donor, donor-acceptor, or other units in either diblock, triblock, or mixed (e.g., di- and tri-) morphology (e.g., multiple polymerized block copolymer units). The block copolymer units described herein may be polymerized to form a conductive polymer, shown generally as reference numeral 100, or may be used as an electrochromic medium or as a component thereof for use within an electrochromic medium. Thus, these compounds may form the electrochromic medium 58, the electro-optic film 70, or components thereof, such as the cathode film 74, the anode film 78, and / or the electrolyte layer 84. However, it is within the scope of the embodiments described herein to incorporate the block copolymers of the present disclosure into any suitable medium. For example, the block copolymers of the present disclosure may be used in a medium that is applied to a substrate for an OLED device or an OFET device. FIG. 2A shows a schematic diagram of the chemical structure of an exemplary diblock compound 110, or block copolymer unit. 2B shows a schematic diagram of the chemical structure of an exemplary triblock compound 120, or block copolymer unit. In a particular example, the diblock copolymer includes a compound of formula (II) and the triblock copolymer includes a compound of formula (III). [ka]

[0032] According to embodiments described herein, the blocks 130 (e.g., "m" 130m, "n" 130n, "y" 130y) that form the diblock and / or triblock copolymers 110, 120 of the present disclosure include R groups (e.g., R1, R2, R3, etc.) that may include any side chain modification, chain transfer agent (CTA), or polymerizable compound suitable for use in conductive polymers. Chain transfer agents include R CTA and Z CTA and R, both of which may form chain transfer agents. In this manner, polymer 100 may be CTA and Z CTAThe CTA is part of a reversible addition-fragmentation chain transfer (RAFT) process and may provide increased control over the molecular weight and polydisperity of the resulting compound. A variety of CTA materials may be used, including but not limited to thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, xanthates, and the like. In accordance with aspects of the present disclosure, the CTA may be substituted with other thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, xanthates, and the like. Specific examples of such compounds include but are not limited to 1-methyl-1-phenylethyl ester, 1-cyano-1-methylethyl ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid. Thus, the CTA may be a component of various compositions, R CTA and Z CTA Although illustrated as including a CTA group, the blocks 130 forming the diblock 110 and / or triblock 120 copolymers of the present disclosure may be formed without the use of a CTA group (e.g., R CTA or Z CTA (not including terminal groups). In this manner, free radical polymerization may be performed, thereby resulting in a random copolymer. The R and Z groups may provide specific functionality that provides benefits (e.g., desirable properties) to the conductive polymer, such as solution strengthening properties. In non-limiting examples, the specific functionality may include increased processability, adhesion, advantageous morphological properties, thermal initiation, light absorption, light stabilization, heat stabilization, antioxidant, oxygen scavenging, thickening, viscosity adjustment, tinting / coloring, redox buffering, and the like. Additionally, the R and Z groups may be in the form of compounds that configure the conductive polymer as an electroactive material (e.g., donor / acceptor compounds). In this manner, the diblock 110 or triblock 120 compounds of the present disclosure may include R and / or Z groups that provide specific desired functionality, and / or R and / or Z groups that are provided to enable further polymerization of the conductive polymer, and / or may include electroactive properties, schematic examples of which are illustrated in Figures 3A-5B.

[0033] Thus, the diblock 110 and triblock 120 copolymers of formulas (II) and (III) can be selected from any suitable CTA or conversion of a CTA (typically from a CTA) R CTA and Z CTA Similarly, the R1, R2, and R3 groups may be any suitable compound. It is understood that the number of R groups depends on the particular diblock or triblock formula. Thus, the diblock compounds 110 and triblock compounds 120 of the present disclosure may contain fewer or more than the three R groups shown in formulas (II) and (III). Additionally, the R or Z groups may function as caps, linkers, or may further react with additional compounds. For example, the diblock 110 copolymer 100 with linker (R2) may contain a compound of formula (IV), and the triblock 120 copolymer 100 may contain a compound of formula (V). [ka]

[0034] FIG. 3A shows a schematic chemical structure of an exemplary electrochromic compound 140 conjugated or covalently bonded with a diblock compound 110 according to an embodiment of the present disclosure. In a particular example, the electrochromic compound 140 conjugated with the diblock compound 110 includes a compound of formula (VI). Specifically, a dioxythiophene is attached to the m block position 130m with a non-limiting example of an R1 attachment. It is understood that the unreacted (e.g., pre-reacted) thiophene unit can undergo further modification and / or polymerization. In this manner, the unreacted thiophene functions as a linker. The unreacted thiophene may also be coupled with an acceptor or donor-acceptor 144 compound to tune the color of the medium 58. [ka]

[0035] In a particular example, the electrochromic compound 140 conjugated with the diblock compound 110 comprises a compound of formula (VII). Specifically, the dioxythiophene is attached to the m block position 130m with non-limiting examples of R1, R2, and R3 attachments. Of course, the unreacted thiophene units can undergo further modification and / or polymerization. [ka]

[0036] In another embodiment, the electrochromic compound 140 conjugated with the diblock compound 110 comprises a compound of formula (VIII). Specifically, a triphenylamine is shown attached to the m position of the m block 130 with non-limiting examples of R1, R2, and R3 attachments. [ka]

