MXPA00000282A - Electrochrome polymer systems - Google Patents

Abstract

The invention relates to electrochrome systems containing soluble electrochrome polymers. Said electrochrome polymers are obtained from electrochrome monomers by means of polymerisation, polycondensation or polyaddition. The inventive electrochrome systems can be used in devices for varying electromagnetic radiation permeability.

Description

SYSTEMS OF ELECTROCROMIC POLYMERS Field of the Invention The present invention relates to electrochromic systems, to monomers and electrochromic polymers, to processes for their preparation, and to the use of electrochromic systems in devices for variable transparency to electromagnetic radiation.

Background of the Invention These are active oxidation-reduction materials that have different colors in their different oxidation states. This phenomenon is referred to as electrochromicity, and the substances that concern have electrochromic properties. This property can be used for the modulation of electromagnetic radiation if at least one oxidation state is colorless and at least one of the other is colored. The devices in which these properties are used are, for example, screens, mirrors obscured by mirrors, Ref: 032447 vehicle safety or variable transparency division screens. These are in principle electrochemical cells These are currently 3 different ways to make devices of this type: a) In the solution type, a soluble dye is generated in the electrolyte by an electrochemical oxidation-reduction reaction. The dye molecules formed in an electrode migrate in the field to the counter electrode, where they are discharged. A medium of this type can always be of low viscosity in order to avoid the transport of disparate material.

If the oxidation-reduction components are selected in such a way that they are in a solution of one form, but are insoluble in the other, a precipitate is electrochemically produced in an electrode and redissolved in reverse of the current direction. c) Finally, an electrode cover can be provided on the outside, and this solid layer can be reversibly colored by the electrochemical reaction.

Method a) is very widespread in today's industry in a particular variant. In this, a system consisting of REDi and 0X2 substances dissolved in a solvent is electrolyzed. If the substance comes together it becomes colorless in the current state of the cell. When a current flows, the substance together becomes the OX1 / RED2 form, which is as intensely colored as possible. The two substances are selected so that both the oxidation and reduction reactions have complementary colors to each other or are colorless. In this way, one species will always be the counter electrode for the other, so that the life of radical free ions is very short. When the current is turned off, the cells quickly become pale again. A joint substance that is suitable for this process with a complementary counter-electrode has been described by Shelepin et al. (Ele trokhimiya 13, 32-37 (1977); 13, 404-408 (1977); 14, 319-322 (1978)), the industrial use thereof for the modulation of electromagnetic radiation in automobile rear-view mirrors being described in patent specifications US-A-, 902, 108 (Gentex) and US-A- 5, 1 0, 55 (Donnelly).

Method b) uses the high association tendency of the free radical ions of viologens, but they do not contain any groups by which they can be anchored to the surfaces. Only their low solubility allows them to be deposited in the electrodes. These covers, however, have a very low stability cycle.

Method c) is the least used in the industry that is widely described. A particular difficulty is that it is tested so that it performs the appropriate cyclic stability. The term "cyclic stability" is taken to mean the frequency at which the ignition of the color / colorless sequence can be carried out without a change in the absorption spectrum or that the time operation takes place. However, in this case, however, considerable improvements are made through a combination of different substances together (O-A-9/23333, Igen Inc.).

Devices that operate on the principle of soluble dyes are widely used as automobile rear-view mirrors (method a). For technical reasons, it is very important that the solutions have the lowest possible viscosity, but safety considerations specify that these may have the highest possible viscosity since, in the event of glass breakage, both the chips and the cell filling can be helped firmly. This requirement is taken into account through the thickness of the solutions by the addition of an appropriate polymer that increases the viscosity of the solutions, as described, for example, in the American Patent Specification No. 4,902,108. The high viscosity is also desirable since the cells, which are generally operated in such a way that the surface of the mirror is parallel to the Earth's gravity field, tend to approach the "color separation" due to convection. This favors, particularly in the case of large dimensions (truck mirrors), the formation of convections, which can result in the separation of cathode and anodic products.

However, a considerable problem occurs in this practice, since viscous solutions can only be introduced into the cells with great difficulty. This is very undesirable for the time spent in the viewpoint and always means a compromise between the reliability and the highest possible viscosity that is desired in the cell.This has been repeatedly proposed accordingly, for example in EP-A - 0 612 826 (Donnelly) and WO-A 96/03475 (Gentex), for filling the cells with monomers and carrying out the polymerization only when the monomers are in the cell.

Description of the invention.

The present invention relates to systems that can be operated as desired by principle a) or c) and which is characterized in that at least one of the substituents REDi and 0X2 are constituted by a soluble, electrochemical polymer.

Polymers containing 0X2 are known as polymeric viologens (P.M.S. Monk, R.J. Mortimer, D.R. Rosseinsky, "Electrochromism", VCH, 1995) Polymers based on acylated 5,10-dihydrofenazines (REDi) have been described in DE-A 4 325 591.

However, these substances have low solubility and can not be used for the proposed application. Surprisingly, the polymers according to the invention are readily soluble in organic solvents and do not precipitate even when the state of the charge changes.

The present invention relates to an electrochromic system comprising at least one REDi electrochemically reversible oxidizable substituent which is converted to OXi by the release of electron at each anode, and at least one reducible electrochemically reversible OX2 substituent which is converted to RED2 by the capture of an electron at a cathode, where an increase in absorbance in the visible region of the spectrum of a colorless or weak color in a colored form with at least one electron released or one electron taken, in each case the colorless or weak color is reformed after the Equalization load, characterized in that at least one of the REDi or 0X2 substituents is covalently linked to a soluble polymer.

The present invention preferably relates to an electrochromic system comprising at least one REDi electrochemically reversible oxidizable substituent which is converted from a colorless or weak color form into an OXi colored form by the release of the electron at an anode, with an increase in absorbance in the visible region of the spectrum, and at least one electrochemically reversible reducible substituent 0X2 which is converted from a colorless or weak color form into a RED2 colored form by electron capture at a cathode, with an increase in absorbance in the visible region of the spectrum, wherein in each case the colorless or weak color is reformed after the equalization charge, characterized in that at least one of the REDi or OX2 substituents is covalently linked to a soluble polymer.

The soluble polymer preferably is formed by the formula I E - [- (BrZ-) a- (B2-Y-) b -] - B-E (I) in which the units -B1.-Z- and -B2-Y- are linked to each other alternately, randomly or in blocks, Y and Z, independently of one another, are a REDX or 0X2 substituent, where OX; is an electrochemically reversible reducible substituent that is converted to RED2 by the capture of an electron at a cathode, where an increase in absorbance in the visible region of the spectrum from a colorless or weak color in a colored form associated with the electron capture, and where the colorless or weak color is reformed after the equalization charge, REDx is an electrochemically reversible oxidizable substituent that is converted to OXi by the release of the electron at the anode, where an increase in absorbance in the visible region of the spectrum from a colorless or weak color in a colored form associated with the release of the electron, and where the colorless or weak color is reformed after the equalization charge, and B is Bi or B2, * Bi and B2 are identical or different link units, is a terminal group of the polymer chain, a and b are the molar fractions of the monomer units -Bi-Z- and -B2-Y-, which have any of the desired values between 0 and 1, where a = 1-b , is the degree of average polymerization number cn and is from 3 to 200,000, where the ratio between cn and the average polymerization weight degree cw (polymaric index) Q = cw / cn is between 1.1 and 100, preferably between 1.2 'and twenty.

The invention also relates to the soluble polymer of the formula I having the aforementioned definition of the variables.

In a preferred embodiment of the electrochromic system and of the soluble polymers, only one of the susb ti tuyent is REDi or OX2 is covalently linked to a polymer chain according to the general formulas (II) and (III): E- (BÍ-Z-JC-BÍ-E (ID E- (-B2-Y-) or-B2-E (III) and the other components are present in a low monomolecular or oligomeric form, where the variables are as defined above.

Preference is further given to an electrochromic system and a soluble polymer in which both REDi and OX2 substituents are covalently bonded in blocks in a polymer chain and conforming to general formula (IV) where the variables are as defined above, and Ci and c2 are an average degree of polymerization, where (ci + c2) < c.

In a further preferred embodiment of the electrochromic system and the soluble polymer, both REDi and OX2 substituents are covalently linked to a polymer chain consisting of two covalently linked blocks. The soluble polymer has the general formula (V) where the variables are as defined above, and ci + c2 Preference is further given to an electrochromic system and a soluble polymer in which both REDi and OX2 substituents are covalently linked alternately in a polymer chain and conforming to the general formula (VI) E- (-B-Z-B-Y-) -B-E (VI) where the variables are as defined above.

Finally, preference is given to an electrochromic system and a soluble polymer in which both REDX and OX2 substituents are covalently linked to a polymer chain where the blocks of substituents are linked by individual units of other substituents, that is, the shaped electrochromic polymers by general formulas VII and VIII where the variables are as defined above.

In formulas (I) through (VIII), Bi and B2, independently of one another, are 0, -CH2-, (CH2) n- - [Y1 S - (CH2) m-Y2- (CH2) e-Y3] o- (CH2) P-Y4q-, where Y1 to Y4 independently of one another are O, S, NR19, COO, OCO, CONH, OCONH, NHCONH, C (= 0), OC (= O) 0, -CH = CH- (trans- or ci s), -CH2-CH = CH-, -C = C-, - CH2-C = C-, cycloalkanediyl- (C4-C7), arylene- (C6-C? 2) or arylalkylene- (C -C? 4), in particular p- and m- dimethylenephenylene or a heterocyclic radical of the structure n is an integer from 1 to 16 m and p, independently of one another are an integer from 0 to 12, is an integer from 0 to 6 and q and s independently of one another are 0 or 1.

In the formulas I-VIII, OX2 is preferably a radical of the formulas (XII) (XIII) (XIV) (XV) (XVI) (XVII) (XVIII) in which R1 to R independently of one another are hydrogen, alkyl- (C? -8), alkenyl- (C2-C? 2), cycloalkyl (C3-C7), aralkyl (C7-C? 5) 'or aryl (C6-) C? 0) R5 and Re or R7 and R8 are hydrogen or together they are a bond - (CH2) 2 ~ o- (CH2) 3-, R9 and R10, independently of one another are hydrogen or in pairs are a bond (CH2) 2-, - (CH2) 3-o-CH = CH-, R11, R12 R17 and Ris / independently of each other are hydrogen, (C? -C4) alkyl, (C1-C4) alkoxy, halogen, cyano, nitro or (C1-C4) alkoxycarbonyl R13 Y R? , independently of one another are 0, N-CN, C (CN) 2 or aryl-N- (C6-C? o) R 15 and R 16 are a bond -CH = CH-CH = CH- Ei is an atom 0 or S, is a direct bond -CH = CH-, C (CH3) = CH-, -C (CN) = CH-, -CC1 = CC1-, - C (OH) = CH-, -CC1 = CH-, -CHsCH -, -CH = N- N = CH-, -C (CH3) = NN = C (CH3) - or -CC1 = N- N = CC1-, is (CH2; p- or m-CH2-C6H4-CH2- is an integer from 1 to 10 and is a colorless anion that is inert to oxidation-reduction under the reaction conditions.

