KR20090040256A - Amorphous polymers with pendant chromogenic groups - Google Patents

Abstract

Amorphous polymers with chromogenic pendant groups are provided. The amorphous polymers can be used to make elastomeric films and coatings that can be incorporated into laminates and used to make articles such as architectural and vehicular glazing, and in applications such as eyewear, displays and signage.

Description

Amorphous Polymer Containing Branched Chromophoric Groups {AMORPHOUS POLYMERS WITH PENDANT CHROMOGENIC GROUPS}

FIELD OF THE INVENTION The present invention relates to amorphous polymers containing side chain chromogenic groups and methods of making such polymers. The polymers can be used to make elastomeric films and coatings that can be used in laminate structures useful in products such as architectural and automotive glazing, eyewear, displays and signs.

Organic conductive polymers and organic electroactive polymers have been used to make electrochromic devices.

International Publication No. WO / 2006/008776 discloses electrochromic compositions prepared by mixing polymers with electrochromic molecules and plasticizers.

There is a need for an electrochromic elastomeric polymer that can be readily prepared, exhibits certain electrochromic properties, can be covalently bonded to an electrode, has a long lifetime, and can be used in fully solid phase electrochromic systems.

Summary of the Invention

The present invention provides a composition comprising an amorphous (co) polymer comprising at least one repeating unit represented by formula (I):

Wherein p and q are independently selected from integers ranging from 0 to 10,000, provided that at least one of p and q is greater than zero;

R is selected from the crowd consisting of H and R ³ ;

R ¹ is selected from the group consisting of H and substituted and unsubstituted alkyl;

R ² is selected from the crowd consisting of H, OH, R ³ , OR ³ , COOR ³ and COOR ⁴ ;

R ³ comprises an electrochromic group;

At least one of R and R ² in at least one repeating unit per polymer chain is OR ³ , R ³ or COOR ³ ;

R ⁴ is selected from the group consisting of H, Na and K;

A is selected from a crowd consisting of O (oxygen atom) and NR ';

R 'is selected from the group consisting of H and substituted and unsubstituted alkyl.

In addition, the present invention

a. A first electrically conductive substrate; And

b. Provided is an article comprising an electrochromic layer in contact with the substrate and containing an amorphous (co) polymer containing at least one repeating unit represented by formula (I):

[Formula I]

Wherein p and q are independently selected from integers ranging from 0 to 10,000, provided that at least one of p and q is greater than zero;

R is selected from the crowd consisting of H and R ³ ;

R ¹ is selected from the group consisting of H and substituted and unsubstituted alkyl;

R ² is selected from the crowd consisting of H, OH, R ³ , OR ³ , COOR ³ and COOR ⁴ ;

R ³ comprises an electrochromic group;

At least one of R and R ² in at least one repeating unit per polymer chain is OR ³ , R ³ or COOR ³ ;

R ⁴ is selected from the group consisting of H, Na and K;

A is selected from a crowd consisting of O (oxygen atom) and NR ';

R 'is selected from the group consisting of H and substituted and unsubstituted alkyl.

1 is a schematic diagram of a fully solid state electrochromic device using an amorphous polymer modified with an electrochromic group.

details

Electrochromism can be defined as a reversible and visible change in the light transmittance and / or reflectivity of a material that occurs as a result of electrochemical oxidation or reduction. The electrochromic material may be an organic or inorganic material exhibiting electrochromic phenomenon.

Amorphous polymers are polymers that exhibit little crystalline domain in the solid state.

According to one embodiment of the present invention, there is provided an amorphous (co) polymer comprising at least one repeating unit represented by formula (I):

[Formula I]

Wherein p and q are independently selected from integers ranging from 0 to 10,000, provided that at least one of p and q is greater than zero;

R is selected from the crowd consisting of H and R ³ ;

R ¹ is selected from the group consisting of H and substituted and unsubstituted alkyl;

R ² is selected from the crowd consisting of H, OH, R ³ , OR ³ , COOR ³ and COOR ⁴ ;

R ³ comprises an electrochromic group;

At least one of R and R ² in at least one repeating unit per polymer chain is OR ³ , R ³ or COOR ³ ;

R ⁴ is selected from the group consisting of H, Na and K;

A is selected from a crowd consisting of O (oxygen atom) and NR ';

R 'is selected from the group consisting of H and substituted and unsubstituted alkyl.

As used herein, "(co) polymer" refers to a homopolymer or copolymer. Specifically, the (co) polymer may contain a repeating unit represented by the following formula (I), (II) or (III), or any combination of formula (I), (II) or (III). . Other repeat units may also exist:

[Formula I]

Suitable alkyl groups include C ₁ -C ₁₀ alkyl groups. Suitable substituents on the alkyl group include halo, hydroxy, carboxy, amino and cyano groups.