[0037] In yet another embodiment, the electrochromic compound conjugated with the diblock compound 110 comprises a compound of formula (IX). Specifically, triphenylamine is added at the m block position 130m of a single diblock copolymer, including non-limiting examples of R2 and R3 attachments. [ka]

[0038] 3B shows a schematic chemical structure of an exemplary electrochromic compound 150 conjugated with a triblock compound 120 according to an embodiment of the present disclosure. In a particular example, the electrochromic compound 150 conjugated with the triblock compound 120 comprises a compound of formula (X). Specifically, a dioxythiophene is attached to the m block position 130m with a non-limiting example of an R1 attachment. Of course, unreacted thiophene units can undergo further modification and / or polymerization. [ka]

[0039] In another example, the electrochromic compound 150 conjugated with the triblock compound 120 comprises a compound of formula (XI). Specifically, a triphenylamine is shown attached to the m block position 130m with non-limiting examples of R1, R2, and R3 attachments. [ka]

[0040] In another embodiment, the electrochromic compound 150 conjugated with the triblock compound 120 comprises a compound of formula (XII). Specifically, different triphenylamines are shown attached to the m-block positions 130m with non-limiting examples of R1, R2, R3, and R4 attachments. [ka]

[0041] In yet another embodiment, the electrochromic compound conjugated with the triblock compound 120 comprises a compound of formula (XIII). Specifically, different triphenylamines are added to the y block positions 130y of a single triblock copolymer 120, including non-limiting examples of R1, R2, R3, and R4 attachments. [ka]

[0042] 4A shows a schematic chemical structure of an exemplary electrochromic compound 160 conjugated with a diblock compound 110, while FIG. 4B shows a schematic chemical structure of an exemplary electrochromic compound 170 conjugated with a triblock compound 120 according to an embodiment of the present disclosure. In a particular example, the electrochromic compound 170 conjugated with the triblock compound 120 includes compounds of formula (XIV), formula (XV), and formula (XVI). Formula (XIV) and formula (XV) show a donor-acceptor compound 144 (in y block 130n) separated by an n block 130n from a donor compound 148 (in m block 130m). [ka]

[0043] Formula (XVI) is a non-limiting example in which triphenylamine (TPA-'1') compounds within the same triblock copolymer 120 are separated from different triphenylamine (TPA-'2') compounds by n-block 130n. In this example, different "colors" and / or monomers are conjugated (e.g., covalently bonded) to the triblock copolymer 120 as a single polymerization. For example, the copolymer can include two or more visibly colored chain transfer agent side chain modifications, each visibly colored chain transfer agent side chain modification comprising a different hue than the other. This is a direct benefit to the effective scalability of compound 120, which may include generating an array of desired colors based on a mixture of two or more chain transfer agent side chain modifications with distinct hues. Another benefit includes the ability to generate monomers that provide the same color or a single color but with different redox potentials compared to compounds that include only a single TPA compound. [ka]

[0044] 5A shows a schematic chemical structure of an exemplary electrochromic compound 180 including an auxiliary material 184 conjugated with a triblock compound 120 according to an embodiment of the present disclosure. Specifically, FIG. 5A illustrates the combination of TPA-1 (e.g., in m-block 130m) separated by an n-block 130m from a donor-acceptor compound 144 (e.g., in y-block 130y). In this manner, different conductive / non-conductive materials used as auxiliary materials 184 can be copolymerized to form compound 180.

[0045] 5B shows schematic chemical structures of an exemplary conductive compound 190 and an auxiliary material 194 conjugated with a triblock compound 120 according to an embodiment of the present disclosure. Specifically, FIG. 5B illustrates combining a conductive (not necessarily electrochromic) polymer 198 in a y block 130y in combination with an auxiliary TPA-2 material 194 (e.g., in an m block 130m) separated by an n block 130n.

[0046] Thus, the exemplary block copolymers 110, 120 disclosed herein may include different materials conjugated to the chemical composition of the polymer 100, which provide solution-enhancing properties. The solution-enhancing properties may impart properties to the solution, or to the polymer 100, and / or the electro-optic medium 58, that provide benefits. Non-limiting examples of beneficial properties include increased processability, adhesion, or advantageous morphological properties, as previously described. In this manner, the exemplary block copolymers 110, 120 disclosed herein allow for the mixing of the conductive polymer 100 with other color materials, which have desirable properties or characteristics, such as UV-visible absorbance in the dark. In some examples, the diblock and / or triblock approaches described may be utilized with thiophene systems, such as dioxythiophene compounds. For example, a single dioxythiophene unit may be tailored with one or more diblock or triblock copolymers, as previously described. In other examples, the diblock and triblock approaches may be utilized with various triphenylamine compounds, as previously described. The diblock and triblock approaches described herein can provide fine control over the properties of cathodic conducting polymers, such as dioxythiophenes, and anodic "coloring" polymers, such as triphenylamines. It should be understood that cathodic or anodic material classifications are generally related to redox potential. In this way, dioxythiophenes may function as anodic materials (e.g., acceptors and thiophene compounds), and tri-phenylamines may function as cathodic materials depending on the redox potential of the compounds.