In the formulas (I) to (VIII), the REDi group is preferably a radical of the formulas (XIX) (XX) (xxi) (XXII) fifteen (XXV) 25 in which R21 and R22 are alkyl (Ci-Cs), alkenyl- (C2-C? 2), cycloalkyl (C3-C7), aralkyl- (C7-C? 5) or aryl- (C6-C? O) c R23 to R2s independently of one another are hydrogen, (C?-C4) alkyl, (C CC) alkoxy, halogen, cyano, nitro, alkoxycarbonyl- (C?-C4) or aryl- (C6-C? 0) Y R 26 is additionally NR37R37, R29 to R35 independently of one another are hydrogen- (C1-C4) alkyl, alkoxy- (Ci- C4), cyano, alkoxycarbonyl- (C? -C) or aryl (Cd-Cio) or R2g and R30 and R34 and R35, independently of one another, together are a bond - (CH2) 3 -, - (CH2) - OR -CH = CH-CH = CH- is an O or S atom or the NB groups, C (CH3) 2, C = 0 or S02, E3 and E4 is a 0 or S atom or the group NR36, independently of one another are alkyl- (C? -CX2), alkenyl- (C2-C8), cycloalkyl- (C3-C7), aralqui lo- (C7- C15) or aryl- (C6-C? o) and R36 it is additionally hydrogen, or R36 and R37 in the meaning of NR3dR37 together with the N atom to which these bond, form a five- or six-membered, saturated ring, which may contain additional heteroatoms R36 is alkyl- (C 1 -C 12), quenil o- (C 2 -C 8), cycloalkyl- (C 3 -C 7), aralkyl- (C 7 -C 5) or aryl (C 6 -C 0 0), and v is an integer from 1 to 20, if B3 is identical to B4, B3 and B4 are identical to Bi or B2, if B3 is not identical to B or B4 is absent, B3 is [Y1s- (CH2) m-Y2- (CH2) e-Y3] o- Y4, where is 0, NR19, COO, OCO, CONH, OCONH, NHCONH, C (= 0), OC (= 0) OR, -CH2-CH = CH- (trans or cis-), - -CH2-C = C- , cycloalkanediyl- (C4-C7), arylene- (C6- C12) or arylalkylene- (C7-Ci4) And < is 0, NR19, COO, OCO, CONH, -CH = CH- (trans or cis), -C = C-, cycloalcanedii 1- (C4-C7) or arylene- (C6-C2), And it is O, NR, 1J9 COO, OCO, CONH or arylene- (C6-C? 2: y is where R 20 is hydrogen, alkyl- (C? -C? 8), alkoxy- (C? -C4), alkoxycarbonyl- (C1-C), aryl- (C6-C? O), halogen or cyano, B, is absent or is hydrogen, alkyl- (Ci-Cis), alkenyl- (C2-C12), alkoxy- (C? -C4), cycloalkyl- (C3-C7), alkoxycarbonyl- (C1-C4), aralkyl - (C7- C 5), aryl- (C6-C? O), halogen, cyano or nitro, and Bi and B2 are as defined in formulas I through VIII. in the formulas I-VIII is the final group of the polymer chain. These groups are determined by the polymer preparation process and can be, independently of one another, hydrogen, -CR336, = CR236, (C3-C7) cycloalkyl, phenyl, alkoxy- (C? -C? 8) or arolcoxy , benzoyloxy, -OH, halogen, -COOH, alkoxycarbonyl- (C1-C4), -N = C = 0, -N = C (= 0) 0-, alkyl- (C1-C4), 2- or 4- pyridyl or -NR. 36 In the aforementioned definitions of substituents, alkyl radicals, including modified ones, for example alkoxy or aralkyl radicals, are preferably those having from 1 to 12 carbon atoms, in particular from 1 to 8 carbon atoms, unless established another thing. These can be straight or branched chain and can, if desired, carry additional substituents, for example alkoxy- (C? -C4), fluorine, chlorine, hydroxy, alkoxycarbonyl- (C1-C4) or COOH.

The term "cycloalkyl radicals" is preferably taken to mean those having from 3 to 7 carbon atoms, in particular having 5 or 6 carbon atoms.

The alkenyl radicals are preferably those having from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.

Aryl radicals, including those in the aralkyl radicals, are preferably phenyl or naphthyl radicals, in particular phenyl radicals. These can be substituted by from 1 to 3 of the following radicals: alkyl- (C? -C6), alkoxy (Ci-C?), Fluoro, chloro, bromo, cyano, hydroxy, alkoxycarbonyl- (Ci-C?) Or nitro. Two adjacent radicals can also form a ring.

The invention also relates to a process for the preparation of soluble polymers of the formula I in which one or more of REDi and / or OX2 contain monomers of the formulas XXVI-XXVIII X1-B6-OX2-B7-X2 (XXVI) X1-B6-RED1-B7-X2 (XXVII) X1-B6-OX2-B8-RED1-B7-X2 (XXVIII) in which OX2 is the radical of an electrochemically reversible reducible oxidation-reduction system, and RED1 is the radical of an electrochemically reversible oxidizable oxidation-reduction system, B6, B7 and B8 are the link units, X1 and X2 are each a group 'which is capable of polymerization, polycondensation or polyaddition, being subject to the polymerization, polycondensation or polyaddition reaction.

The preparation of the polymers of the formulas (I) to (VIII) is a polymerization, polycondensation, polyaddition or polymer-like reaction of the RED- and / or OX2- containing monomers. It is also possible for at least one electrochromic component (REDi and / or OX2) to be formed directly during the formation of the polymer chain.

The preferred process is the polymerization of the chain, particularly radical free polymerization, of the RED- and / or OX2 containing monomers, which have at least one polymerizable double bond C = C. The polymerization of the monomers proceeds in appropriate solvents, for example aromatic hydrocarbons, such as toluene or xylene, aromatic halogenated hydrocarbons, such as chlorobenzene, ethers, such as tetrahydrofuran and dioxane, ketones, such as acetone and cyclohexanone, alcohols, such as methanol and ethanol, and / or dimethylformamide, N-methyl-2-pyrrolidone or 1,2-propylene carbonate, in the presence of polymerization initiators, in particular polymerization initiators that supply free radicals, for example azobisisobutyronitrile or benzyl peroxide, a high temperatures, generally from 30 to 130 ° C, preferably from 40 to 70 ° C, if possible with the exclusion of water and air. Precipitation isolation can be effected using appropriate agents, for example water, methanol, cyclohexane or dioxane. The products can be purified by reprecipitation.

A preferred process in the same way is the polycondensation to give polyamides, polyimides, polyamines, polyesters, polyethers or polycarbonates of the RED- and / or 0X2- containing monomers having at least two corresponding reactive groups in their structure, such as halogen, - OH, -O ", -COOH, -COO- (C? ~ C4) -alkyl, -OC (= 0) - (C1-C4) -alkyl, -C00", '-NH2- or -NH- (d -C4) -alkyl.

Particular preferences are given to the preparation of polyester from the aforementioned electrochromic monomers having two OH groups. The reaction between these monomers and any desired dicarboxylic acid dichlorides, for example adipoyl dichloride, proceeds in a solution that removes the hydrogen chloride with the corresponding linker, for example triethylamine or pyridine, in the temperature range between 20 ° and 120 ° C, preferably from 30 to 70 ° C. The solvents used are generally aromatic hydrocarbons, such as toluene or xylene, ethers, such as dioxane, halogenated hydrocarbons, such as chloroform and 1,2-dichloroethane, and / or dimethylformamide, N-methyl-2-pyrrolidone, or 1,2 -propylene carbonate. Isolation can be effected by precipitation using appropriate agents, for example water, methanol, cyclohexane or dioxane.

Another particularly preferred process is the preparation of polyester and polyether from electrochromic monomers having two primary halogen groups. The reaction between these monomers and any desired metal salts of dicarboxylic acid, for example sodium adipate, or any of the desired metal salts of the bisphenols, for example dipotassium salt, 4 '-isopropilidenodifenol, proceeds in solvents aprotic such as dimethylformamide, anhydrous dimethyl diphenyl, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide phoric fos, 1,3-dime tiltetrahidro-2 (1H) -pyrimidinone, at elevated temperature, generally from 30 to 130 ° C, preferably from 40 to 80 ° C, and excluding air and water. The isolation can be effected by precipitation using appropriate agents, for example water, methanol or dioxane.

A further preferred process is the polyaddition to give polyurethanes, polyurethanes or polyammonium compounds from RED- and / or 0X2-containing monomers that also have at least two corresponding reactive groups in the structure, such as halogen, -OH , -N = C = 0 or -NH2, or a tertiary nitrogen atom carrying three identical or different alkyl substituents- (C? ~ Ci2), aralkyl- (C-7-C15) or aryl- (C6-C10) or is a member of a ring of 4-7 atoms, which may also contain additional heteroatoms.

A particularly preferred process is the preparation of polyurethane from the electrochromic monomers having two primary or secondary OH groups. The reaction between these monomers and any of aliphatic or aromatic diisocyanates desired, for example hexamethylene diisocyanate or 4'-metilenbis (phenyl isocyanate), are necessary additional solvent or in appropriate solvents, for example aromatic hydrocarbons such as toluene or xylene ethers such as tetrahydrofuran and dioxane, ketones such as acetone and cyclohexanone, and / or dimethylformamide, N-methyl-2-pyrrolidone or carbonate 1, 2 -propylene, without a catalyst or in the presence of a catalyst, e.g. tin (II) octanoate (Desmorapid 10®) or dibutyltin dilaurate (Desmorapid 7 ©), at elevated temperatures, generally from 30 to 150 ° C, preferably from 60 to 130 ° C, with the exclusion of water and air.

Another particularly preferred process is the preparation of polyammonium compounds from electrochromic monomers having two primary halogen groups. The reaction between these monomers and any of the desired aliphatic or aromatic compounds having two tertiary nitrogen atoms which carry three identical or different substituents alkyl- (Ci-Ci2), aralkyl- (C7-C15) -aryl or (CSS-Cio ) or are ring members of 4- to 7-atoms, which may also contain additional heteroatoms, for example N, N, N ', N'-tet ramethylethylenediamine or 4,4'-bipyridyl, proceeds in appropriate solvents, such as, for example, acetone, cyclohexanone, dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, propioni trilo, 3-methoxypropionitrile, hydroxypropionitrile, glutaronitrile, nitromethane, 1, 2-ethanediol or diethylene glycol, at elevated temperatures, generally from 50 to 190 ° C, preferably from 70 to 150 ° C, with the exclusion of water and air.

A further preferred process is the reaction of analogous polymer of polymers carrying functional groups, such as -OH, halogen, -COOH, -COCÍ, -C (= 0) -OC (= 0) -, -N = C = 0 , -NH2, a secondary or tertiary nitrogen atom bearing identical or different alkyl substituents- (C? -C? 2), aralkyl- (C7-C15) or ari lo- (C6-C? O) or are members of rings of 4-7 atoms, which may also contain additional heteroatoms, with RED1- and / or OX2- containing monomers, which carry at least one corresponding reactive group in their structure, such as halogen, -OH, - COOH, -COCÍ, -N = C = 0, -NH2, a secondary or tertiary nitrogen atom bearing identical or different alkyl- (C? -C? 2), aralkyl- (C7-C15) or aryl- ( C6-C? O) or are members of rings of 4-7 atoms, which may also contain additional heteroatoms.

A particularly preferred process is the reaction of analogous polymer of polymers bearing -N = C = 0 groups with monomers carrying an -OH group. This reaction proceeds without additional solvent or in suitable solvents, for example in aromatic hydrocarbons, such as toluene or xylene, ethers, such as tetrahydrofuran or dioxane, ketones, such as acetone or cyclohexanone, and / or dimethylformamide, N-methyl-2. -pyrrolidone or 1,2-polypropylene carbonate, without a catalyst or in the presence of a catalyst, for example tin (II) octanoate (Desmorapid 10®) or dibutyltin dilaurate (Desmorapid 7®), at elevated temperatures, generally from 30 to 150 ° C, preferably from 60 to 130 ° C, with the exclusion of water and air.

Another particularly preferred process is the reaction of analogous polymer of polymers bearing -COCÍ group with monomers carrying -OH groups. This reaction proceeds in a solution with removal of the hydrogen chloride with a corresponding linker, for example triethylamine or pyridine, in the temperature range between 20 ° and 120 ° C, preferably from 30 to 70 ° C. The solvents used are generally aromatic hydrocarbons, such as toluene or xylene, ethers, such as dioxane, halogenated hydrocarbons, such as chloroform and 1,2-dichloroethane, and / or dimethylformamide, N-methyl-2-pyrrolidone, or 1-carbonate. , 2 -propylene. The isolation can be effected by precipitation using appropriate agents, for example water, methanol, cyclohexane or dioxane.

Another particularly preferred process is the reaction of analogous polymer of polymers bearing -NH2, a secondary or tertiary nitrogen atom bearing identical or different substituents, alkyl- (C? -C12), aralkyl- (C7-C15) or aryl-? (Cß-Cio) or are members of a ring of 4-to-7 atoms, which may also contain additional heteroatoms, with monomers bearing halogen atoms. This reaction proceeds in suitable solvents, such as, for example, acetone, cyclohexanone, dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, propionitrile, 3-methoxypropionitrile, hydroxypropionitrile, glutaronitrile, nitromethane, 1,2-ethanediol or diethylene glycol, at elevated temperatures, generally from 50 to 190 ° C, preferably from 70 to 150 ° C, with the exclusion of water and air.

In the preparation of the polymers of formulas (I) to (VIII), it is also possible to use a combination of the aforementioned processes, for example the synthesis of the polyester / ter prepolymer carrying end groups OH, with the Subsequent extension of the chain using diisocyanates.

The term "monomers" is taken to mean substances that can be converted into a soluble polymer by the aforementioned polymerization processes and according to the formulas XXVI -XXVIII: X1-B6-OX2-B7-X2 (XXVI) X1-B6-RED1-B7-X2 (XXVII), X1-B6-OX2-B8-RED1-B7-X2 (XXVIII) in which OX is an electrochemically reversible reducible substituent, and RED is an electrochemically reversible oxidizable substituent, and B < B and B are link units, and X1 and X2 are each a group that is capable of polymerization, polycondensation or polyaddition.