An "electrochromic group" is a group that causes the (co) polymer to exhibit a reversible and visible change in light transmittance and / or reflectivity upon electrochemical oxidation or reduction. It is not necessary for every repeat unit to contain electrochromic groups, the polymer chains only need to contain at least one side chain electrochromic group.

Each electrochromic group comprises a redox active group and any linker group interposed between the redox active group and the polymer backbone. Suitable linking groups include-(CH ₂ ) _n -,-(CH ₂ O) _m -,-(CH ₂ CH ₂ O) _m- , -CH ₂ -OC (O) (CH ₂ ) _r- , and-( CH ₂ CH ₂ NH)-(wherein n, m and r are each an integer of 1 to 1000). Branched chain structures represented by the following formula (1), such as structures in which n is an integer of 0 to 1000, are also included in such linking groups:

In addition, a linking group is formed between the (co) polymer backbone and the linking group, such as an ester (-CO _2- ), amide (-N (CO)-), ether (-O-) or thioether (-S-) group. Or a connecting group interposed between the linking group and the redox activating group.

In addition to the redox activating group and the linking group, the electrochromic group may include a functional group for improving the binding to the electrode. In addition, the electrochromic group is independently substituted with functional groups such as -SH, pyridine, -CN and -SCN, so as to adsorb the polymer on the electrode surface (e.g. Au, Cu, Pd, Pt, Ni and Al) and / Or self-assembly. Other functional groups, such as -COOH and -P (O) (OH) ₂ , may also be used to enhance bonding or self-assembly of the polymer onto ITO (indium tin oxide) or Al ₂ O ₃ surfaces. Alcohol and amine functionalities are useful for binding to the Pt surface. Direct contact and good bonding in a solid state system between the (co) polymer and the electrode can increase the coloration efficiency, thus providing a stronger color for a given load voltage.

(Co) polymers containing electrochromic groups may also contain functional groups such as -SO ₃ K or -ClO ₃ Li to provide self-doped (co) polymers. When such (co) polymers are used to assemble an electrochromic device, little or no additional electrolyte is required as dopant.

In the (co) polymers of the invention, the electrochromic group is present in the side chain from the polymer backbone. Each (co) polymer may contain more than one electrochromic group. (Co) polymers containing more than one electrochromic group may contain more than one type of electrochromic group, such as electron donors and electron acceptors. The density of the electrochromic groups (ie the number of electrochromic groups per unit chain length) is determined by the choice of groups R and R ² for each repeating unit. That is, the greater the number of repeat units in which R and / or R ² comprises electrochromic groups, the greater the density of the electrochromic groups in the (co) polymer. The distance between adjacent electrochromic groups can be controlled by the density of the electrochromic groups, by using connectors of different sizes, and by the syn / anti relationship of the connectors present along the polymer chain. .

Suitable redox active groups include bipyridylium-based; Electroactive conductive polymers such as polyaniline, polypyrrole, polythiophene and polythiophene copolymers, and polycarbazoles; Carbazole; Methoxy biphenyl compound; Quinones; Diphenylamine; Phenylenediamine; Pyrazoline; Tetracyanoquinomimethane (TCNQ); And tetrathiafulbarene (TTF).

Suitable redox active groups include substituted and unsubstituted aromatic and heteroaromatic groups represented by the following formulas IV to IX:

The compound represented by the formula (VI) has two bondable points. Generally, one nitrogen atom of the bipyridyl system is bonded to the polymer backbone, linking group or linking group. The other nitrogen atoms are generally alkyl, aryl, halogen, p-toluenesulfonyl, hexafluorophosphate, trifluoromethanesulfonate (CF ₃ SO _3- ), trifluoromethanesulfonimide ((CF ₃ SO ₂ ) ₂ N-), or H, either covalently or ionically, directly or in the state via a linking group and / or a linking group.

Suitable substituents on the aromatic ring of the redox active group include: C ₁ -C ₁₀ alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and isopentyl; Aromatic groups such as phenyl and substituted phenyl; -CN; And amines such as the -N (C ₂ H ₅ ) ₂ and -N (CH ₃ ) ₂ groups. Substituents bonded to aromatic or heteroaromatic groups can affect the reaction of the (co) polymer to the conductivity and voltage variations of the (co) polymer. Various substituents can be used to provide (co) polymers of various colors. By changing the redox active groups and / or substituents of the aromatic gas phase of the electrochromic group, the (co) polymer compositions of the present invention can be prepared in a wide variety of colors.