[0047] Further aspects of the present disclosure relate to electrochromic functionalization blocks (e.g., 144 in 130n, 130m, 130y, etc.) separated by various functional moieties (e.g., auxiliary materials 184, 194, non-distributed styrene, sulfone, aliphatic, aromatic, etc.). In some examples, the electrochromic functionalization blocks (e.g., 144 in 130n, 130m, 130y, etc.) may include styrene blocks, acrylate blocks, ether blocks, ester blocks, acrylamide blocks, and methacrylate blocks, etc. The functional moieties may include solution enhancing properties. In other examples, the functional moieties may be utilized to incorporate compounds such as triphenylamines and colored or non-colored conductive additives (e.g., side chain modifications). In this manner, various tailored triphenylamines (e.g., with redox potential and / or color modifications) may be combined into a single block copolymer for further polymerization into electrochromic functionalization blocks (e.g., styrene) with various spacers and side chain modifications. Specific examples of side chain modifications include chain transfer agent side chain modifications.

[0048] In other words, the diblock copolymer 110 and triblock copolymer 120 of the present disclosure may include a chain transfer agent side chain modification. For example, the diblock copolymer 110 or triblock copolymer 120 may impart a change in the oxidation state of the first donor compound or the second donor compound, which may include dioxythiophene or triphenylamine. In another example, the diblock copolymer 110 or the first triblock copolymer 120 includes a visibly colored chain transfer agent side chain modification.

[0049] The following examples illustrate various features and advantages provided by the present disclosure and are not intended to limit the scope of the invention and the appended claims in any way. EXAMPLES

[0050] Working Example

[0051] Example 1

[0052] FIG. 6 for Example 1 shows an exemplary synthetic scheme (200) for synthesizing the donor compound 3,3-bis(bromomethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin ("Br2-PDOT"). It is understood that Br2-PDOT may be synthesized according to other processes. It is also understood that Scheme 1 (200) may include additional or alternative steps without departing from the scope of the present disclosure.

[0053] In the initial step, 5.0 grams of 3,4-dimethoxythiophene, 10.9 grams of 2,2-bis(bromomethyl)propane-1,3-diol, and 6.75 grams of p-toluenesulfonic acid were added to 150 milliliters of anhydrous toluene and stirred until completely dissolved. The solution was degassed three times using a Schlenk line with vacuum pump / N2 purge cycles. The solution was heated to reflux, thereby removing methanol by distillation and maintaining a vapor temperature of approximately 60°C during the synthesis. The reaction was then cooled to room temperature, followed by the addition of water. The organic layer was separated from the aqueous layer, followed by an additional water wash with 3 wt% NaHCO3. The organic layer was again washed with water and separated from the aqueous layer. The final water wash step was repeated to ensure removal of impurities, etc. The separated organic layer was rotary evaporated to remove the solvent and dried under vacuum to give a solid product. The product was purified by column chromatography using a hexane / ethyl acetate mixture. The purity of the resulting Br2-PDOT by gas chromatography-mass spectrometry (GC-MS) was greater than 99%.

[0054] Example 2

[0055] FIG. 7 for Example 2 shows an exemplary synthetic scheme 300 for synthesizing {3-[(4-ethenylbenzoyloxy)methyl]-2H,3H,4H-thieno[3,4-b][1,4]dioxepin-3-yl}methyl 4-ethenylbenzoate ("PDOTBE"), which may function as a monomer with a vinyl group (e.g., X linker), which may react to carry blocks such as n block 130n and m block 130m, or function as a CTA. Such an example is illustrated in connection with FIG. 8. It is understood that PDOTBE may be synthesized according to other processes. It is also understood that Scheme 2 (300) may include additional or alternative steps without departing from the scope of the present disclosure.

[0056] In the initial step, 5.0 grams of Br2-PDOT, 4.7 grams of vinyl benzoic acid, and 9.76 grams of K2CO3 were added to 300 milliliters of anhydrous N,N-dimethylformamide and stirred for 1 hour. The solution was degassed three times with vacuum pump / N2 purge cycles using a Schlenk line. The solution was heated to 110-115 °C for at least 48 hours. The reaction was then cooled to room temperature, followed by filtering off the K2CO3. The filtrate was extracted into diethyl ether, followed by washing with H2O three times. The organic layer was separated from the aqueous layer and rotary evaporated to remove the solvent. The remaining contents were dissolved in acetone, followed by precipitation with excess methanol. The solid was purified by column chromatography with hexane / ethyl acetate. The final product was dried under vacuum at 50 °C overnight. The purity of the resulting PDOTBE, as measured by high performance liquid chromatography (HPLC), was greater than 99%.

[0057] Example 3

[0058] 8 for Example 3 shows an exemplary synthetic scheme 400 for synthesizing poly(PS-co-PDOTBE-co-VBA) copolymer, which may function as diblock copolymer 110. It is understood that poly(PS-co-PDOTBE-co-VBA) may be synthesized according to other processes. It is also understood that Scheme 3 (400) may include additional or alternative steps without departing from the scope of the present disclosure.