Preference is given to the monomers that are formed by the formulas XXVI-XXVIII in which OX2 is a radical of formulas IX-XVIII, and RED is a radical of the formulas XIX - XXV, where B and B are replaced by the linking units B < B and B \ X1 and X2 are halogen, -OH, -0", -COOH, -C00- (Cx-C4) -alkyl, -0-C (= 0) - (C1-C) -alkyl, -COO-, -NH2 , -NH- (C1-C4) -alkyl, -N = C = 0, or the tertiary nitrogen atom carrying three identical substituents d different alkyl- (C1-C12), aralkyl- (C7-C5) or aryl- (C6-C10) or is a member of a ring of 4-7 atoms, which may also contain additional heteroatoms, or X1 or X2 is a double bond C = C-, a group -0-C (= 0) - CH = CH2 or a group -0-C (= 0) -C (CH3) = CH2-.

Particular preference is given to monomers that are shaped by the formula XXIX in which X1 = X -OH n = 2 11 is halide, tetrafluoroborate, tetraphenylborate, cyanotriphenylborate, perchlorate, dodecylsulfonate, hexadecylsulfonate, toluenesulfonate, butylbenzenesulfonate, dodecylbenzenesulfonate, hexafluorophosphate, 7.8- or 7, 9 -dicarba. nest-undecarborate (1-).

These monomers are prepared by direct quaternization of 4,4'-bipyridine using a? -halo-1-alkanol, preferably using a? -bromo-1-alkanol, in an aprotic solvent, preferably N, N-dimethylformamide, N, N -dimethylacetamide or N-methyl-2-pyrrolidone, at elevated temperatures, generally from 120 to 200 ° C, preferably from 150 to 180 ° C, with the subsequent ion exchange, which is effected by precipitation in alcohol or by extraction of water using an organic solvent, such as toluene or methylene chloride.

Particular preference is also given to monomers which are formed by the formula XXIX in which B < = B = o- m- or P-CH2-C.3H4-CH2- X1 = X2 = halogen, preferably -Cl, is halide, tetrafluoroborate, tetraphenyl borate, cyanotriphenyl borate, perchlorate, hexafluorophosphate, 7,8- or 7,9-dicarba-nido-undecaborat or (1-).

These monomers are prepared by direct quaternization of 4,4'-bipyridine using the excess of a, a'-halo-o-, -m- or -p-xylene, preferably using a, a'-chloro-m- or - p-xylene, in an aprotic solvent, preferably acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide or N-methyl-2-pyrrolidone, particularly preferably acetonitrile, at elevated temperatures, generally from 40 to 150 ° C, preferably from 70 to 100 ° C, with subsequent ion exchange, which is effected by precipitation in alcohol, preferably in methanol, ethanol or propanol.

Particular preference is also given to the monomers which are formed by the formula XXIX in which B '- (CH2) n, where n = 2 - 11, B7 = aryl- (Cß-Cio) / aryl- (C6-C? 0) substituted, alkyl- (C? -C? 8), alkenyl- (Ci-Ci?) Or aralkyl- (C7-C2), X1 = -OH, • X 'is absent and G "is selected from the group consisting of halide, tetrafluoroborate, tertiaryphenylborate, cyanotriphenylborate, perchlorate, dodecylsulfonate, hexadecylsulfonate, toluenesulfonate, butylbenzenesulfonate, dodecylbenzenesulfonate, hexafluorophosphate, 7,8- or 7,9-dicarba-nido-undecarborate ( 1-) .

These monomers are obtained by the direct quaternization of two steps of 4,4'-bipyridine. The first quaternization is carried out using a co-healo-1-alcohol in aromatic hydrocarbons, preferably toluene or o-xylene, generally from 100 to 200 ° C, preferably from 120 to 160 ° C. The second quaternization is carried out using a primary halide, preferably benzyl halide, in an aprotic solvent, preferably N, N-dimethylformamide, N, N-dimethylacetamide or N-methyl-2-pyrrolidone, at elevated temperatures, generally from 120 to 200 ° C, preferably from 150 to 180 ° C. Subsequently, the ion exchange is carried out by precipitation in alcohol or by extraction of the water using an organic solvent, such as toluene or methylene chloride.

Particular preference is also given to the monomers which are formed by the formula XXIX in which B6 = o-, m- or p-C6H4-CH2- or a mixture of the isomers, XJ = -CH = CH 2 / X is absent, and Bs = - (CH2) n-, n = 2 - 18 or B8 = o-, m- or p-CH2-C6H4-CH2-, and is halide, tetrafluoroborate, tetraphenyl borate, cyanotriphenyl borate, perchlorate, hexafluorophosphate, 7,8- or 7,9-dicarba-nido-undecarbora to (1-).

These monomers are prepared in the following manner. The reaction of phenazine with phenyllithium and subsequently with an α, α-dihaloalkane or with an α, α '-haloxylene gives a (α-haloalkyl) - or (a'-haloxyl) -1 O-phenyl-5, 10- dihydrofenazine. The reaction proceeds in anhydrous ethers, such as diethyl ether, THF, 1,2-dimet- and 1,2-diethoxyethane, preferably in THF, at temperatures between -10 ° and 40 ° C, preferably from 0 ° to 30 ° C., under an argon atmosphere. Quaternization of 4,4'-bipyridine using these products in acetonitrile at 70 ° C gives the halide of 1 - [α- (10-phenyl-5,10-dihydro-5-phenazyl) alkyl] -4- (4 ') -pyridyl) pyridinium or the halide of 1- [a '- (10-phenyl-5,10-dihydro-5-phenazyl) -a-xylyl] -4- (4'-pyridyl) pyridinium. Finally, these substances are reacted with a vinylbenzyl halide, preferably with vinylbenzyl chloride or vinylbenzylbromide, in N, N-dimethylformamide, N, N-dimethylacetamide or N-methyl-2-pyrrolidone, particularly preferred in N-me til-2-pyrrolidone, from 50 to 120 ° C preferably from 60 ° C to 80 ° C, under an argon atmosphere.

Particular preference is given to the monomers that are formed by the formula XXX in which B '= B' = - (CH2) n-, n = 2 - 18, B6 = B7 = - (CH2) 2-0- (CH2) 2- or o-, m- or p-CH2-C6H < CH2-, and X1 = X2 = halogen, preferably -Cl or Br.

The preparation is carried out by the reaction of phenazine with sodium in anhydrous ethers, such as 1,2-dimet- and 1,2-diethyloxyethyl and diethylene glycol dimethyl ether, at temperatures between 40 ° and 140 ° C, preferably from 7.0 ° to 130 ° c, under an argon atmosphere, and subsequently with an excess of 2- to 5- folds of the corresponding dihalide at temperatures between 10 ° and 100 ° C, preferably from 20 ° to 70 ° C.

Particular preference is also given to the monomers that are formed by the formula XXX in which B6 = B7 = - (CH2) n-, n = 2 - 18, B6 = B7 = - (CH2) 2-0- (CH2) 2- or o-, m- or p-CH2-C6H4- CH2-, X1 = X2 -0-C (= 0) -alkyl- (C1-C4), -0-C - (= 0) - CH = CH2, or -0-C (= 0) -C (CH3) = CH2 • The preparation is carried out by the reaction of dihalides of the monomers with the sodium or potassium salts of the corresponding acids in an aprotic, anhydrous solvent, such as N, N-dimethylformamide, N, -dimetiacetamide, dimethyl. sulfoxide, N-methyl-2-pyrrolidone or 1,3-di et il-tert-rahydro-2 (1H) -pyrimidinone, at elevated temperatures, generally from 30 to 130 ° C, preferably from 40 to 80 ° C, and with the exclusion of air and water.

Particular preference is also given to the monomers that are formed by the formula XXX in which B '= - (CH2) n = 2 - 18, B7 = -Ph, substituted Ph or CnH2n + i / X1 = -0-C (= 0) -CH = CH2 -0-C (= 0) -C (CH3) = CH2, and X2 is absent These monomers are prepared by the reaction between the aforementioned (α-haloalkyl) -10-phenyl-5,10-dihydrofenazin and the sodium or potassium salts of the corresponding acids in an aprotic, anhydrous solvent, such as N, N -methylformamide, N, N-dimethylacet amide, dimethyl sulfoxide, N-methyl-2-pyrrolidone or 1,3-dimethyl-tetrahydro-2 (1H) -pyrimidinone, at high temperatures, generally from 30 to 130 ° C, preferably from 40 to 80 ° C, and with the exclusion of air and water.

Particular preference is also given to the monomers that are formed by the formula XXX in which B6 = - (CH2) n-, where n = 2 - 11, B7 = -aryl- (C6-C? O), -a ril o- (C6-C? O) substituted, -alkyl- (C1-C18) ) or -aralkyl- (C7-C24), X1 -OH, and x "is absent These monomers are prepared by the reaction of phenazine with the corresponding lithium compound, for example with phenyllithium, and subsequently 1-boron-β-tetrahydropyranyloxyalkanes, at temperatures between -10 ° and 40 ° C, preferably from 0 ° C to 30 ° C. ° C, under an argon atmosphere, to give 5- (β-tetrahydropyranyloxy-n-alkyl) -10-phenyl-5,10-dihydrophenazines. The reaction proceeds in anhydrous ethers, such as diethyl ether, THF, 1,2-dimet- and 1,2-diethyloxy, preferably in THF. The tetrahydropyranyl group is subsequently completely cut off by treatment with hydrochloric acid, benzene or toluene-phonic acid in a solvent, such as methanol, THF, dioxane, and mixtures of the solvent with water, from 10 ° to 100 ° C under an atmosphere of argon.

Particular preference is also given to the monomers that are formed by the formula XXX in which B6 = B7 (CH2) n-, n 3 - 11 and X1 = X2 = -OH These monomers are prepared in the following manner. The reaction of phenazine with sodium in anhydrous ethers, such as 1,2-dimet- or 1,2-diethoxyethane or diethylene glycol dimethyl ether, at temperatures between 40 ° and 140 ° C, preferably from 70 ° to 130 ° C, under an argon atmosphere, and the subsequent reaction with 1-bromo-β-te trahídropiranilosialcanos at temperatures between 10 ° and 100 ° C, preferably from 20 ° to 70 ° C, gives the 5, 10 -bi s (? - 1 etrahydropy ranyloxy-n-alkyl) -5,10-dihydrofenaz inas. The tetrahydropyranyl group is subsequently completely cut off by treatment with hydrochloric acid, benzene or toluene sulphonic acid in a solvent, such as methanol, THF, dioxane, and in mixtures of the solvent with water, from 10 ° to 30 ° C under a argon atmosphere. The homologue in which n = 3 is also prepared if the trimethylene oxide is used directly in place of 5,10-bis (ε-tetra-idropyranoloxy-n-alkyl) -5,10-dihydrophenazine.

The other particularly preferred monomers which are in accordance with formula XXX in which B '= B' -CH2-CH (CnH2n +?) - n = 1-18, and X1 = X2 = -OH they are prepared analogously - by direct reaction of dihydrofenazin disodium with a-oxiranes.

The electrochromic system according to the invention may contain a solvent, preferably a bipolar aprotic solvent.

The appropriate solvents are all solvents that are inert to oxidation-reduction under the selected voltages and that do not eliminate the electrophiles or nucleophiles or by themselves react as electrophiles or nucleophiles strong enough and therefore can react with the free ions of colored radicals. Examples are propylene carbonate, β-butyrolactone, acetonitrile, propionitrile, glutaronitrile, methylglycitrile, 3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methyl-sulfolane, or mixtures thereof. Preference is given to propylene carbonate and mixtures thereof with glutaronitrile and 3-me tilsulfolane.

The polymers according to the invention are preferably soluble in at least one bipolar aprotic solvent, in particular at room temperature.

In a particularly preferred embodiment, the polymers according to the invention are soluble in the solvent present in the electrochromic system.

The electrochromic system according to the invention can contain at least one inert conductive salt.

Suitable inert conductive salts with lithium, sodium and tetraalkylammonium salts, in particular the latter. The alkyl groups may have from 1 to 18 carbon atoms and may be identical or different. Preference is given to the tetrabutylammonium salts. The appropriate anions for these salts, but also as G anions in the formulas (IX) - (XV), are all colorless anions, inert to the oxidation-reduction.