In one embodiment of the invention, the (co) polymer mainly comprises repeating units of the structure represented by formula (III), such as when the polymer backbone is poly (ethylene oxide) or poly (epichlorohydrin) do. In this type of (co) polymer, the electrochromic group can be bonded directly to the polymer backbone or can be spaced apart from the polymer backbone via a linking group and any linking group. The electrochromic groups do not need to be bound to all repeating units, nor do all the electrochromic groups need to be identical.

In another embodiment of the present invention, the (co) polymer mainly comprises repeating units of the structure represented by the formula (II). In such (co) polymers, the electrochromic group is generally bonded to the polymer backbone via a linking group or through a linking group and any linking group. In one embodiment of the invention having the structure represented by formula X, R ³ is an electrochromic group having two linking groups (— (CH ₂ ) — and — (CH ₂ CH ₂ O) _m −) and a bonding group (— Bound to the polyvinyl butyral skeleton via CO ₂₋ ). Polyvinyl butyral copolymers are commercially available (Sigma-Aldrich Co.) Such copolymers are characterized by elastomeric properties attributable to the linking group and electrochromic properties imparted by R ³ as side chain electrochromic properties. Plasticizers may be added to elevate the elastomeric properties.

In another embodiment of the invention, the polymer backbone is a copolymer comprising poly (ethylene oxide-co-epichlorohydrin) and repeating units derived from salt forms of ethylene, methacrylic acid and methacrylic acid (eg : It is a copolymer containing the repeating unit of the structure represented by the said Formula (II), and the repeating unit of the structure represented by the said Formula (III), as in the case of a Surlyn ^® copolymer ionomer resin).

In one embodiment of the present invention for a copolymer comprising a repeating unit of the structure represented by the formula (II) and a repeating unit of the structure represented by the formula (III), the polymer backbone is represented by the following formula (XI) As indicated, it is derived from ethylene oxide and epichlorohydrin repeat units:

In Example 5 described below, the electrochromic group R ³ is an N-carbazolyl group and is bonded to the polymer backbone via a linking group (—CH ₂ —OC (O) (CH ₂ ) ₂ —). In other embodiments, R ³ is a redox active group as defined above.

The (co) polymers can be prepared by any of several different methods known to those skilled in the art. For example, electrochromic substitution of a (co) polymer containing a backbone derived from repeating units of the structure represented by the formula (I) and reactive side chain groups (e.g., OH, amine or haloalkyl groups) with appropriate functional groups And react with the groups, linkers and / or linkers. This method is particularly easy when (co) polymers containing the desired backbone structure and reactive side chain groups are commercially available.

In some embodiments, the redox activator itself may be directly bonded to the (co) polymer backbone. In other embodiments, it may be necessary or desirable for the linking group to be bonded to a redox active group to provide the desired molecular structure or to provide a more reactive group that facilitates the binding of the electrochromic group to the (co) polymer. have. For example, the examples described below describe methods of coupling several different types of linking groups to carbazole nitrogen atoms to promote the binding of redox activating groups to the (co) polymer backbone. Condensation reactions that form ester, amide or ether linkages are useful reactions for linking linking groups, linking groups and / or redox active groups to one another and / or to the polymer backbone. Such reactions can be carried out under relatively mild conditions. The reaction of alkyl halides with amines or N-aryl compounds may also be used to form tetravalent bonds between redox active groups or linking groups and (co) polymers.

As another example, monomers corresponding to repeating units may be substituted with suitable side chain electrochromic functional groups and the monomers formed may be incorporated into the (co) polymers using standard polymerization techniques such as addition polymerization or condensation polymerization. The same type of reaction used to bind the electrochromic group to the (co) polymer can be used to bind the electrochromic group to the monomer (s) used to form the (co) polymer. Suitable reactions include, but are not limited to, condensation reactions and alkylation reactions.

In another embodiment of the invention, the (co) polymer comprising repeating units of the structure represented by formula (I) is an oligomer, the oligomer being grafted to a second polymer (e.g. polyvinyl butyral) For example, a film forming polymer is provided. This method can provide an easy way to obtain a polymer that combines both the physical properties of the second polymer and the electrochromic properties of the oligomer. The method of incorporating electrochromic groups into the oligomer is similar to the method described above for functionalization after or before polymerization. Oligomers are generally low molecular weight polymers containing from 2 to 100 repeat units.

Another chemical modification of the (co) polymer is also possible. For example, poly (ethyleneoxide-epichlorohydrin) copolymers having side-chain N-carbazole groups can be electropolymerized in solution or in the solid state to form crosslinks through carbazole groups.

In some applications, the (co) polymer may be added with additives such as salts such as lithium perchlorate, plasticizers, electron mediators such as ferrocene, other metallocenes, derivatives and mixtures thereof, or phenazines and derivatives thereof. Mixtures). Adding salts to the self-doped (co) polymer can significantly improve the ionic conductivity of the mixture, thereby improving the electrochromic properties of the mixture.