[0059] In the initial step, 1.0 grams of PDOTBE, 0.218 grams of styrene (including PS), 0.309 grams of 4-vinylbenzoic acid ("VBA"), and 0.005 grams of azobisisobutyronitrile ("AIBN") (equivalents) were dissolved in 50 milliliters of THF. The mixture was heated to reflux and allowed to react for various times. The reaction was then cooled to room temperature and the solvent was removed by rotary evaporation. The solid was precipitated using diethyl ether and filtered to remove unreacted monomer. The solid was redissolved in THF, rotary evaporated, and reprecipitated using diethyl ether. The final solid was dried under vacuum at 50°C. In Scheme 3 (400), blocks n and m are of different molar equivalents, and X (410) refers to PDOTBE as a linker to other monomeric or polymeric units. It is within the scope of this disclosure that the X unit 410 may or may not be connected.

[0060] Example 4

[0061] FIG. 9 for Example 4 illustrates an exemplary synthetic scheme (500) for synthesizing a poly(PS-CTA) block. It is understood that the poly(PS-CTA) block may be synthesized according to other processes. It is also understood that Scheme 4 (500) may include additional or alternative steps without departing from the scope of the present disclosure. As shown in Scheme 4 (500), the chain transfer agent (CTA) 510 is a carboxyl group consisting of R CTA Groups 514 and Z CTAThe poly(PS-CTA) block may then be further processed into repeating polymers, each of which may include R CTA Group 514 and Z CTA It inserts and propagates between groups 518, thereby generating a block (eg, 130n) that can be stored for further reaction to obtain a block copolymer (eg, 110, 120).

[0062] In the initial step, 2.0 grams of styrene, 0.004 grams of 2-(dodecylthiocarbonothioylthio)propionic acid chain transfer agent (CTA), and 0.001 grams of AIBN were dissolved in 50 milliliters of THF. The mixture was heated to reflux and allowed to react for various times. The reaction was then cooled to room temperature and the solvent and unreacted monomer were removed by rotary evaporation, distillation, and filtration. The solid was redissolved in THF and reprecipitated using diethyl ether to remove unreacted monomer and impurities. The final solid was dried under vacuum at 50°C.

[0063] Example 5

[0064] FIG. 10 for Example 5 illustrates an exemplary synthetic scheme 600 for synthesizing a poly(BA-CTA) block. It is understood that the poly(BA-CTA) block may be synthesized according to other processes. It is also understood that Scheme 5 (600) may include additional or alternative steps without departing from the scope of the present disclosure. As shown in Scheme 5 (600), the poly(BA-CTA) block may be synthesized according to other processes. CTA Groups 614 and Z CTA The CTA 610 has a group 618. Thus, the polymers each have R CTA Base 614 and Z CTA It inserts and propagates between groups 618, thereby generating a block (eg, 130m) that can be stored for further reaction to obtain a block copolymer (eg, 110, 120).

[0065] In the initial step, 0.5 grams of 4-vinylbenzoic acid (VBA), 0.004 grams of 2-(dodecylthiocarbonothioylthio)propionic acid chain transfer agent (CTA), and 0.001 grams of AIBN were dissolved in 50 milliliters of THF. The mixture was heated to reflux and allowed to react for various times. The reaction was then cooled to room temperature and the solvent and unreacted monomer were removed by rotary evaporation and distillation. The solid was precipitated using diethyl ether. The solid was redissolved in THF and reprecipitated using diethyl ether to remove the unreacted monomer. The final solid was dried under vacuum at 50°C.

[0066] In other examples of Scheme 4 (500) and Scheme 5 (600), the styrene or 4-vinylbenzoic acid blocks shown in PS-CTA and BA-CTA, respectively, are replaced or may be substituted with non-limiting examples such as 2-ethylhexanoic acid vinyl ester, methacrylic acid 2,2,6,6-tetramethyl-4-piperidyl ester, isooctyl vinyl ether, cyclohexyl vinyl ether, benzoic acid vinyl ester, propyl vinyl ether, isobutyl vinyl ether, vinyl methacrylate, vinyl propionate, vinyl pivalate, sodium 4-vinylbenzenesulfonate, 3-sulfopropyl methacrylate potassium salt, 4-aminostyrene, 4-bromostyrene, 3-(trimethoxysilyl)propyl methacrylate, and the like. Additionally, the chain transfer agents may be replaced or substituted with other thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, xanthates, non-limiting examples include 1-methyl-1-phenylethyl ester, 1-cyano-1-methylethyl ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid, and the like.

[0067] Example 6

[0068] FIG. 11 for Example 6 shows an exemplary synthetic scheme (700) for synthesizing the poly(PS-b-BA)-1 diblock. It is understood that the poly(PS-b-BA)-1 diblock may be synthesized according to other processes. It is also understood that Scheme 6 (700) may include additional or alternative steps without departing from the scope of the present disclosure. As shown in Scheme 6 (700), the CTAs are each R CTA Groups 714 and Z CTA Contains group 718.