Examples are tetrafluoroborate, tetraphenylborate, cyanotriphenylborate, tetramethoxyborate, phenoxyborate, perchlorate, chloride, nitrate, sulfate, phosphate, methanesulfonate, tanosulphone, tetradecanesulfonate, pentadecane sulphonate, trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, benzenesulfonate, chlorobenzenesulfonate. , toluenesulfonate, butylbenzenesulfonate, tert-butylbenzenesulfonate, dodecylbenzenesulfonate, naphthalenesulfonate, biphenylsulphonate, benzenedisulfonate, naphthalenedisulfonate, biphenyldisulfonate, nitrobenzenesulfonate, dichlorobenzenesulfonate, trifluoromethylbenene sulphonate, hexafluorophosphate, hexafluoroarsethate, hexafluorosilicate, 7,8- or 7,9-dicarba-nido- undecabora to (1-) or (2-), which may optionally be substituted on the boron and / or carbon atoms by one or two methyl, ethyl, butyl or phenyl groups, dodecahydro-dicarbadodecoborate (2 -) or B-methyl- C-phenyldodecahydrodicatedcarbora to- (1 -). In the case of polyvalent anions, G ~ is an equivalent of this anion, for example 1/2 SiF6.

Preferred anions are tetrafluoroborate, pentadecane sulphonate, dodecylbenzenesulphonate, cyanotriphenyl borate and 7, 8 -dicarba-nido-undecaborate (1-).

The conductive salts are preferably used in the range from 1 to 1 molar.

As additional additives, the electrochromic system may contain thickeners to control the viscosity. This may be important in order to avoid segregation, that is, the formation of streaks or spots in the spreading operation of an electrochromic device containing the electrochromic system according to the invention in the on state and to control the range of discoloration after it has been turned off.

Suitable thickeners are all the usual compounds for this purpose, for example polyacrylates, polymethacrylates (Luctite L®), polycarbonate and polyurethane.

The additional additives suitable for the electrochromic system are the UV absorbers to improve the stability to light. Examples are Uvinil® 3000 (2, 4-dihydroxybenzophenone, BASF), SANDUVOR® 3035 (2-hydroxy-n-octyloxybenzophenone, Clariant), Tinuvin® 571 (2 - (2H-benzothiazol-2-yl) -6-dodecyl-4-methylphenol, Ciba ), Cyasorb 24® (2,2'-dihydroxy-4-metoxibenzophenone, American Cyanamid Company), UVINUL® 3035 (2-cyano-3, 3-diphenylacrylate ethyl, BASF), Uvinul® 3039 (2-cyano- 3, 3-phenylacrylate of 2-ethylhexyl, BASF), UVINUL® 3088 (2-cyano-3, 3-diphenylacrylate 2-ethylhexyl, BASF), UVINUL® 3088 (2-ethylhexyl p-methoxy cinnamate, BASF ), and CHIMASSORB®90 (2-hydroxy-2-metoxibenzophenone, Ciba).

UV absorbers are used in the range from 0.01 to 2 mol / l, preferably from 0.04 to 1 mol / l, these can also be used as mixtures, for example UVINUL®3939 and CHIMAS SORB®90.

The electrochromic system according to the invention contains each of the substances of the formula (I), in particular of the formulas (II) - (VIII), in a concentration of at least 10-4 mol / 1, preferably 0.001 mol 1, it is also possible to use mixtures of a plurality of electrochromic substances of the formula (I).

The electrochromic system according to the invention is highly suitable as a constituent of an electrochromic device. Accordingly, the present invention further relates to electrochromic devices containing the electrochromic system according to the invention. The construction of an electrochromic device, which may be in the form of, for example, a window glass, automobile sunroof (sunroof), automobile rear view mirror or screens, is known in principle. The electrochromic device according to the invention consists of two sheets of glass or plastic which are transparent to the light coated one another, one of which is optionally reflected and whose sides coated one another are provided with an electrically conductive cover, for example of indium-tin oxide (ITO), and among which the electrochromic system according to the invention is located. Other suitable conductive materials are tin oxide added with antimony, tin oxide added with fluorine, zinc oxide added with antimony, zinc oxide added with aluminum, and tin oxide, and conductive organic polymers, such as the optionally substituted poly thienyls, polypyrroles, polyanilines, and polyacefinene. If one of the sheets is reflected, this can also be used as the conductive layer.

The electrochromic device according to the invention has, for example, the following construction. A distinction is made between the basic types: Type 1: full-area electro-chromic device, for example window glass, Type 2: reflex devices that obscure electrically, for example automotive mirrors, Type 3: electrochromic display devices, for example a segment or matrix of a screen.

In type 2, use is made of glass or plastic sheets that are covered with a transparent conductive layer over the entire area on one side.

In type 2, the sheets used are as in the case of type 1. In addition, one of the two sheets is reflected. This reflection can be applied to the second covered, non-conductive side of one of the two leaves. However, it can also be applied to one of the two sheets instead of the mentioned conductive covers and can thus be taken simultaneously in the function of the conductive layer and the reflection. For reflection, silver, chromium, aluminum, palladium or rhodium or even palladium in chrome or rhodium in chromium or other known materials may be used. In this way, a reflective electrochromic device is obtained.

In the case of type 3, the construction can be selected as type 1 or 2. In this way, a transmissive or reflective electrochromic screen device is obtained. In any case, however, at least one of the two conductive layers is divided into electrically separated segments provided with individual contacts. However, it is also possible for only one of the two trays that are provided with a conductive cover and divided into segments. The segments can be separated, for example, by mechanical removal of the conductive layer, for example by scratching, chopping, scraping or grinding, or chemically, for example by chemical etching using, for example, a solution of hydrochloric acid FeCl2 and SnCl ? This removal of the conductive layer can be controlled locally by means of masks, for example comprising photoresists. However, it is also possible to produce the electrically separated segments by the objective application, for example by means of masks, for example by sputtering or printing, of the conductive layer. The segments are provided with contacts, for example by means of thin bands of conductive material, by means of which the segment is connected in an electrically conductive manner to a contact at the end of the electrochromic device. These fine contact bands consist of the same material as the conductive layer itself and can be produced, for example, during the division thereof into segments, as described above. However, these may also consist of another material, such as fine metallic conductors, for example of copper or silver, in order, for example, to improve the conductivity. A combination of metallic material and the material of the conductive cover is also possible. These metallic conductors can, for example, be applied, for example bonded adhesively, either in the form of fine yarns, or they can be printed. All these techniques that are described are known in general terms of the production of liquid crystal displays (LCD).

The screens can be viewed in transmitted lights or reflectively by means of reflection.

The two trays are placed one on top of the other with the sides of the conductive covers which are divided into segments coated one to another, separated by, for example, a sealing ring, and are linked together at the end. The sealing ring may consist, for example, of plastic or thin glass or other material that is inert to the electrochromic liquid. However, the separation between the trays can also be established by means of other spacers, for example plastic or glass beads or certain fractions of sand, in which case these spacers are applied together with an adhesive and then they are joined to form the ring sealing. The sealing ring contains one or two holes, which serve to fill them with the electrochromic device. The separation between the two trays is between 0.005 and 2 mm, preferably from 0.01 to 0.5 mm. In the case of long-range screen devices, in paular made of plastic, the constant separation of the trays by means of spacers, for example plastic beads of the same diameter as those distributed over the area of the display device, can be advantageously taken care of. .

This screen device is filled with the electrochromic system by means of the opening in the sealing ring, being necessary to carry out all the work with the exclusion of humidity and oxygen. The filling can take place, for example, by means of fine cannulas or alternatively by the method of vacuum filling, in which the device and the liquid, placed in a flat dish, is introduced into a container that is capable of being evacuated. The container is evacuated. The screen device, which only contains a filling opening, is immersed with this opening in the liquid. With the removal of the vacuum, the liquid is forced into the screen device.

The filling opening is hermetically sealed subsequently and adhesively bonded.

However, an alternative method is to apply the electrochromic system in the form of, for example, a solution or mixture as a cover in the conductive cover pan or film, for example using a cutter knife or spin cover. All or some of the solvents used in this are removed. The second tray or film is then pressed into the electrochromic system by means of its conductive side, and the support is adhesively bonded in an appropriate manner. However, it is also possible for a conductive, for example metal, to be covered with a vapor deposit, sputtered or applied in the electrochromic system by means of, for example, a dispersion. Examples are aluminum or conductive polymers, for example based on polythiophene.

If appropriate, the end will be against the seal using an adhesive or a resin.

All these operations can be carried out under an inert gas, for example N2 or Ar, and with the exclusion of moisture.

The special embodiments of the aforementioned types 1 to 3 can be, for example, the following, which are likewise the subject matter of the invention: Type 1: light protection area / light filter: window glass, for example for buildings, road vehicles, airplanes, trains, boats, glass roof, car sunroofs (sunroof), greenhouse glass and conservatories , light filters of any desired type; From the security / confidentiality area; division guards, for example for division of rooms in, for example, offices, road vehicles, airplanes, trains, eye protection screens, for example in bank windows, glass doors, visors, for example for motorcycles or pilot helmets; From the design area: oven glasses, microwave equipment, other domestic applications, furniture; Type 2: mirrors of all types, for example of road vehicles, trains, in paular planes, spherical and aspherical mirrors and combinations thereof, for example spherical glass mirrors / as ferieos in furniture.

Type 3: display devices of all types, for example segment or matrix screens, for example for watches, computers, electrical equipment, electronic equipment, such as radios, amplifiers, TV set, CD players, screens intended for buses and trains, exit screens in stations and airports, flat screens, all the applications mentioned under type 1 and 2 that contain at least one static or variable ignitable screen device, such as partition screens containing screens such as, for example, "Please do not disturb", "Closed window", for example car mirrors containing screens of any desired type, for example temperature display, vehicle faults (eg oil temperature, open doors), time, compass address.

The single-cell electrochromic device, which is extinguished by itself, according to the invention can, in addition to the electrochromic polymers of the formula (I), in particular of the formulas (II) - (VIII), described above, also contain other electrochemical polymers, as described, for example, in US-A-, 902, 108, Topics in Current Chemistry (Topics in Current Chemistry), Vol. 92, pages 1-44 (1980), and Angew. Chem. 90_, 927 (1978). Other suitable electronic mixture components are, for example, tetrazolium salts or metal ion complexes or salts, for example [Fe (C5H5) 2] 0/1 + • The mixture of such oxidation-reduction systems may be advantageously, for example in order to correct or intensify the hue, for example of the screen, in the on state in the electrochromic device according to the invention.

The polymers according to the invention can be used for the preparation of high color density solutions, which are advantageous for the production of thin screen layers. These solutions additionally allow the construction of electrochromic systems that are leak proof, but nevertheless can be refilled without problems.

The systems of the present invention are not separated during continuous operation under gravity (for example convection), even in the case of large dimensions of the devices. In addition, the electrochromic polymers according to the invention have the advantage of being simple to produce.

The invention of the present application is explained in more detail with reference to the following examples.

E jem lo 1 Synthesis of monomers 1. 1 5, 10 -Bis (5-bromo-n-pentyl) -5,10 dihydrophenazine g (0.11 mol) of phenazine are dissolved in 400 ml of 1,2-diethoxyethane anhydrous at 80 ° C under an argon atmosphere. 7.4 g of sodium is added. The reaction mixture is vigorously stirred at 120 ° C under reflux for 24 hours and cooled to room temperature. A solution of 69 g (0.3 mol) of 60 in 100 ml of 1,2-diethyloxygen is rapidly emptied into the resulting suspension of 5,10-dihydrophene zine of 5,10-disodium. After the reaction mixture is stirred for 30 minutes, the precipitate is removed by filtration. All 1, 2-anhydrous toxin is completely distilled using a rotary evaporator and used for further synthesis. The product is purified by chromatography (silica gel column, cyclohexane / dioxane = 9/1) and recrystallized from 50 ml of n-butanol. the yield of pale yellow crystals is 11.7 g. 15 Elemental analysis: C22H28Br2N2 (480.3) Calculated: C55.02; H5.88; Br33.27; N5.83. Found: C55.10; H5.85; Br32.70; N5.80 20 1. The by-product in this reaction is 1,5-di [5- (5-hromopenthyl) -5,10-dihydro-10-phenazyl] pentane, which is separated from the product principal by chromatography. The yield is 3.5 'g.

Elemental Analysis: C39H46Br2N4 (730.64) Calculated: C64.ll; H6.35; Br21.87; N7.67.