The (co) polymers can be used to prepare electrochromic elastomeric films by standard film forming techniques, which can also be useful in laminate structures ("laminates") useful for building or vehicle use. For example, an electrochromic elastomeric film can be laminated between glass layers coated with a transparent electrode (eg ITO). When a low voltage, typically about 0.5 V to about 6.0 V, is loaded onto the electrode, the transparency and / or color of the glass-film laminate structure may change. The type of change (eg color or opacity) and the degree of change (eg optical density and / or color of transmitted light) will depend not only on the thickness of the film but also on the properties of the electrochromic group. Removing the voltage source or reversing the polarity will generally return the color and / or opacity to its original state. Due to the possibility of reversibly changing the optical properties of the polymer by loading such low voltages, the film is very useful for products such as sunglasses, helmets, visors, goggles, architectural glazing, automotive glazing, displays, signs and mirrors. Done.

1 is a schematic diagram of a typical electrochromic device 100 comprising a composition of the present invention. In the illustrated embodiment, the substrate layer 110 is coated with a conductive layer 120. Layer 130 is in contact with both conductive layers and includes the amorphous polymer of the present invention and optional additives. Discoloration occurs when a power source is attached to the conductive layer and a voltage is loaded.

Suitable film forming techniques include casting, extrusion, spraying and dip coating. In some applications a freestanding film is preferred. Self-assembly of self-doped (co) polymers into monolayers or multilayers can be accomplished by standard methods, including microcontact printing and / or floating of metal or ITO surfaces.

Lamination methods are also well known in the art and can be used to produce laminate structures with an electrochromic elastomer film interposed between two substrates. Suitable substrates include glass and polymer sheets or films. Polymeric substrates are particularly useful for making flexible laminate structures, and suitable substrate polymers include polyesters such as poly (ethylene terephthalate), poly (ethylene naphthalate), poly (butylene naphthalate) and poly (ethylene- Isosorbide terephthalate) (polymer containing repeat units derived from ethylene glycol, isosorbide and terephthalate moieties and having a higher glass transition temperature than poly (ethylene terephthalate)); polyimide (e.g. Kapton ^® Polyimide); polyamide (e.g., Nomex ^® polyamide, Kevlar ^® polyimide); polycarbonate; polyphenylene oxide; polysulfone; polyester-amide; polyester-imide Polyester ethers, polyether sulfones, polyetherether ketones (PEKs), polyetherimides, cellulose polymers, and polymer blends Compound, such as polystyrene / polyphenylene oxide.

The process of making the article from the laminated structure or coated substrate can be performed using standard techniques for cutting and / or forming glass or polymeric substrates.

In most applications, in order to increase the mobility of the ions, the Tg of the amorphous polymer is preferably lower than the ambient temperature at which devices made from the polymer are used. In some embodiments of the invention, the Tg is less than 100 ° C .; In particular circumstances it is preferred that the Tg of the amorphous polymer is below 50 ° C, or below 25 ° C but below 0 ° C. Certain Tg can be obtained by using plasticizers and / or other additives.

Suitable plasticizers include tetraethylene glycol diheptanoate; Triethylene glycol-di-2-ethyl hexanoate; 2-ethyl-1-hexanol; Polyethylene glycols and derivatives thereof; Adipates such as dihexyl adipate and dioctyl adipate; Phosphates such as 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, triaryl phosphate ester mixtures, tricresyl phosphate, and triphenyl phosphate; Phthalates such as alkyl benzyl phthalate, butyl benzyl phthalate, dibutyl phthalate and dioctyl phthalate; Sebacates such as dibutyl sebacate; And sulfonamides such as toluene sulfonamide and n-ethylsulfonamide.

Hereinafter, embodiments of the present invention will be described based on examples. The examples described below are merely exemplary as representing some embodiments of the present invention. Those skilled in the art will be able to understand the essential features of the present invention through the detailed description and examples, and various modifications and variations of the present invention to fit various uses and conditions without departing from the spirit and scope of the present invention. Modifications may be made.

Unless otherwise noted, all reaction reagents were purchased from Sigma-Aldrich Company, St. Louis, Missouri and used as is.

The meaning of the abbreviations used is as follows: "min" stands for minutes, "hr" stands for hours, "mL" stands for milliliters, "L" stands for liters, and "μL" stands for microliters, "mM "Mmol", "M" represents molarity, "mmol" represents millimoles, "g" represents grams, "mg" represents milligrams, "V" represents volts, and "℃" represents degrees Celsius Indicates the temperature.