[0069] In the initial step, 0.25 grams of poly(BA-CTA), 0.25 grams of poly(PS-CTA), and 0.001 grams of AIBN were dissolved in 50 milliliters of THF. The mixture was heated to reflux and allowed to react for various times. The reaction was then cooled to room temperature and the solvent and unreacted monomer were removed by rotary evaporation and distillation. The solid was precipitated using diethyl ether. The solid was redissolved in THF and reprecipitated using diethyl ether to remove the unreacted monomer. The final solid was dried under vacuum at 50° C. The advantage of the process of Scheme 6 (700) is the additional control over molecular weight and polydispersity.

[0070] Example 7

[0071] FIG. 12 for Example 7 shows an exemplary synthetic scheme 800 for synthesizing the diblock poly(PS-b-VBA)-1. It is understood that the diblock poly(PS-b-VBA)-1) may be synthesized according to other processes. It is also understood that Scheme 7 (800) may include additional or alternative steps without departing from the scope of the present disclosure. In some examples, Scheme 7 (800) is an alternative synthetic route to Scheme 6 (700). Thus, the method steps according to Scheme 6 (700) are also applicable to Scheme 7 (800). As shown in Scheme 7 (800), the CTAs are each R CTA Groups 814 and Z CTA Contains group 818.

[0072] Example 8

[0073] FIG. 13 for Example 8 shows an exemplary synthetic scheme 900 for synthesizing diblock 110 with poly(PS-b-PDOTBE-b-BA)-1 thiophene linker. It is understood that diblock 110 with poly(PS-b-PDOTBE-b-BA)-1 thiophene linker may be synthesized according to other processes. It is also understood that Scheme 8 (900) may include additional or alternative steps without departing from the scope of the present disclosure. As shown in Scheme 8 (900), the CTAs are each R CTA Groups 914 and Z CTA It includes group 918. Additionally, one may create "wavy" lines as shown in the drawing, which represent a connection to another entity, this being the polymer in FIG.

[0074] In the initial step, 1.0 gram of PDOTBE, 0.25 grams of poly(BA-CTA), 0.25 grams of poly(PS-CTA), and 0.001 grams of AIBN were dissolved in 50 milliliters of THF. The mixture was heated to reflux and allowed to react for various times. The reaction was then cooled to room temperature and the solvent and unreacted monomer were removed by rotary evaporation and distillation. The solid was precipitated using diethyl ether. The solid was redissolved in THF and reprecipitated using diethyl ether to remove the unreacted monomer. The final solid was dried under vacuum at 50°C.

[0075] Example 9

[0076] FIG. 14 for Example 9 shows an exemplary synthetic scheme 1000 for synthesizing diblock 110 with poly(PS-b-PDOTBE-b-VBA)-2 thiophene linker. It is understood that diblock 110 with poly(PS-b-PDOTBE-b-VBA)-2 thiophene linker may be synthesized according to other processes. It is also understood that Scheme 9 (1000) may include additional or alternative steps without departing from the scope of the present disclosure. In some examples, Scheme 9 (1000) is an alternative synthetic route to Scheme 8 (900). Thus, the method steps according to Scheme 8 (900) are also applicable to Scheme 9 (1000). As shown in Scheme 9 (1000), the CTAs are each R CTA Groups 1014 and Z CTA Contains group 1018.

[0077] Example 10

[0078] FIG. 15 for Example 10 shows an exemplary synthetic scheme 1100 for synthesizing poly(PS-co-PDOTBE-co-PSS) copolymer, which may function as the diblock copolymer 110. It is understood that poly(PS-co-PDOTBE-co-PSS) copolymer may be synthesized according to other processes. It is also understood that scheme 10 (1100) may include additional or alternative steps without departing from the scope of the present disclosure. For example, the polymers of the present disclosure (e.g., sulfonate salts described in the following procedure) may be modified. For example, the polymers may be covalently functionalized with quaternized amines or ammonium cations, which may be primarily attached to blocks of the copolymer (e.g., polystyrene blocks). Thus, the blocks of the polymer (e.g., 130) may be physically crosslinked (e.g., via weak interactions such as ionic bonds) and not chemically crosslinked (e.g., covalently bonded) to each other. Optionally, other types of cations, such as pyridinium or imidazolium groups, may be used to modify or functionalize the polymer. Additionally, Na +While exemplified as above, the cationic counterions in the synthetic schemes according to the present disclosure include, but are not limited to, H + , Li + etc. Similarly, the anionic counterions of the synthetic schemes according to the present disclosure may be any suitable cation.

[0079] In the initial step, 1.0 grams of PDOTBE, 0.208 grams of styrene (PS), 0.412 grams of sodium 4-vinylbenzenesulfonate (PSS), and 0.005 grams of AIBN (equivalents) were dissolved in 10 milliliters of THF and 20 milliliters of n-propanol. The mixture was heated to reflux and reacted for various times. The reaction was then cooled to room temperature and the solvent was removed by rotary evaporation. The solid was precipitated using diethyl ether. The solid was then redissolved in 100 milliliters of ethanol and reprecipitated using diethyl ether to remove unreacted monomer. The solid was filtered and dried under vacuum at 50° C. In Scheme 10 (1100), 130n and 130m are different molar equivalents and X refers to PDOTBE as a linker to other monomeric or polymeric units. It is within the scope of this disclosure that the X unit may or may not be connected. In carrying out Scheme 10 (1100), it was unexpected that the PDOTBE compound could be treated in an oxidizable form (eg, rather than in a reduced form).