Found: C64.60; H6.40; Br21.20; N7.70 The following is prepared analogously: 1. 2 5, 10 -Bis [2 (2-chloroethoxy) ethyl] -5, 10-20 dihydrofenazine melting point = 105 ° C Elemental analysis: C20H24Cl2N2? 2 (395.33) Calculated: C60.76; H6.12; C117.94; N7.09; Found: C60.70; H6.20; C118.00; N7.10; 1. 3 5, 10 -Bis [p- (cl oromethyl) benzyl] -5, 1O-dihydro f at a z zin point of melting = 180 ° C (with decomposition) Elemental analysis: C28H24C12N2 (59.42) Calculated: C73.20; H5.27; C115.43; N6.10; Found: C72.90; H5.60; C115.40; N5.90; 10 1.4 5 r 10 -Bis [m- (chloromethyl) benzyl] -5, 10-dihydro f at a z zin point melting = 148-149 ° C Elemental analysis: C28H2 C12N2 (459.42) Calculated: C73.20; H5.27; C115.43; Nß.10; Found: C73.70; H5.40; C114.10; N5.20. 1. 5 5, 10 -Bis [5 - (me tacrolyl iloxy) pentyl] -5, 10-20 dihydrophenazine 7.41 g (0.0182 mol) of the monomer 1.1 and 4.52 g (0.0364 mol) of potassium methacrylate in 40 ml of DMPU for 2 hours at 100 ° C under an argon atmosphere, transferred in a separate funnel, mixed with ether, washed times with water and dried using magnesium sulfate. After the solvent is removed by distillation, the product is purified by chromatography (silica gel column; cyclohexane / dioxane = 9/1). The yield of the pale green liquid is 4.2 g.

Elemental analysis: C30H38N2O4 (490.65 25 Calculated: C73.44; H7.81; N5.71; Found: C73.80; H8.00; N5.30 1. 6 5- (4-methacrylobutyl) -10-phenyl-5, 10-dihydrofenaz ina a) 29.9 g of phenazine are suspended in 195 ml of anhydrous THF under an argon atmosphere. 100 ml of phenylephium solution at 20% concentration is added per weight in cyclohexane / diethyl ether (7: 3) during the course of 90 minutes, during which the temperature is maintained at a maximum of 35 ° C. The reaction solution is stirred at room temperature for an additional 30 minutes. 98.2 ml of 1,4-dibromobutane is added in one portion at 15 ° C. After the mixture has been taken care of at room temperature for 6 hours, 600 ml of water is added, and the mixture is acidifies to a pH of 7.0. The organic phase is completely separated, washed with water and evaporated under reduced pressure. Finally, the excess 1,4-dibromobutane is distilled completely at a pressure of 17 mbar. The residue is purified by chromatography (silica gel column, cyclohexane / dioxane = 9/1). The yield of the yellow or green crystals of 5 - (4-20 bromobu t il) -1 0f n i l -5, l 0 -dihydro f 'en a z zine is 23.6 g.

Melting point = 115 ° C Elemental analysis: C22H2? BrN2 (393.33) Calculated: C67.18; H5.38; N7.12; Found: C67.10; H5.70; N6.70; b) 12.0 g (0.0305 mol) of this product and 7.57 g (0.0610 mol) of potassium methacrylate in 40 ml of DMPU are stirred for 2 hours at 100 ° C under an atmosphere of argon and is treated analogously up to 1.5 '. 6.4 g of yellow-green crystals are obtained.

Melting point = 73 ° C 15 Elemental analysis: C26H26 2O2 (398.51 Calculated: C78.36; H6.58; N7.03; Found: C78.70; H6.60; N7.00; 1. 6.1 5- (3-Hydroxypropyl) -10-phenyl-5, 10 -20 dihydrofenaz ina The synthesis is carried out analogously to 1.6a, but with the addition of l-bromo-3-tetrahydropyranyloxypropane instead of 1,4-diborbutane. Purification is carried out by chromatography (column AI2O3; cyclohexane / dioxane = 9/1) with subsequent crystallization from methanol. The yield of pale green crystals of 5- (3-tetrahydro-pyranyloxy-n-propyl) -10-phenyl-5,10-dihydro-phenazine is 42% theory. 36 g of this product and 25.7 g of p-toluenesulfonic acid monohydrate are heated at reflux temperature for 2 hours in 300 ml of methanol. The reaction mixture is neutralized using NaHCO 3, chloroform is added, and the mixture is washed twice with water and dried using magnesium sulfate. After the solvent has been removed by distillation, the product is purified by chromatography (silica gel column, cyclohexane / dioxane = 7/3) and crystallized from methanol. The yield of the pale green crystals is 14.2 g.

Melting point = 135 ° C Elemental analysis: C2? H2ON 0 (316. '41 Calculated: C79.72; H6.37; N8.85; Found: C79.30; H6.60; N8.80; 1. 6.2 5 - (11-hydroxydecyl) -10-phenyl-5,10-dihydro-phenazine Melting point = 70 ° C Elemental analysis: C29H36N2? 2 (428.62 Calculated: C81.27; H8.47; N6.54. Found: C80.00; H8.60; N6.60. 1. 7 5, 1 0 -Bi s (2-h idroxipropi l) -5, 1 0 - dih i dro f a a z in a 4 g (0.22 mol) of phenazine are dissolved in 500 ml of anhydrous 1,2-diethoxyethane at 80 ° C under an argon atmosphere. 14 g of sodium is added. The mixture of The reaction is vigorously stirred under reflux temperature at 120 ° C for 24 hours and cooled to room temperature. A solution of 39 g (0.66 mol) of 1,2-propylene oxide in 50 ml of 1, 2 -dietoxy ethane in the resulting 5,10-dihydrophenazine suspension of 5,10-disodium. After the reaction mixture has been stirred at room temperature for 1 hour and at 50 ° C for 2 hours, The precipitate is removed by filtration.

All anhydrous 1,2-diethoxyethane is completely distilled in a rotary evaporator and used for further synthesis. The solid residue, together with the completely filtered precipitate, are mixed with 500 ml of methanol, and the mixture is stirred for 30 minutes. the solution is then evaporated on a rotary evaporator and transferred into In a separate funnel, chloroform is added, and the mixture is washed a number of times with water and dried using magnesium sulfate. After the solvent has been completely distilled, the product is purified by chromatography (silica gel column, cyclohexane / dioxane = 1/1) and recrystallized from 150 ml of an acetone / water mixture (2/1). The performance of pale green crystals is 22.5 g.

Melting point = 156 ° C Elemental analysis: C? 8H22N2? 2 (298.39) Calculated: C72.46; H7.43; N9.39. 25 Found: C72.50; H7.30; N9.20 The following is prepared analogously: , 10 -Bis (2-hydroxyethyl) -5,10-dihydrophenazine Melting point = 179 ° C Elemental analysis: C? 6H? 8N2? 2 (270.33 Calculated: C71.09; H6.71; NIO.36.10 Found: C71.00; H6.50; NIO.10. 1. 9 5, 10 -Bis (3-hydroxypropyl) -5,10-dihydrofenaz ina * In accordance with mass spectroscopy and elemental analysis data, containing about 30% of 5- (3-hydroxypropyl) -10- [- (3-hydroxypropox i) propyl] -5, 10 -dihydro- 20 fena z ina melting point = 158 ° C 1. 9a 5, 10 -Bis (3-hydroxypropyl) -5,10- 25 dihydro f 'en a z zin Disodium dihydrofenazine, prepared analogously to 1.7 from 20 g of Phenazine and 7 g of sodium were reacted with 53 g of l-bromo-3-tetrahydropyranyloxypropane. The additional treatment was carried out analogously to 1.1. 16.8 g were obtained of colorless crystals of 5,10-bis (3-tetrahydropyranyl oxy-n-propyl) -5,10-dihydrofenazin.

Melting point = 80 ° C 25 Elemental analysis: C28H38N2O4 (466.63) Calculated: C72.07; H8.21; N6.00 Found: C72.20; H8.20; N5.90 g of this product was stirred at room temperature for 24 hours in 36 ml of a mixture of 2N HCl and THF (1:10). The reaction mixture was neutralized using NaHCO 3, chloroform was added, and the mixture was washed twice with water and dried using magnesium sulfate. The additional treatment was carried out analogously to 1.7. The yield of pale green crystals was 0.7 g.

Melting point 154 ° C 1. 9b. 5, 10 -Bis (6-hydroxyhexyl) -5,10-dihydrophenazine Melting point = 95 ° C Elemental analysis: C24H34N2? 2 (382.55 Calculated: C75.35; H8.96; N7.32. Found: C75.30; H8.70; N7.20. and 1.9c. 5, 10 -Bis (11-hydroxydecyl) -5,10- dihydrofenaz ina Melting point = 86 ° C Elemental analysis: C34H5 N2O2 (522.82) Calculated: C78.ll; H10.41; N5.36. Found: C78.10; H10.30; N5.30. are prepared analogously. 1. 10. difluoroborate of l, l'-Di [p- (chloromethyl) benzyl] -4,4 '-bip ir idin i o a) 34.3 g (0.22 mol) of 4,4'-bipyridyl and 106 g (0.66 mol) of a, a'-dichloro-p-xylene are stirred in 500 ml of acetonitrile at 90 ° C for 4 hours under one atmosphere of argon. After cooling, the precipitate is completely filtered and sufficiently washed with acetonitrile. Drying gives 88.1 dichloride of 1,1'-di [p- (chloromethyl) benzyl J -4, 4 '-10 bipyr idinio. b) 50.6 g of this substance is dissolved in 200 ml of methanol. A concentrated solution of 131 g (0.4 mol) is added of tetrabutylammonium tetrafluoroborate in methanol. After one hour, the white precipitate is filtered completely, washed with methanol and dried. The yield of monomer 1.10 is of 40 g.

Elemental Analysis: C26H2, B2C12F8 2 (609.01 Calculated: C51.28, H3.97, N4.60, Found: C50.40, H4.20, N4.70.25, 1.11 dibromide of 1, 1 '-Di [11-] (hydroxyundecyl) 4, 4 r -bipir idínio it was prepared analogously to 1.10a using DMF instead of acetylitric and at 160 ° C in the reaction time of 2 hours.

Elemental analysis: C32H54Br2N202 (658.61) Calculated: C58.36; H8.26; Br24.26; N4.25. Found: C58.20; H8.20; Br24.10; N4.25.

The following monomers were prepared analogously to 1.10b based on the product of 1.11: 1. 12. difluoroborato de l, l, -Di [ll (hydroxy undecyl) - 4, 4 '- ipir idin i o Elemental Analysis: C32H54B2F8N2? 2 (672.4) Calculated: C57.16; H8.09; N4.17. Found: C58.20; H8.50; N4.25 1. 13. 1,1-ditetraphenylborate-Di [11 (hydroxyundecyl) -4,4'-bipyridinium Elemental Analysis: C80H94B2N2? 2 (1137.28) Calculated: C84.49; H8.33; N2.46. Found: C84.50; H8.50; N2.50. 10 1.14 di (Cyanotr ifenilborato) of l, lr-Di [ll (hydroxy undecyl) -4,4 '-bipir idinio Elemental analysis: C7oH84B2N4? 2 (1035.1 Calculated: C81.23; H8.18; N5.41. Found: C80.70; H8.20; N5.20. 1. 15. didodecylsulphonate 1, 1 '-Di [11- (hydroxyundecyl) -4,4'-bipyr idinium 20 g (0.03 mol) of monomer 1.9 and 19.8 g (0.072 mol) of sodium dodecylsulfonate were dissolved in 150 ml of a methanol / water mixture (1: 2) while was stirred under reflux temperature.

This solution was added to a two-phase system comprising 600 ml of methylene chloride and 200 ml of water, and the mixture was stirred vigorously under reflux for 2 hours. After cooling, the organic layer was completely separated and evaporated to dryness under reduced pressure. The residue was washed with acetone, dried at room temperature under reduced pressure and at 150 ° C under high vacuum (10 ~ 3 mbar) 'for 5 hours. The yield was 20.6 g.

Elemental analysis: C56H? 04N2O8S2 (997.6 15 Calculated: C67.42; H10.51; N2.81. Found: C65.80; H10.50; N2.50. 1. 16. dihexadecylsulphonate 1, 1 f -Di [11 - (hydroxyundecyl) -4,4'-b ip ir idinio s e prepare analogously. 1. 17 1 - (Vinylbenzyl) -1'-benzyl-4,4'-bipyr i din i o dichloride a) 15.6 g of 4,4'-bipyridyl and 12.7 g of benzyl chloride in 300 ml of toluene were stirred under reflux for 4 hours.The precipitate was completely filtered from the hot solution, washed with abundant hot toluene and dried under reduced pressure. The yield of 1-benzyl-4- (4'-pyridyl) -pyridinium chloride is 25.2 g.

Elemental analysis: C17H? 5N2Cl (282.78) Calculated: C71.21; H5.35; N9.91; Cl 12.54 Found: C71.90; H5.60; N9.70; Cl 12.60 b) Dissolve 20 g (0.056 mol) of this product in 200 ml of DMF at 150 ° C, add 10.3 g (0.067 mol) of vinylbenzyl chloride, and stir the reaction mixture for 4 hours. After the mixture has cooled to 100 ° C, the precipitate is filtered off completely, washed with DMF and toluene and dried. The pink product is stirred for 15 minutes in water containing activated carbon, removing the activated carbon by filtration, and evaporating to dryness under reduced pressure. The yield of 1 - (vinylbenzyl) -1'-benzyl-4,4'-bipyridiyl dichloride is 15.3 g.