Example 1

Preparation of 2- (N-carbazolyl) propionitrile

2- (N-carbazolyl) propionitrile was synthesized through cyanoethylation of carbazole and acrylonitrile in the presence of benzyltrimethylammonium hydroxide (Triton B) used as catalyst ( See the procedure in FC Whitmore, et al., J. Amer. Chem. Soc., 66: 725 (1944).

Carbazole and acrylonitrile (20 g) were placed in a 100 mL round bottom flask equipped with a stirrer. The flask was placed in an ice bath and cooled for 15 minutes. Triton B (40% by weight in MeOH) was then added dropwise (4 drops) to a total volume of 40 μL through a 40 μL syringe. The paste caused a discoloration from white paste to yellow. The reaction mixture was allowed to slowly warm but no sign of exothermic reaction. After 2 hours, heat was supplied through the heating mantle. Once the temperature reached 65 ° C., the paste turned into a solution to give an orange solution. The flask was heated at 70 ° C. for 1 hour. The product precipitated in the flask after cooling. The precipitate was then filtered off and recrystallized from acetonitrile.

Example 2

Preparation of the potassium salt of 2- (N-carbazolyl) propionitrile

KOH (1.7 g) was dissolved in water (10 g) and then added to a mixture of EtOH (15.8 g) and N-propionitrile carbazole (0.293 g) in a 100 mL round bottom glass flask under stirring. After addition of KOH, the condenser was attached and the reaction mixture was heated to reflux for 3 hours. The flask was then attached to a rotary evaporator and the EtOH and water removed until a precipitate formed. The precipitate was filtered off and recrystallized from EtOH. The recrystallized material was dried under nitrogen at room temperature overnight.

Example 3

Synthesis of 2- (2-carbazol-9-yl-ethoxy) -ethanol

The title compound was prepared in two steps. In the first step 2 [2- (chloroethoxy) ethoxyl] tetrahydropyran was prepared as follows:

In a dry box, 2- (2-chloroethoxy) ethanol (50.0 g, 0.401 mol) and 135 mL of chloroform were added to a 500 mL three neck flask equipped with a stir bar, addition funnel and septum. 3,4-Dihydro-2H-pyran (39.7 g, 0.472 mol) in 35 mL of chloroform was added dropwise over 30 minutes using an addition funnel. At the end of the addition period the flask was warmed. The addition funnel was removed from the flask, replaced with a stopper, and the flask was transferred to a hood and placed under nitrogen atmosphere. 12 drops of concentrated HCl were added dropwise via syringe. The bulkhead was then replaced with a water condenser. The reaction mixture was heated at 40 ° C. for 1 hour and then cooled to room temperature. The flask was opened in air, 9 g of K ₂ CO ₃ was added to the reaction mixture, and the mixture was stirred for 2 minutes before filtering. The solvent was removed via a rotary evaporator and the product was dried under vacuum at room temperature for 8 hours to give 84 g (0.406 mol) of 2 [2- (2-chloroethoxy) ethoxyl] tetrahydropyran.

In the second step, 2- (2-carbazol-9-yl-ethoxy) -ethanol was prepared as follows:

Carbazole (20 g, 0.12 mol), 2 [2- (chloroethoxy) ethoxyl] tetrahydropyran (38 g, 0.12 mol), benzyltriethylammonium chloride (TEBA) (4.2 g, 0.025 mol), NaI (1.0 g, 0.0055 mol), 100 mL of 50% NaOH solution, and 100 mL of benzene were added to the flask equipped with a stir bar, condenser and nitrogen inlet. This mixture was refluxed under nitrogen for 6 hours. The reaction mixture was diluted with 100 mL of benzene and the organic phase was separated, washed with water and dried over MgSO ₄ and filtered through acidic Al ₂ O ₃ . The solvent was removed via a rotary evaporator. The product was dissolved in 400 mL of MeOH. Concentrated HBr (2 mL) was added to the flask and the reaction mixture was stirred overnight at room temperature. The reaction mixture was neutralized with 10% aqueous NaOH. MeOH was removed via a rotary evaporator to give a dark orange oil. The final product was purified by recrystallization twice from methanol.

Example 4

Preparation of 2- (2-carbazol-9-yl-ethoxy) -ethanol carboxylic acid

2- (2-carbazol-9-yl-ethoxy) -ethanol was converted into its carboxylic acid derivative in two steps as shown in the following scheme:

 In the first step, 2- (2-carbazol-9-yl-ethoxy) -ethanol (0.584 g, 0.00227 moles) and 12.5 mL of THF were placed in a 100 mL round bottom flask equipped with a stirring device in a dry box. Separately, sodium hydride (0.0546 g, 0.00227 moles) was mixed with 12.5 mL of THF. The resulting slurry was added slowly to the flask. After the addition was completed, the reaction mixture was stirred at room temperature overnight (16 hours) under nitrogen. Next, 0.3256 g of methylchloroacetate in 25 mL of THF was added dropwise to the mixture at room temperature under nitrogen. The mixture was stirred for 4 hours at room temperature. The flask was then removed from the dry box, 30 mL of distilled water was added to the flask, followed by 75 mL of brine solution. The solution formed was transferred to a separatory funnel. THF was then separated. The extraction was performed two more times using 100 mL of THF. THF extract was purified by column chromatography to obtain a purified carboxylic acid derivative.