[0080] Example 11

[0081] FIG. 16 for Example 11 shows an exemplary synthetic scheme 1200 for synthesizing triblock 120 with poly(PDOTBE-PS-b-VP-b-VBA)-1 thiophene linker. It is understood that triblock 120 with poly(PDOTBE-PS-b-VP-b-VBA)-1 thiophene linker may be synthesized according to other processes. It is also understood that scheme 11 (1200) may include additional or alternative steps without departing from the scope of the present disclosure. As shown in scheme 11 (1200), the CTAs are each RCTA Groups 1214 and Z CTA Contains group 1218.

[0082] In the initial step, 1.0 gram of PDOTBE, 0.25 gram of poly(PS-CTA), 0.25 gram of 4-vinylbenzoic acid (VBA), 0.1 gram of vinyl propionate (VP), and 0.003 gram of AIBN were dissolved in 50 milliliters of THF. The mixture was heated to reflux and allowed to react for various times. The reaction was then cooled to room temperature and the solvent and unreacted monomers were removed by rotary evaporation and distillation. The solid was precipitated using diethyl ether. The solid was redissolved in THF and reprecipitated using diethyl ether to remove the unreacted monomers. The final solid was dried under vacuum at 50°C.

[0083] Example 12

[0084] FIG. 17 for Example 12 shows an exemplary synthesis scheme 1300 for synthesizing a diblock 110 copolymer to a conjugate polymer 1310, poly(PS-co-PDOTBE-co-PSS)-graft-poly(Br2PDOT2-co-BDT). Of course, the diblock 110 copolymer to the conjugate polymer 1310, poly(PS-co-PDOTBE-co-PSS)-graft-poly(Br2PDOT2-co-BDT), may be synthesized according to other processes. It is also understood that Scheme 12 (1300) may include additional or alternative steps without departing from the scope of the present disclosure. For example, the designation "block copolymer (110 / 120)" indicates a molecular structure beyond this point in Scheme 12 (1300) that is applicable to a polymer according to the present disclosure (e.g., conductive polymer 100, etc.). Additionally, the depicted "a" and "b" blocks may include different diblock / triblock attachments 110 / 120 onto the thiophene. For example, the depicted "b" block may include groups that do not include the depicted R1.

[0085] In the initial step, 1.04 grams of poly(PS-co-PDOTBE-co-PSS), 0.691 grams of Br2PDOT2 (donor compound), 0.1178 grams of Br2-BDT (acceptor compound), 0.8559 grams of potassium carbonate, 0.076 grams of pivalic acid, and 0.0100 grams of palladium acetate were dissolved in 80 milliliters of N,N-dimethylacetamide. The solution was degassed three times with a vacuum pump / N2 purge cycle using a Schlenk line. The reaction was allowed to proceed for various times. The reaction was then cooled to room temperature, followed by the addition of methanol to precipitate the polymer. The polymer was washed multiple times with methanol, hexane, and acetone to remove impurities. The polymer was then redissolved in N,N-dimethylacetamide and reprecipitated into methanol. The polymer was then washed again with methanol and hexane. The final polymer was dried overnight under vacuum at 75°C.

[0086] Example 13

[0087] FIG. 18 for Example 13 shows an exemplary synthetic scheme 1400 for synthesizing the diblock 110 copolymer into the conjugate polymer 1410, poly(PS-co-PDOTBE-co-VBA)-2-graft-poly(Br2PDOT2-co-BDT). Of course, the diblock 110 copolymer may be synthesized into the conjugate polymer 1410, poly(PS-co-PDOTBE-co-VBA)-2-graft-poly(Br2PDOT2-co-BDT) according to other processes. It is also understood that Scheme 13 (1400) may include additional or alternative steps without departing from the scope of the present disclosure.

[0088] In the initial step, 2.04 grams of poly(PS-co-PDOTBE-co-VBA)-2, 0.691 grams of Br2PDOT2, 0.1178 grams of BDT, 0.8559 grams of potassium carbonate, 0.076 grams of pivalic acid, and 0.0300 grams of palladium acetate were dissolved in 80 milliliters of N,N-dimethylacetamide. The solution was degassed three times with a vacuum pump / N2 purge cycle using a Schlenk line. The reaction was allowed to proceed for various times. The reaction was then cooled to room temperature, followed by the addition of methanol to precipitate the polymer. The polymer was washed multiple times with methanol, hexane, and acetone to remove impurities. The polymer was then redissolved in N,N-dimethylacetamide and reprecipitated into methanol. The polymer was then washed again with methanol and hexane. The final polymer was dried overnight under vacuum at 75°C.

[0089] 19 is an infrared spectroscopy plot of absorbance intensity as a function of wavenumber for PDOTBE according to an embodiment of the present disclosure. Specifically, FIG. 19 shows the results of infrared spectroscopy of a PDOTBE sample highlighting unreacted vinyl groups, which are suitable for further reaction into a block copolymer. As shown in the plot, the vinyl peak 1900 occurs at approximately 915 cm -1 and 1990cm -1 The carbonyl ester peak (1910) is at approximately 1710 cm -1 The ether / ester peak is at about 1100–1300 cm -1 It exists in.