The following monomers were prepared analogously to 1.10b based on this product: 1. 1 1- (Vinylbenzyl) -1'-benzyl-4, 4'-bipir diorfluoroborate Elemental analysis: C26H24B2N2F8 (538.09 Calculated: C58.04; H4.50; N5.21 Found: C57.10; H4.60; N5.30. ditetraphenylborate 1 - (Vinylbenzyl) -1 'benzyl-4, 4' -bipir idinio 1 - (Vinylbenzyl) -1 '- [4 -, (10-phenyl-5,10-dihydro-5-phenacyl) -butyl] -4,4'-bipyridyl difluoroborate a) 20.3 g of 4,4'-bipyridyl and 24.9 g of 5- (4-bromobutyl) -10-phenyl-5, 10-dihydrofuran (1.6.a) in 330 ml of at 70 are stirred. ° C for 24 hours under an argon atmosphere. The mixture is cooled and filtered by suction, and the product is washed with 150 ml of acetone. Drying gives 28.6 g of 1 - [4 - (1-phenyl-5,1-dihydro-5-phenazyl) -bu tyl] -4- (4'-pyridyl) pyridinium bromide Elemental analysis: C3'2H29N4Br (549.51) Calculated: C69.94; H5.32; N 10.20; Br 14.54; Found: C69.60; H5.50; N10.0; Brl4.90. B) 27 g of this product and 38 ml of vinylbenzyl chloride in 310 ml of N-methyl-2-pyrrolidone are stirred at 70 ° C for 15 hours under an argon atmosphere. The The mixture is cooled and diluted with 600 ml of toluene. The precipitated product is filtered completely, washed with toluene and hexane, and dried under reduced pressure, giving 21.2 of a gray product dark. 3.95 g of the same are dissolved in 100 ml of methanol, and a methanol solution of 18.2 g of tet rabbutylaluminum tetrafluoroborate is added. The pale gray product that precipitates is completely filtered, washed with abundant methanol, and dried. The yield is 1.35 g.

Elemental analysis: C4iH38B2F8 4 (760.39 Calculated: C64.76; H5.04; N7.37; Found: C64.40; H5.30; N7.30. 1. 21 Diphenylphenylborate 1- (Vinylbenzyl) - l '- [4- (10-phenyl-5,10-dihydro-5- 15 fe to cyl) -but il] -, - bipir idinio it is prepared similarly 1. 22. 1- (11-Hydroxyundec il) -1 'dibromide benzyl-4, 4 '-bipir idinio a) Add 70 g of 11-bromoundecanol in 50 ml of o-xylene with stirring to a refluxing solution of 56.6 g (30% excess) of, 4'-bipyridyl in 100 ml of o-xylene. xylene, and the mixture of The reaction is stirred for an additional 2 hours. After the mixture has cooled to 100 ° C, the precipitate is filtered completely from the hot solution, washed with hot o-xylene and subsequently with abundant toluene, and dried under reduced pressure. The yield of 1- (11-hydroxy undecyl) -4- (4'-pyr idyl) pyriminium bromide is 83 g. 25 Elemental analysis: C2iH32BrN20 (O 8.4) Calculated: C61.76; H7.90; Brl9.56; N6.86. Found: C61.20; H7.70; Br20.20; N6.70 b) 35 g of this product are dissolved in 100 ml of N-methyl-2-pyrrolidone at 150 ° C. 17.7 g of benzyl bromide are added dropwise to this solution. The reaction mixture is stirred for an additional 0.5 hours. After the mixture has cooled to 100 ° C, the precipitate is completely filtered from the hot solution, washed with abundant hot NMP and subsequently with abundant hot dioxane, and dried under reduced pressure. The yield of the pale yellow product is 50 g.

The following monomers were prepared analogously on the basis of this product 1.10b: 1. 23. 1- (11-Hydroxyundecyl) -1'-benzyl-4,4'-bip ir idinium difluoroborate Elemental analysis: C28H38B2F8N20 (592.23) Calculated: C56.79; H6.47; N4.73. Found: C56.80; H6.40; N4.70. 1. 24. di (cyanotriphenyl borate) of 1- (11 Hydroxyundecyl) -1'-benzyl-4, 4'-bipir idinio Elemental analysis: C66H68B2N40 (954.93 Calculated: C83.02; H7.18; N5.87. Found: C82.60; H7.20; N5.90.

Example 2 Synthesis of the polymers 1) G = CI, Br, G '= Cr, Br "2) G- = BF 2.1, B = - (CH2) 5 ~ G" = BF4"3.25 g (0.0208 mol) of 4,4'- were stirred. bipyridine and 10 g (0.0208 mol) of monomer 1.1 for 4 hours in 30 ml of diethylene glycol at 180 ° C under an argon atmosphere and cooled, 300 ml of dioxane was added, and the mixture was refluxed by After 30 minutes, the precipitate was completely separated from the solution and dissolved in 50 ml of methanol.This solution was added dropwise with good stirring to the solution of 30 g of tetrabutylammonium tetrafluoroborate in 300 ml of methanol.

A green precipitate was completely filtered with suction, washed a number of times with methanol, and dried under reduced pressure. Yield: 8.2 g.

The polymer 2. 2. B = - (CH2) 2-0- (CH2) 2-; G = BF4 was prepared analogously based on monomer 1.2. 2. 3. B = p- (-CH2-C6H4-CH2- = BF .. 3.4 g (0.0218 mol) of 4,4'-bipyridine and 10 g (0.0218 mol) of monomer 1.3 were stirred for 24 hours in 30 ml of DMF at 50 ° C under an argon atmosphere. The surplus of the synthesis is analogous to 2.1. Yield: 12.7 g- The polymer 2. 4. B = m- (-CH2-C6H4-CH2-); G = BF4 ~ is prepared analogously based on monomer 1.4.

In an electrochromic device as described in Example 10, a blue gray coloration with maximum absorption at 453, 482, 565, 606 and 662 nm is obtained from polymer 2.4.

All polymers of Example 3 exhibit a similar green blue coloration under these conditions, with a plurality of maximum absorption, the two strongest of these being in the range of 455-490 nm and 590-620 nm. 2. 5. 1.0 g (0.00217 mol) of monomer 1.3, 1.32 g (0.00217 mol) of monomer 1.10 and 0.801 g (0.00435 mol) of l, 2-bis (4-pyridyl) ethane in 10 ml of DMF at 80 ° were stirred. C for 4 hours under an argon atmosphere: 1) G = CI, G "= CI 2) G- = BF; The reaction mixture was evaporated to dryness under reduced pressure and further treated analogously to 2.1. Yield 0.9 g. .72 g (0.005 mole) of monomer 1.13, 1.5 g (0.005 mole) of monomer 1.7 and 2.52 g (0.01 mole) of 4,4 '-methylenebis (phenylisocyanate) in 15 ml of DMF at 80 ° C for 48 hours were stirred. under an argon atmosphere.

The reaction mixture was evaporated to dryness under reduced pressure. The residue was boiled three times with methanol, filtered thoroughly and dried under reduced pressure. The yield is 7.78 g. 2. 7. was prepared analogously to 2.6 from monomers 1.12 and 1.7. Performance: 66.8% theory.

E p e 3 Synthesis of polymers. 9.4 g (0.06 mol) of 4,4'-bipyridine and 18 g (0.06 mol) of 1,1-dibromodecane in 30 ml of diethylene glycol were stirred at 190 ° C for 4 hours under an argon atmosphere and cooled, 300 ml of dioxane was added, and the mixture was refluxed for 30 minutes. The precipitate was completely separated from the solution and dissolved in 100 ml of methanol. This solution was added dropwise with good stirring to the solution of 60 g of tetrabutylammonium tetrafluoroborate in 600 ml of methanol. The precipitate was completely filtered off with suction, washed a number of times with methanol, and dried under reduced pressure. Yield: 5.0 g.

In an electrochromic device as described in Example 5, a blue-green coloration with maximum absorption at 435, 450, 462, 570, 604 and 660 nm is executed by the polymer 3.1 in a solution with 5, 10-dimetho- 5, 10-dihydrofenazine.

All the other polymers of Example 3 exhibit a similar green blue coloration under these conditions, with a plurality of maximum absorption, the most intense of which are in the 455-490 nm and 590-620 nm regions.

A polymer that have the following structure: is prepared analogously to 2.6 from 3 g (0.00264 mol) of monomer 1.13 and 0.66 g (0.00264 mol) of 4,4'-methylenebis (phenylisocyanate). The yield is 3.3 g.

A polymer is prepared in which G ~ = BF4 ~ analogously to 3.2 from 5.45 g (0.0081 mol) of monomer 1.12 and 2.03 g (0.0081 mol) of 4, '-me tilenbis - (phenylisocyanate). The yield is 2.2 g.

G "= BF¿ 1.0 g of monomer 1.18 and 0.05 of a, a-azoisobutyroniyl trile in 10 ml of DMF are stirred at 70 ° C for 48 hours under an argon atmosphere, and evaporated to dryness under reduced pressure. The residue is boiled three times with methanol, filtered thoroughly, and dried under reduced pressure. The yield is 0.09 g.

Example 4 Synthesis of the polymers 4. 1.2 g (0.00435 mol) of monomer 1.3 and 1.325 g (0.00435 mol) of dipotassium salt of 4,4'-isopropylendi phenol: The mixture is stirred in 6 ml of 1,3-dimeti 1 -3, 5,6-tetrahydro-2 (1H) -pyrimidinone at 110 ° C for 4 hours under an argon atmosphere and cooled, 200 ml are added of water. The precipitate is completely separated from the solution, refluxed a number of times in methanol, and dried at 150 ° C for 2 hours under high vacuum. Yield: 0.65 g.

The polymer of the following structure is prepared analogously to 3.2 from monomer 1.7 and 4, 4 '-me t ilenbis- (phenylisocyanate). Performance: 43% theory.

Example 5 An electrochromic cell is constructed from two glass pans covered with ITO and a sealing ring (0.2 mm thick), as described in US-A 4,902,108 in Examples 1 to 3.

This is filled with a solution of 94 mg of the polymeric electrochromic compound 3.1 and 42 mg of the dihydrophenazine of the formula in 10 ml of anhydrous propylene carbonate by means of an opening in the roof of the seal. The color of the solution in the cell was pale yellow. After application of a voltage of 0.9 V, the solution quickly turned to a blue-green color, and then the applied current was turned off, the contained cell became colorless again within about 30 seconds and resulted in the pale yellow color original. More than 100,000 ignition cycles of this type survived without any change.

The blue-green coloration exhibited maximum absorption at 435, 450, 462, 570, 604 and 660 nm.

When the glass sheets were plated on the opposite side of the side of the ITO cover, a darkened mirror was obtained.

Example 6 An experiment was carried out as described in Example 5 using polymer 3.3 instead of polymer 3.1. After the application of a direct voltage of 0.9 V, the pale yellow contained cell quickly turned a blue-green color. This color disappeared again after the voltage was turned off, with a short circuit of the cell resulting in rapid discoloration.

Example 7 An electometrochromic cell was constructed from two glass trays covered with ITO. This was carried out using an appropriate adhesive as sealing material in which the spacer (finely ground quartz earth having a defined particle diameter distribution d (max.) = 200 μm) was stirred.

The filling of the cell with a solution that was 0.02 molar with respect to the polymeric electrochromic compound 2.7 in anhydrous dimethylformamide (DMF) was carried out under a nitrogen atmosphere in a glove box. The cell is sealed, in the same way in the glove compartment, using an appropriate sealing material. The cell contained pale yellow until discoloration before the application of a voltage. After the application of a direct voltage of 0.9 V, the contained cell rapidly turned a blue-green color. This color disappeared again after the voltage was turned off, with a short circuit of the cell resulting in rapid discoloration. The final state of cell coloration was when the pale yellow returned, as at the beginning.

Example 8 An experiment was carried out as described in Example 7 using polymer 2.6 instead of polymer 2.7. The color changed from the contained cell after the application and off of a direct voltage of 0.9 V analogously to Example 7.

Example 9 An experiment was carried out as described in Example 7 using a solution of 2 polymers 3.3 and 4.2 (each 0.01 molar) instead of 0.02 molar solution of polymer 2.7. The color changed from the contained cell after the application and off of a direct voltage of 0.09 V analogously to Example 7.

Example 10 An electrochromic screen device was built.