Example 5

Preparation of Poly (Epichlorohydrin-co-ethylene Oxide) Containing Side Chain Carbazole Groups

The scheme for preparing the title compound is as follows:

Poly (Epichlorohydrin-co-ethylene oxide) (PECH) contained about 66% epichlorohydrin and Tg was -30 ° C. The solution was prepared from 0.46 g (0.005 mol) of PECH in 30 mL of dry THF. The solution was completely dissolved by stirring overnight at room temperature. This solution was prepared with the carboxylic acid potassium salt (0.293 g, 0.001 mol) of 2- (N-carbazolyl) propionitrile prepared as described in Example 1 (CH ₂ Cl / KOOC ratio = 1: 1 ), In the presence of stoichiometric amounts (0.322 g, 0.001 mol) of tetrabutyl ammonium bromide. The reaction mixture was heated at 60 ° C. for 96 h. The formed polymer was precipitated in water, filtered and dried in a vacuum oven. 22 mg of sample was dissolved in approximately 0.7 mL of deuterated THF. This sample was heated to 60 ° C. until dissolved and analyzed by ¹ H NMR. The spectrum was in agreement with the presented structure and showed 57% conversion.

Example 6

This example describes a method by which a (co) polymer having a crosslinked electrochromic system of side chains can be prepared.

Electrolyte elastomer networks containing polyelectrochromic groups derived from carbazole units can be obtained by electropolymerizing side chain chromophore groups as shown in the following scheme:

The electropolymerization reaction can be carried out in solution or in the solid state. In solution, a solution of methylene chloride of 0.01 M carbazole-modified elastomer and 0.1 M tetraethylammonium tetrafluoroborate or LiClO ₄ is placed in a vial and purged with nitrogen gas for 10 minutes to produce a polycarbazole unit. You can. The working electrode is cleaned ITO coated glass or PET. The counter electrode is a platinum lead. A constant voltage potentiostat was set to a potential of + 2.2V. This voltage was loaded for about 2 minutes to conduct the electropolymerization reaction. The device can be manufactured using a substrate / ITO / electropolymerized film as one electrode. The other electrode may be a transparent (eg ITO coated glass) or opaque (eg metal foil) electrode, which is disposed on the electropolymerized material.

As another example, the electropolymerization reaction can be carried out in the solid state. In this case, a film is cast onto ITO coated glass (or PET) from a solution of carbazole-modified elastomer and LiClO ₄ . Another electrode is placed on the film and a voltage (2.2 V) is loaded across the film to cause the electropolymerization reaction of carbazole.

Example 7

Reaction of Carbazole with Sodium Salt of Poly (ethylene-co-methacrylic Acid)

Tetrabutylammonium bromide (2.622 g) and NaOH (50%, 3 mL) were placed in a 50 mL round bottom flask. 1,6-dibromohexane (4.3916 g), benzene (3 mL) and carbazole (1 g) were mixed to form a suspension. The suspension was then injected into the reaction flask under stirring. Then, the flask was capped and stirred at room temperature. The reaction was continued for 1.5 hours at room temperature and overnight (16 hours). The reaction product was extracted three times with methylene chloride (25 mL) and then finally washed with water (pH = 7). ¹ H NMR spectra obtained from the obtained compound showed that further purification was necessary to remove unreacted dibromohexane. To purify this product, the crude product was fed to a silica column. The column was then washed with 500 mL of hexane to remove unreacted dibromohexane compound. The eluent was then changed to a 50/50 hexane / methylene chloride mixture to collect the final product. The oily product was separated and diluted with EtOH. The precipitate formed upon cooling was removed by filtration and dried under vacuum. ¹ H NMR spectrum of the obtained compound was consistent with the predicted compound.

The carbazole derivatives thus prepared were reacted with poly (ethylene-co-methacrylic acid) sodium salt according to the following scheme:

Poly (ethylene-co-methacrylic acid) sodium salt (0.5 g, Delaware, EI Dupont de Nemuaze, Wilcotten, Inc.), DMAc (1.4 g), and 1,2-dichlorobenzene (8.1 g) was added to a 25 mL round bottom glass flask attached to the condenser. This mixture was heated at 110 ° C. for 1 hour until the copolymer completely dissolved. Tetrabutylammonium bromide (0.0281 g) and bromobutane carbazole (0.0263 g, prepared as described above) were added with stirring. The reaction mixture was heated for 4 hours and stirred overnight at room temperature under N ₂ . About 0.5 mL of the reaction mixture was added to 20 mL of a 1: 9 methylene chloride: hexane solution. The precipitated polymer was filtered off, washed with CH ₂ Cl ₂ and hexane and dried under vacuum at room temperature.