[0090] 20 is an infrared spectroscopy plot of absorbance intensity as a function of wavenumber for an exemplary diblock 110 copolymer (e.g., polymer 100) 2000 according to an embodiment of the present disclosure. Specifically, FIG. 20 shows infrared spectroscopy results for two different poly(PS-co-PDOTBE-co-VBA) diblock 110 copolymer samples, highlighting the different blocks within the copolymer. As shown in the plot, the vinyl peak is located at approximately 915 cm -1 or 1990cm -1No styrene blocks were found to be present at about 690 cm, indicating that they had reacted completely (see arrow A). -1 and 750cm -1 There is a strong hydroxyl extension indicating the presence of the VBA block 2000.

[0091] 21A and 21B are images of two different scales showing the morphology of a polymer synthesized according to Scheme 13 (1400) according to an embodiment of the present disclosure. Specifically, FIG. 21A and 21B show the morphology of poly(PS-co-PDOTBE-co-VBA)-graft-poly(Br2PDOT2-co-BDT) using atomic force microscopy (AFM). As shown, microphase separation shows a uniform bicontinuous morphology resulting from different blocks of polymer and low surface roughness.

[0092] FIG. 22A is a plot of current (left axis) and −log(CIEY / 100) (right axis) as a function of time for an exemplary electrochromic device 14 including poly(PS-b-PDOTBE-b-VBA)-2-graft-poly(Br2PDOT2-co-BDT) copolymer as the conductive polymer 100 according to an embodiment of the present disclosure. FIG. 22A shows the current response for a + / −1.0V switching potential (left axis). The corresponding absorbance for CIEY is illustrated on the right axis. The response shows fast switching times, including switching times of less than 25 seconds from a completely dark state to a completely clear state (e.g., the second state and the first state, respectively). FIG. 22B is a plot of absorbance at two different voltages (e.g., + / −1.0V) representing the first and second states of the electrochromic device as a function of wavelength according to an embodiment of the present disclosure. FIG. 22B shows the specific absorbance across UV-visible wavelengths for two different states / conditions (+ / −1.0V). The states may be considered "bistable states" that may remain dark or transparent at open circuit (e.g., indicating memory). States between these potentials may also be maintained, and even outside the + / - 1.0V range.

[0093] The structure of the exemplary electro-optical device 14 in Figures 22A and 22B includes a cathode layer (e.g., cathode film 74) containing poly(PS-b-PDOTBE-b-VBA)-2-graft-poly(Br2PDOT2-co-BDT), which was prepared in various solvents having concentrations ranging from 0.5 to 6 wt%. The electro-optical device 14 also includes an electrolyte layer (e.g., electrolyte layer 84) containing a poly(methyl methacrylate) polymer and a salt (e.g., lithium triflate, lithium perchlorate, sodium triflate, sodium perchlorate, etc.), and a vanadium-titanium oxide (VTiO x ) layer. However, other exemplary electro-optical devices 14 with polymers of FIG. 22A have been constructed with other anodes, such as TPA. It is within the scope of this disclosure for the cathode layer, anode layer, or electrolyte layer to be sputtered, coated from a sol-gel material, or applied with any other suitable technique. In certain examples, the cathode layer is deposited on a transparent conductive oxide (TCO) layer, such as indium tin oxide, and the anode layer, VTiO x The layer is deposited on another TCO layer. The electrolyte layer is disposed between the cathode layer and the anode layer.

[0094] It will be understood that any described process or step within a described process may be combined with other disclosed processes or steps to form structures within the scope of the present device. Similarly, it will be understood that any described compound (e.g., blocks, donors, acceptors, R groups, side chain modifications, etc.) may be combined with other disclosed compounds to form structures. The exemplary structures and processes disclosed herein are for illustrative purposes and are not to be construed as limiting.

[0095] It is also to be understood that modifications and variations can be made to the structures and methods described above without departing from the concepts of the present apparatus, and that these concepts are intended to be covered by the following claims unless the language of those claims expressly states otherwise.

[0096] The above description is to be considered as only a description of the illustrated embodiment. Modifications of the device will occur to those skilled in the art and to those who make or use the device. Therefore, it will be understood that the embodiments shown in the drawings and the above description are merely for illustrative purposes and are not intended to limit the scope of the device, which is defined by the following claims, which are to be interpreted in accordance with the principles of patent law, including the doctrine of equivalents.

Claims

1. A medium for an electro-optical device, comprising: A first electrochromic block copolymer unit, at least one selected from the group consisting of a first diblock copolymer and a first triblock copolymer; a first electrochromic block copolymer unit comprising at least one of a first donor compound and a first acceptor compound conjugated with the at least one of the first diblock copolymer and the first triblock copolymer, wherein the at least one of the first donor compound and the first acceptor compound is electrochromic, thereby forming the first electrochromic block copolymer unit; a second electrochromic block copolymer unit, at least one selected from the group consisting of a second diblock copolymer and a second triblock copolymer; a second electrochromic block copolymer unit comprising at least one of a second donor compound and a second acceptor compound conjugated with the at least one of the second diblock copolymer and the second triblock copolymer, wherein the at least one of the second donor compound and the second acceptor compound is electrochromic, thereby forming the second electrochromic block copolymer unit; A medium for an electro-optic device, wherein the first electrochromic block copolymer unit is polymerized with the second electrochromic block copolymer unit, thereby forming a repeating polymer.