A glass tray covered with ITO (resistance 12 O /) was sprayed on the side of the cover with a commercially available photoresistor, for example Positiv® 20 (Kontakt Chemie, Iffezheim), and dried in the dark for 1 hour at from 50 to 70 ° C. The resistant layer was then covered with a film containing, as shown in Figure 1, black segments in a transparent environment. This film was printed with a laser printer in accordance with a master procedure produced on the computer. The photosurface layer was then exposed to UV light (from a mercury lamp, for example a HBO® 200/2 high-pressure xenon lamp (Osram) or an XBO® 75W / 2 (Osram)) by "From 1 to 15 minutes." The film was removed, and the resistant layer was treated in a bath of sodium hydroxide solution (7 g of sodium hydroxide per liter of water) in such a way that the unexposed areas were rinsed. The glass tray prepared in this way was then placed in a bath consisting of 67 g of FeCl 2 x 4 H20, 6 g of SnCl 2 x 2 H 2 O, 104 ml of water and 113 ml of hydrochloric acid at a concentration of 37%. by weight, which caused the ITO layer to separate in the previously unexposed areas, free of resistance.The resistant layer that was left over was removed using acetone.A glass tray (1) carrying segments (4), connections was obtained. conductor (3) and contacts (2). ' A rectangular ring of a polyethylene film with a thickness of 0.05 mm was cut. Long pieces (5) of about 1-2 cm were removed from the long sides. This film was then placed on the covered ITO side of a second tray (7). A two-component adhesive, for example UHU® plus dryer 300 (UHU GmbH, Bühl) was applied outside the film with the exception of the opening (6). The engraved glass tray (1) produced as described above was then placed on the film in such a way that the ITO layer was placed on the side of the film (see Figure 2). The two-component adhesive was then allowed to be, if necessary, through a pleasant heat of about 40 ° C.

The cell is then filled, under a nitrogen atmosphere, with a solution of 572 mg of the polymeric electrochromic substance 2.4 in 10 ml of anhydrous propylene carbonate by means of the opening (6), for example with the aid of a thin pipette. or by emptying the solution under reduced pressure. The filler opening (6) was then filled with a piece of polyethylene film filler and hermetically sealed using a two component adhesive.

By applying a voltage of 0.9 V to the contacts (2) of the segments (negative pole) and the second non-engraved tray (7) (positive pole), a deep gray-blue image of the contact segments was formed within the 2 seconds. In this way, all the letters and numbers that can be placed by means of 7 segments were placed in blue gray a pale yellow background. By turning off the voltage and short circuit of the contacts, the image disappeared again in a few seconds. The segments were imagined with sharp ends. Even after continuous operations for a number of hours in the vertical position of the display device, the segments were uniformly colored and exhibited sharp ends.

More than 100,000 ignition cycles of this type survived without any change. The blue gray coloration exhibited a maximum absorption at 453, 482, 565, 606 and 662 nm.

Example 11 Example 5 was repeated, but 1.44 g of the UV absorber of the formula was added. to the electrochromic solution. The operation of the display device during power on and off remained unchanged.

While the cell of Example 5 turned brown after only 14 days of exposure in the quenched state in the xenon tester, this cell remained colored and completely unchanged in this function under identical conditions.

E 12 Example 10 was repeated, but 1.16 g of the UV absorber of the formula was added. to the electrochromic solution. The operation of the display device during power on and off remained unchanged. While the cell of Example 10 turned brown after only 14 days of exposure in the quenched state in the xenon tester, this cell remained colored and completely unchanged in this function under identical conditions.

Example 13 A glass tray covered with ITO was engraved as described in Example 6. A glass tray (1) was obtained carrying segments (4), conductor connections (3) and contacts (2).

In a glove box, a second ITO covered glass tray (7) was constantly covered on the side of the ITO cover about the area with a solution at 30% concentration by weight of the electrochromic polymer used in Example 6 in dimethylformamide. The tray (1) was placed, in the same way in the glove box, in this cover solution by means of each engraved side so that the two trays were placed one on top of the other as shown in Figure 2. The two trays were pressed then manually tightly against each other and gently rubbed against each other so that any included air bubbles had the ability to escape. During this, some of the viscous solution was pressed out and was carefully cleaned thoroughly with a tissue paper. The thickness of the solution layer between the two trays was then 30 μm. the four ends of the solution layer closed between trays (1) and (7) were then sealed in the glove box using a hot adhesive gun Pattex Supermatic® (Henkel KgaA, Dusseldorf). The cured hot adhesive gasket was subsequently sealed with an epoxy adhesive Kórapox 735® (Kommerling, Pirmasenz) and thus mechanically stabilized. The epoxy adhesive was cured overnight at room temperature.

In this way, a cell was obtained which is similar to that of Example 10, but with a small separation layer.

By applying a voltage of 1.2 V to the contacts (2) of the segments (negative pole) and the second non-recorded tray (7) (positive pole), a deep gray-blue image of the contact segments was formed within the one second. In this way, all the letters and numbers that can be placed by means of 7 segments were placed in blue gray a pale yellow background. By switching off the voltage and short circuit of the contacts, the image disappeared again within 1 second. The segments were imagined with sharp ends. Even after continuous operations for a number of hours in the vertical position of the display device, the segments were uniformly colored and exhibited sharp ends.

More than 100,000 ignition cycles of this type survived without any change. The blue gray coloration exhibited a maximum absorption at 453, 482, 565, 606 and 662 nm.

Example 14 In a glove box, two ITO-covered trays (resistance 12 O /) were covered in the 5 5 cm2 format constantly on the ITO side about the area with 0.075 molar of a solution of the electrochromic polymer used in Example 6 in dimethylformamide , and it was stored precisely horizontally. During the course of 4-5 hours, all solvents were evaporated in the nitrogen atmosphere and a clear, pale yellow coating of the electrochromic polymer was obtained in the trays. 5 drops of a solution in concentration of 25% by weight of lithium perchlorate in acetonitrile were then applied to one of these covers in the glove box. The second tray was placed in this solution by means of its cover side in such a way that the polymer-covered surfaces were located one below the other and the surfaces discovered on each side. The trays were then pressed together, and the solution that emerged was completely wiped off a cloth fabric. The separation between the two glass trays was then 10 μm. as described in Example 13, the device was then sealed at all four ends using hot mix adhesive and protecting using epoxy adhesive.

An electrochromic device was obtained in this manner. By applying a voltage of 1.5 V to the two outer exposed surfaces of the two trays, an intense gray-blue color was obtained over the entire area within 1-2 seconds. It completely disappeared again within 1-2 seconds after the voltage was turned off and the cell had a short circuit.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (20)

Claims

1. An electrochromic system, comprising at least one electrochemically reversible oxidizable RED] substituent, which is converted to OXi by the release of electron at each anode, and at least one reducible electrochemically reversible 0X2 substituent that is converted to RED2 by the capture of an electron at a cathode, where an increase in absorbance in the visible region of the spectrum of a colorless or weak color in a colored form with at least one electron released or an electron taken, in each case the colorless or weak color is reformed after the burden of equalization characterized in that at least one of the REDi or OX2 substituents is lently linked to a soluble polymer.

2. The electrochromic system according to claim 1, characterized in that the soluble polymer is preferably formed by the formula I -g (B, -Z-) a ... (B Y-) b 0H - B-E (I) in which the units -B? ~ Z- and -B2-Y- are linked to each other alternately, randomly or in blocks, Y and Z, independently of one another, are a REDi or OX2 substituent, where OX2 is an electrochemically reversible reducible substituent that is converted to RED2 by taking an electron into a cathode, where an increase in absorbance in the visible region of the spectrum from a colorless or weak color in a colored form associated with the electron capture, and where the colorless or weak color is reformed after the equalization charge, REDi is an electrochemically reversible oxidizable substituent that is converted to OXi by the release of the electron at the anode, where an increase in absorbance in the visible region of the spectrum from a colorless or weak color in a colored form associated with the release of the electron, and where the colorless or weak color is reformed after the equalization charge, and B is Bi or B2, Bi and B2 are identical or different link units, E is a terminal group of the polymer chain, a and b are the molar fractions of the monomer units -B? ~ Z- and -B2-Y-, which have any of the desired values between 0 and 1, where a = 1-b, is the degree of average polymerization number cn and is from 3 to 200,000, where the ratio between cn and the average polymerization weight degree cw (polymaric index) Q = cw / cn is between 1.1 and 100.

3. The electrochromic system according to claim 1, characterized in that the soluble polymer is selected from the compounds of the formulas (II) to (VIII) E- (BÍ-Z-JC-BÍ-E (II) E- (-B2-Y ~) (III) E- (-B-Z-B-Y-) c-B-E (VI) E-f z Br-y- B2-E (VII), -2 Jc / (1 + c,) where B, Bi, B2, E, Y, Z, c, a and b are as defined in claim 1, and cx and c2 represent an average degree of polymerization, where (ci + c2) < 1.

4. The electrochromic system according to claim 1, characterized in that Bi and B2, independently of one another, are 0, -CH2-, - (CH2) n- or - [Y's- (CH2) m-Y2- (CH2) e -Y3] o- (CH2) P-Y4q-, where Y1 to Y independently of one another are O, S, NR19, COO, OCO, CONH, OCONH, NHCONH, C (= 0), OC (= 0) 0, -CH = CH- (t rans - or ci s) , -CH2-CH = CH-, -C = C-, - CH2-C = C-, cycloalkanediyl- (C4-C7), arylene- (C6-C? 2) or arylalkylene- (C7-C? 4) , in particular p- and m- dimethylenephenylene or a heterocyclic radical of the structure n is an integer from 1 to 16 m and p, independently of one another are an integer from 0 to 12, is an integer from 0 to 6 and q and s, independently of one another are 0 or 1.

5. The electrochromic system according to claim 1, characterized in that the polymers of the formulas (I) - (VIII) contain at least one substance 0X2 selected the formulas (IX) - (XVIII) (XI) (X11I) (XV) (XVI) (XVII) (XVIII) in which Ri to R independently of one another are hydrogen, alkyl- (C? -C8), alkenyl- (C2-C12), cycloalkyl (C3-C7), aralkyl (C7-C? 5) or aryl (C6-C? ) R5 and Rg or R7 and R8 are hydrogen or together they are a bond - (CH2) 2-o- (CH2) 3-, R9 and Rio, independently of each other are hydrogen or in pairs are a bond (CH2) 2-, ~ (CH2) 3-o-CH = CH-, R11, 12 Ri7 and Ris, independently of one another are hydrogen, to which 1 o- (C ~ C), alkoxy- (C1-C4), halogen, cyano, nitro or alkoxycarbonyl- (C? ~ C4) Ri3 AND RI4 ? independently of one another are 0, N-CN, C (CN) 2 or aryl-N- (C6-C? o) R15 and Rie are a bond -CH = CH-CH = CH- is an O or S atom, is a direct bond -CH = CH-, C (CH3) = CH-, -C (CN) = CH-, -CC1 = CC1-, • C (OH) = CH-, -CC1 = CH-, -CH = CH-, -CH = N- N = CH-, -C (CH3) = N- = C (CH3) - or -CC1 = N- N = CC1-, is - (CH; p- or m-CH2-C6H4-CH2- is an integer from 1 to 10 and is a colorless anion that is inert to oxidation-reduction under reaction conditions - at least one REDi substance selected from formulas (XIX) through (XXV) (XIX) (XX) (XXI) (XXII) (XXV) in 1 to which R21 and R22 are (C? -C8) alkyl, (C2-C? 2) alkenyl, (C3-C) cycloalkyl, (C7-C? 5) aralkyl or (C6-C? 0) aryl, R23 to R28 independently of one another are hydrogen, (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy, halogen, cyano, nitro, alkoxycarbonyl- (C 1 -C 4) or aryl- (Ce-Cio) R29 to R35 independently of one another are hydrogen- (C1-C4) alkyl, alkoxy- (Ci- C), cyano, alkoxycarbonyl- (C1-C4) or aryl (C6-C6O), or R29 and R30, and R34 and R35, independently of one another, together are a bond ~ (CH2) 3 -, - (CH2) - or -CH = CH-CH = CH- AND; is an atom O or S or the groups N-B4 or C (CH3) 2, E3 and E is a 0 or S atom or the group NR36, R36 is alkyl- (C? -C-? 2), alkenyl- (C2- C8), cycloalkyl- (C3-C7), aralkyl- (C7-C15) ) or aryl (C6-C? o), and v is an integer from 1 to 20 if B3 is identical to B4, B3 and B are identical to Bi or B2, if B3 is not identical to B4 or B4 is absent, B3 is [- (CH2) m-Y2- (CH2) 'e-Y3] or-Y4, where Y 'is O, NR19, COO, OCO, CONH, OCONH, NHCONH, C (= 0), OC (= 0) O, -CH2-CH = CH- (trans or cis-), -CH2-C = C -, cycloalkanediyl- (C-C7), arylene- (C &-12 C) or arylalkylene- (C7-C?) Y 'is O, NR19, COO, OCO, CONH, -CH = CH- (trans or cis), -C = C-, cycloalcanediyl- C -C7 arylene- (Cg-C 12) 1 is O, NR, 1193, COO, OCO, CONH or arylene- (C6-C12) and is where R 20 is hydrogen, alkyl- (C? -C? 8), alkoxy- (C? ~ C), alkoxycarbonyl- (C? ~ C4), aryl- (C6 ~ C? O), halogen or cyano, B, is absent or is hydrogen, alkyl- (C? -C? 8), alkenyl- (C2-C12), alkoxy- (C1-C4), cycloalkyl- (C3-C7), alkoxycarbonyl- (C1-C4) , aralkyl- (C-C15), aryl- (Ce-Cio), halogen, cyano or nitro, and Bi and B2 are as defined in claim 4.