In a dry box, a film was prepared on Pt foil by dissolving the dried polymer at 110 ° C. in a mixture of 81% 1,2-dichlorobenzene and 14% DMAc. After evaporating the solvent, the film was tested for redox properties in an electrochemical cell (CVC, CV-50W, available from Bioanalytical Systems). The counter electrode was also set to Pt. The reference electrode was a silver lead. The test solution was acetonitrile containing 0.1 M tetrabutylammonium hexafluorophosphate carrying an electrolyte. The film-formed Pt foil was immersed in the acetonitrile solution as a working electrode. Voltage was applied to the working electrode and the counter electrode, and the EV curve was measured using the standard CV protocol. CVs of the carbazole compound, poly (ethylene-co-methacrylic acid) sodium salt, and poly (ethylene-co-methacrylic acid) sodium salt modified with carbazole were measured. The CV of the poly (ethylene-co-methacrylic acid) sodium salt compound showed no redox activity. In contrast, the poly (ethylene-co-methacrylic acid) sodium salt modified with butyl carbazole showed two redox peaks (1.75 V and 0.4 V), when the bromobutyl carbazole compound alone was used. It was also compatible with the redox activity present.

Example 8

Reaction of Polyvinyl Butyral (PVB) with Carbazole Propionic Acid

Polyvinyl butyral (0.185 g, EI Dupont de Nemuazu) was placed in a 100 mL round bottom flask with a stir bar. THF (10 mL) was added to make the PVB solution after 15 minutes. 9-propionate carbazole (0.239 g), 4- (dimethylamino) -pyridine (0.0092 g) and 1,3-dicyclohexylcarbodiimide (0.206 g) were added in this order. The solution was uniform and colorless. A further 15 mL of THF was added after 20 minutes. The reaction mixture was stirred for 2 days at room temperature under N ₂ scavenging. The reaction mixture was then poured into 150 mL of distilled water. The precipitated compound thus obtained was washed twice with 100 mL of distilled water, separated by filtration, and then dried at 85 ° C. under vacuum overnight.

Example 9

Reaction of polyvinyl butyral (PVB) with 2- (2-carbazol-9-yl-ethoxy) -ethanol carboxylic acid

Polyvinyl butyral (1 g, EI Dupont de Nemuazu) was placed in a 100 mL round bottom flask equipped with a stir bar. DMSO (10 mL) was added and PVB was solubilized under stirring. 1,3-dicyclohexylcarbodiimide (0.206 g) was dissolved in 1.5 mL of DMSO. 4- (dimethyl-amino) -pyridine (0.0092 g) was also dissolved in 1.5 mL of DMSO. Once these solutions were homogenized, they were added to a solution of PVB in DMSO under nitrogen under stirring. Then, carboxylic acid (0.00198 mol, 0.62 g) of 2- (2-carbazol-9-yl-ethoxy) -ethanol prepared as described in Example 4 was added to the reaction mixture. The reaction mixture was stirred and left under N ₂ atmosphere for 2 days. The reaction mixture was then poured into 150 mL of distilled water. The water was decanted off and the polymer washed twice more with 100 mL of water. The water was decanted off and the polymer was dried overnight at 85 ° C. in a vacuum oven.

Claims (22)

A composition comprising an amorphous (co) polymer comprising at least one repeating unit represented by formula (I): [Formula I]

Wherein p and q are independently selected from integers ranging from 0 to 10,000, provided that at least one of p and q is greater than zero; R is selected from the crowd consisting of H and R ³ ; R ¹ is selected from the group consisting of H and substituted and unsubstituted alkyl; R ² is selected from the crowd consisting of H, OH, R ³ , OR ³ , COOR ³ and COOR ⁴ ; R ³ comprises an electrochromic group; At least one of R and R ² in at least one repeating unit per polymer chain is OR ³ , R ³ or COOR ³ ; R ⁴ is selected from the group consisting of H, Na and K; A is selected from the crowd consisting of O and NR '; R 'is selected from the group consisting of H and substituted and unsubstituted alkyl. The method of claim 1, wherein at least one R ³ is an ester group, an amide group, an ether group, a thioether group,-(CH ₂ ) _n -,-(CH ₂ O) _m -,-(CH ₂ CH ₂ O) _m A linker selected from the group consisting of-, -CH ₂ -OC (O) (CH ₂ ) _r- , and-(CH ₂ CH ₂ NH)-(where n, m and r are each an integer from 1 to 1000). A composition further comprising. The composition of claim 1, wherein at least one R ³ further comprises a linking group having a branched chain structure represented by the following formula (1): [Formula 1]