2. The medium for an electro-optical device according to claim 1 , wherein the medium is in the form of a film.

3. 3. A medium for electro-optical devices as described in claim 1 or claim 2, wherein the at least one of the first diblock copolymer and the first triblock copolymer includes at least one side chain modification that imparts at least one of increased processability, adhesion, or advantageous morphological properties to the medium.

4. A medium for electro-optical devices according to any one of claims 1 to 3, wherein said at least one of said first diblock copolymer and said first triblock copolymer comprises a chain transfer agent side chain modification.

5. 5. The medium for an electro-optical element according to claim 1, wherein the at least one of the first diblock copolymer and the first triblock copolymer comprises at least one of a styrene block, an acrylate block, an ether block, an ester block, and a methacrylate block, the at least one block including at least one side chain modification.

6. 6. The medium for an electro-optic device of claim 5, wherein said at least one of said first diblock copolymer and said first triblock copolymer comprises a visibly colored chain transfer agent side chain modification.

7. 7. The medium for an electro-optical device of claim 6, wherein the at least one of the first diblock copolymer and the first triblock copolymer comprises two visibly colored chain transfer agent side chain modifications, each visibly colored chain transfer agent side chain modification comprising a different hue than the other.

8. 8. The medium for an electro-optical element according to claim 1, wherein at least one of the first diblock copolymer and the first triblock copolymer imparts a change in the oxidation state of one of the first donor compound and the second donor compound, and the one of the first donor compound or the second donor compound comprises at least one of dioxythiophene and triphenylamine.

9. the at least one of the first diblock copolymer and the first triblock copolymer is 9. The medium for an electro-optical element according to claim 1, comprising a first block and a second block, the first block and the second block being crosslinked by at least one of physically crosslinking and chemically crosslinking.

10. 10. A medium for electro-optical devices according to any one of claims 1 to 9, wherein a chemical compound of the following formula (I) links said first electrochromic block copolymer unit with said second electrochromic block copolymer unit: 【Chemistry 1】

11. An electro-optical element, a first substrate defining a first surface and a second surface, a first conductive layer disposed on the second surface; a second substrate defining a third surface and a fourth surface, a second conductive layer disposed on the third surface; a medium disposed between the second surface and the third surface, A first block copolymer unit, at least one selected from the group consisting of a first diblock copolymer and a first triblock copolymer; a first block copolymer unit comprising at least one of a first donor compound and a first acceptor compound conjugated to the at least one of the first diblock copolymer and the first triblock copolymer, thereby forming the first block copolymer unit; A second block copolymer unit, at least one selected from the group consisting of a second diblock copolymer and a second triblock copolymer; a second block copolymer unit comprising at least one of a second donor compound and a second acceptor compound conjugated with the at least one of the second diblock copolymer and the second triblock copolymer, thereby forming the second block copolymer unit; and a medium comprising: An electro-optic element, wherein the first block copolymer unit is polymerized with the second block copolymer unit.

12. 12. The electro-optic element of claim 11, wherein the medium is in the form of a cathodic film, an anodic film, or an electrochromic film.

13. 13. The electro-optic element of claim 11, wherein at least one of the first diblock copolymer and the first triblock copolymer includes side chain modifications that impart at least one of increased processability, adhesion, or advantageous morphological properties to the medium.

14. 13. The electro-optical element of claim 11, wherein at least one of the first diblock copolymer and the first triblock copolymer comprises a side chain modification that produces an effect on the UV-visible absorbance in the dark state of the electro-optical element.

15. the at least one of the first diblock copolymer and the first triblock copolymer; 15. The medium for an electro-optical element according to any one of claims 11 to 14, comprising a first block and a second block, the first block and the second block being physically crosslinked.

16. the at least one of the first diblock copolymer and the first triblock copolymer; 15. The medium for an electro-optical element according to any one of claims 11 to 14, comprising a first block and a second block, the first block and the second block being chemically crosslinked.

17. A medium for electro-optical devices according to any one of claims 11 to 14, wherein a chemical compound of the following formula (I) links said first block copolymer unit and said second block copolymer unit: 【Chemistry 2】

18. A medium for an electro-optical device comprising a chemical compound of formula (I): 【Chemistry 3】

19. 20. The medium for an electro-optical device of claim 18, further comprising a first block copolymer unit polymerized with a second block copolymer unit, wherein formula (I) links the first block copolymer unit and the second block copolymer unit.

20. 20. The medium for an electro-optical device according to claim 19, comprising at least one of poly(PS-co-PDOTBE-co-PSS) copolymer and poly(PS-co-PDOTBE-co-VBA)-2-graft-poly(Br2PDOT2-co-BDT) copolymer.

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