6. The electrochromic system according to claim 1, characterized in that it comprises a solvent inert to oxidation-reduction, one or more conductive inert salts, thickeners and / or UV absorbers.

7. An electrochromic device, characterized in that they contain the electrochromic system in accordance with claim 1.

A soluble polymer of formula I .. (Bl-Z-) a- (B2-Y-) b "] - B-E (I), characterized because the units -B? -Z- and -B2-Y- are linked to each other alternately, randomly or in blocks, Y and Z, independently of each other, are a REDi or OX2 substituent, where OX2 is an electrochemically reversible reducible substituent that is converted to RED2 by taking an electron into a cathode, where an increase in absorbance in the visible region of the spectrum from a colorless or weak color in a colored form associated with the electron capture, and where 'the colorless or weak color is reformed after the equalization charge, REDi is an electrochemically reversible oxidizable substituent that becomes OX? by the release of the electron at the anode, where an increase in absorbance in the visible region of the spectrum from a colorless or weak color in a colored form associated with the release of the electron, and where the colorless or weak form of color is reformed after the equalization charge, "B is Bi or B2, Bi and B2 are identical or different link units, is a terminal group of the polymer chain, a and b are the molar fractions of the monomer units -Bi-Z- and -B2-Y-, which have any of the desired values between 0 and 1, where a = 1 -b, is the degree of average polymerization number cn and is from 3 to 200,000, where the ratio between cn and the average polymerization weight degree cw (polymaric index) Q = cw / cn is between 1.1 and 100.

9. A process for the preparation of soluble polymers according to claim 8, characterized in that one or more RED- and / or 0X2-contain monomers of the formulas XXVI-XXVIII X1-B6-OX2-B7- (XXVI) X1-B6-RED1-B7-X2 (XXVII) X1-B6-OX2-B8-RED1-B7-X2 (XXVIII) in which OX is the radical of an electrochemically reversible reducible oxidation-reduction system, and RED1 is the radical of an electrochemically reversible oxidizable oxidation-reduction system, Bd, B7 and B8 are the link units, X1 and X2 are each a group that is capable of polymerization, polycondensation or polyaddition, they are subject to the polymerization, polycondensation or polyaddition reaction.

10. The process according to the rei indication 9, characterized in that, in the monomers of the formulas XXVI to XXVIII, OX is a radical of formulas IX through XVIII, (IX) (X) (XII) (xpi) (xvi) (XVII) (XVIII) in which Ri to ta R4, independently of one another are hydrogen, alkyl- (C? -8), alkenyl- (C2-C12), cycloalkyl (C3-C-7), aralkyl (C7-C? 5) or aryl (C6) -C? 0) R5 and Re or R7 and R8 are hydrogen or together they are a bond - (CH2) 2-o- (CH2) 3-, R9 and Rio, independently of one another are hydrogen or in pairs are a bond (CH2) 2 -, - (CH2) 3-o-CH = CH-, Rii, 12 17 and Ris, independently of one another are hydrogen, alkyl - (C? ~ C4), alkoxy- (C1-C4), halogen, cyano, nitro or alkoxycarbonyl- (C? ~ C4) R13 and Ri4 / independently of one another are 0, N-CN, C (CN) 2 or aryl-N- (Ce-Cío) R 15 and Rie are a bond -CH = CH-CH = CH- Ei is an atom O or S ', is a direct bond -CH = CH-, C (CH3) = CH-, -C (CN) = CH-, -CC1 = CC1-, C (0H) = CH-, -CC1 = CH-, -CH = CH-, -CH = N- N = CH-, -C (CH3) = NN = C (CH3) - or -CC1 = N- N = CC1-, it's CH; p- or m-CH2-C6H4-CH2-, is an integer from 1 to 10 and is a colorless anion that is inert to oxidation-reduction under RED reaction conditions "is a radical of the compounds of formulas XIX to XXV (XIX) (XX) (XXI) (XXII) (XXIII) (XXIV) in which R21 and R22 are (C? -C8) alkyl, (C2-C12) alkenyl, (C-C7) cycloalkyl, (C7-C15) aralkyl or (Cg-Cio) aryl, R23 to R8 independently of one another are hydrogen, (C1-C4) alkyl, (Ci- C4) alkoxy, halogen, cyano, nitro, (C1-C4) alkoxycarbonyl or (C6-C10) aryl R 26 is additionally NR37R37 R29 to R35 independently of one another are hydrogen- (C1-C) alkyl, (C?-C4) alkoxy, cyano, alkoxycarbonyl- (C?-C4) or aryl (C6-C? O) or R g and R30, and R34 and R35, independently of each other, together are a bond ~ (CH2) 3 -, - (CH2) 4- or -CH = CH-CH = CH- E- is an atom O or S or the groups N-B4, C (CH3) 2, C = 0 or S02, E3 and E4 is a 0 or S atom or the group NR3.5, independently of one another are alkyl- (C1-C12), alkenyl- (C2-C8), cycloalkyl- (C3-C7), aralkyl- (C7- C15) or aryl- (C6-C? 0) and R3s is additionally hydrogen, or R36 and R37 in the meaning of NR36R37 together with the N atom to which these bond, form a five or six membered, saturated ring, which may contain additional heteroatoms 36 is alkyl- (C? -C-12), alkenyl- (C2-Cs), cycloalkyl- (C3-C7), aralkyl- (C7-C15) or aryl (C6-C? O), and v is an integer from 1 to 20, if B3 is identical to B4, B3 and B4 are identical to Bi or B2 / if B3 is not identical to B4 or B4 is absent, B3 is [Y1s- (CH2) ra-Y2- (CH2) e-Y3] o- Y4, where Y "is 0, NR19, COO, OCO, CONH, OCONH, NHCONH, C (= 0), OC (= 0) O, -CH2-CH = CH- (trans or cis-), -CH2-C = C -, cycloalkanediyl- (C4-C7), arylene- (C6- C12) or arylalkylene- (C7-C14) Y 'is 0, NR19, COO, OCO, CONH, -CH = CH- (trans or cis), -C = C-, cycloalkanediyl- (C4-C7) or arylene- (C6-Ci2), is O, NR 1- 19 COO, OCO, CONH or arylene- C6-C? 2. Y! is where B. is Bi or B2, and R 2o is hydrogen, alkyl- (C 1 -C 8), alkoxy- (C 1 -C 4), alkoxycarbonyl- (C 1 -C 4), aryl- (C 6 -C 0), halogen or cyano, B < is absent or is hydrogen, alkyl- (C? -C? 8), alkenyl- (C2-C? 2), alkoxy- (C1-C4), cycloalkyl- (C3-C7), alkoxycarbonyl- (C? -C4) ), aralkyl- (C7- C15), aryl- (Cß-Cio), halogen, cyano or nitro, and Bi and B2 are as defined in formulas I through VIII, B3 and B4 are replaced by link units B6, B7 and B8, X1 and X: are halogen, -OH, -O ", -COOH, -COO- (C1-C4) -alkyl, -0-C (= 0) - (C? -C4) -alkyl, -COO-, -NH2, -NH- (C1-C4) -alkyl, -N = C = 0, or the tertiary nitrogen atom carrying three identical or different substituents- (C1-C12) alkyl, aralkyl- (C7-C15) or aryl- (Cß-Cio) or is a member of a ring of 4-7 atoms, which may also contain additional heteroatoms, or XJ X 'is a double bond C = C-, a group -O- C (= 0) -CH = CH2 or a group -0-C (= 0) - C (CH3) = CH2-.

11. Electrochromic monomers of the formulas (XXVI to XXVIII) X1-B6-OX2-B7-X2 (XXVI) X1-B6-RED1-B7-X2 (XXVII) X1-B6-OX2-B8-RED1-B7-X2 (XXVIII) in which OX is an electrochemically reversible reducible substituent, and RED is an electrochemically reversible oxidizable substituent, and B6, B7 and B8 are liaison units, and X and X are each a group that is capable of polymerization, polycondensation or polyaddition.

12. The electrochromic monomers according to claim 11, characterized in that they are formed by the formula XXIX in which B6 = B7 = - (CH2) n-, X1 = X2 = -OH, n - 2 11 are selected from halide, tetrafluoroborate, tetraphenylborate, cyanotriphenylborate, perchlorate, dodecyl sulphonate, hexadecyl sulphonate, toluenesulfonate, butylbenzenesulfonate, dodecylbenzenesulphonate, hexafluorophosphate, - or 7, 9-dicarba nido-undecarborato (1-) Bb = - (CH2) n, where n = 2 - 11, B7 = aryl- (Cß-Cio), aryl- (C6-C? O) substituted, alkyl- (Ci-Cis), alkenyl- (C? -Ci8) or aralkyl- (C7-C24), X1 = -OH, X is absent, and G is selected from the group consisting of halide, tetrafluoroborate, tetraphenyl borate, cyanotriphenyl borate, perchlorate, dodecylsulfonate, hexadecyl sulphonate, toluenesulfonate, butylbenzenesulfonate, dodecylbenzenesulphonate, hexafluorophosphate, 7,8- or 7,9-dicarba. nest-undecarborate (1-), BD m- or p-C6H4-CH2- a mixture of the isomers, X1 = • CH = CH2, X is absent, Ba = - (CH2) n-, n = 2 - 18 or B8 = o-, m- or p-CH2-C6H4-CH2-, and G "are selected from halide, tetrafluoroborate, tetraphenylborate, cyanotriphenyl borate, perchlorate, hexafluorophosphate, 7,8- or 7,9-dicarba-nido-undecarborate (1-).

13. The electrochromic monomers according to claim 11, characterized in that they are formed by the formula XXX in which B < = B '= - (CH2) n-, where n = 2 - lí B' B (CH2) 2-0- (CH2) 2- o- m- p-CH2-C6H¿ CH2-, and X1 = X2 = halogen, B6 - B7 ~ (CH2) n ~ / where n 18 Bb = B; = - (CH2) 2-0- (CH2) 2- or o-, m- or p-CH2-C6H4- CH2-, X- X -0-C (= 0) -alkyl- (C? -C4), -0-C- (= 0; CH = CH, or -0-C (= 0) -C (CH3) = CH2 , or B6 = - (CH2) n-, where n = 2 - 18, B7 = -Ph, X1 = -O-C (= 0) -CH = CH2 or -0-C (= 0) -C (CH3) = CH2, and X is absent, or B '(CH2) n-, where n = 2 - 11 B = -aryl- (C6-C? O), -aryl- (C6-C? 0) substituted, -alkyl- (C? -C? 8) or -aralkyl- (C7-C24), X1 = -OH, and X¿ is absent B6 = B7 (CH; where n 3 - 11 and x- Xz = -OH, B6 = B7 = -CH2-CH (CnH2n +?) -, where n = 1 - 18, and X1 = X2 = -OH

14. The process according to claim 9, characterized in that the electrochromic monomers having two primary or secondary OH groups are polycondensed with aliphatic or aromatic diisocyanates.

15. The process according to claim 9, characterized in that the electrochromic monomers having two primary halogen groups are subjected to a polyaddition reaction with aliphatic or aromatic compounds having two tertiary nitrogen atoms which may themselves carry three identical or different substituents alkyl- (C? -C? 2), aralkyl- (C7-C? 5), aryl- (C6-C? 0) or are members of a ring of 4-7 atoms.

16. The process according to claim 9, characterized in that the electrochromic monomers having at least one C = C double bond are polymerized by free radical polymerization.

17. The process according to claim 9, characterized in that the electrochromic monomers having two OH groups are polycondensed with dicarboxylic acid dichlorides.

18. A solution, characterized in that it comprises a dipolar, aprotic solvent and a polymer according to claim 8, dissolved in it.

19. Films or covers characterized in that they comprise the polymers according to claim 8.

20. An electrochromic device characterized in that they contain films or covers according to claim 19.