Wherein n is an integer of 0 to 1000, respectively. 2. The composition of claim 1, wherein A is O. The composition of claim 1, wherein R ¹ is H, R ² is OH, and the (co) polymer further comprises a repeating unit represented by the following general formula (XI): Formula XI

The electrochromic group according to claim 1, wherein the electrochromic group is bipyridylium-based, polyaniline, polypyrrole, polythiophene, polythiophene copolymer, polycarbazole, carbazole, methoxybiphenyl compound, quinone, diphenylamine, phenylenediamine , Pyrazoline, tetracyanoquinodimethane and tetrathiafullbarene. The composition of claim 1 wherein the electrochromic group is selected from the group consisting of substituted and unsubstituted aryl and heteroaryl compounds represented by the following formulas (IV) to (IX): [Formula IV]

[Formula V]

[Formula VI]

[Formula VII]

[Formula VIII]

[Formula IX]

8. The composition of claim 7, wherein the substituent is selected from the group consisting of -SH, -CN, -NH ₂ , -COOH and -P (O) (OR) ₂ . The composition of claim 1, wherein the amorphous (co) polymer further comprises a functional group selected from the group consisting of -SO ₃ K and -ClO ₃ Li. The method of claim 1 wherein the amorphous (co) polymer comprises one or more-(CH ₂ CH ₂ )-repeating units and one or more-(CH ₂ C (CH ₃ ) (CO ₂ H))-repeating units Composition. The composition of claim 1 further comprising at least one additive selected from the group consisting of salts, plasticizers, electron mediators and conductive particles. The composition of claim 1 wherein the polymer has a Tg lower than 100 ° C. a. A first electrically conductive substrate; And b. A laminate comprising an electrochromic layer in contact with the substrate and comprising an amorphous (co) polymer containing at least one repeating unit represented by formula (I): [Formula I]

Wherein p and q are independently selected from integers ranging from 0 to 10,000, provided that at least one of p and q is greater than zero; R is selected from the crowd consisting of H and R ³ ; R ¹ is selected from the group consisting of H and substituted and unsubstituted alkyl; R ² is selected from the crowd consisting of H, OH, R ³ , OR ³ , COOR ³ and COOR ⁴ ; R ³ comprises an electrochromic group; At least one of R and R ² in at least one repeating unit per polymer chain is OR ³ , R ³ or COOR ³ ; R ⁴ is selected from the group consisting of H, Na and K; A is selected from the crowd consisting of O and NR '; R 'is selected from the group consisting of H and substituted and unsubstituted alkyl. The laminate of claim 13, wherein the first electrically conductive substrate comprises a glass substrate coated with a conductive material. 15. The laminate of claim 14, wherein the conductive layer comprises at least one material selected from the group consisting of ITO, titanium oxide, copper, aluminum, gold, platinum, silver, cobalt, palladium, iridium and rhodium. The method of claim 13, wherein the first electrically conductive substrate comprises a conductive layer coated on a polymeric substrate, wherein the polymer comprises polyester, polyimide, polyamide, polycarbonate; Polyphenylene oxides; Polysulfones; Polyester-amide, polyester-imide, polyester ether, polyether sulfone, polyether ether ketone (PEK), polyetherimide, cellulose polymer; And polystyrene / polyphenylene oxide. The laminate of claim 16, wherein the conductive layer comprises a material selected from the group consisting of ITO, titanium oxide, copper, aluminum, gold, platinum, silver, cobalt, palladium, iridium, and rhodium. The laminate of claim 13, further comprising a second electrically conductive substrate. 19. The method of claim 18, wherein the second electrically conductive substrate comprises a conductive layer coated on a glass substrate or a polymer substrate, wherein the polymer comprises polyester, polyimide, polyamide, polycarbonate; Polyphenylene oxides; Polysulfones; Polyester-amide, polyester-imide, polyester ether, polyether sulfone, polyether ether ketone (PEK), polyetherimide, cellulose polymer; And polystyrene / polyphenylene oxide. The method of claim 19 wherein the amorphous polymer is a. Polyvinyl butyral; or b. Poly (ethylene oxide-co-epichlorohydrin); or c. A laminate comprising a copolymer comprising repeating units derived from salt forms of ethylene, methacrylic acid and methacrylic acid. An article comprising the laminate as defined in claim 12. 22. The product of claim 21, wherein the product is selected from the crowd consisting of eyewear, automotive glazing, architectural glazing, mirrors, signs and displays.

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