RU972815C - 1,1*98'-dimethyl-4,4*98'-dypyridyliumdicarbaundecaborate as component for electrochrome composition and electrochrome composition - Google Patents

Abstract

1-, 1, G-Dimethyl-4,4-dipyridylidicarboxone decarborate of the formula cCH-N N-CHJ. shttt-pttt & LIOG ON as a component for the electrochromic composition. 2. The electrochromic composition, which includes the quaternary salt of dipyridyl, a derivative of ferrocene and γ-butyrolactone, is excluded and so that, in order to obtain a constant relaxation time of the induced absorption of the composition during prolonged exposure to electric voltage, it as a quaternary salt, dipyridyl contains 1, V-dimethyl-4,4-dipyridylidicarboundecaborate in the following ratio of ingredients, mSg%; 1,1-Dimethyl-4,4-dipyridylidicarboundecaborate 2-10 Ferrocene derivative 1-4 y-Butyrolactone.

Description

H GO 00

ate

A new chemical compound, specifically 1,1-dimethyl-4,4-dipyryl or idicarboundecaborate of the formula

4 / .

whitefish OKZn-SNZ gSgVdN ,,

as a component for the electrochromic composition, as well as the electrochromic composition thereof. v.

The indicated 8th thing: your and electrochromic leave can be used to create devices with variable light fading, which changes when electrical voltage is applied, for example, variable optical density light filters for solar and laser radiation, stabilizers, different types of radiation, etc.

Of 1% natural, the use of 1,1-ditetyl 4, 4-dipyridyl with the anions GIO4 and BF4 as a component in non-aqueous electrochromic compositions.: /;

Of the known nonaqueous, zlocrochromic compositions, the composition closest to the proposed one, including 18 quaternary salt of dit11, was formed with CI04 anions and a derivative of ferrocene, 6utirolac: tone (solvent), polymethylmethacrylate (viscosity increasing substance) in the following ratio of ingredients, May. %:

Quaternary SALT;

dipyridyl 1-2

Derivative fer

,,; RotsNal.:.;.:. :: .. ::; -3-6 .-; ..

Polymethylmethacrylate 0.5-2 y-ButyrolacTone

The use of Salt 1, G-dimethyl-4,4-dipyridyl with the anions Bp4 or CJD allows one to obtain a constant relaxation time of the induced absorption of the composition made on their basis to the concentrations of the colored salt form “TO m (l / l (or dO single optical density with a thickened colored spruce of about 100 μm) independently of the duration of exposure to electric voltage, however, with increased values of optical density, the effect of stratification occurs over time, when the concentration of the colored salt form is consequential. eska density uncontrollably lovysch eets in the upper part of volume of the composition and decreases in its lower portion, the relaxation time of the induced absorption increases uncontrollably. A similar phenomenon is observed with

all electrochromic compositions based on quaternary dipyridyl salts with anions CI04, BF4.

To slow down the effect

delamination (prototype) increased the viscosity of the electrochromic composition by dissolving the polymethyl methacrylate. However, this introduced additional operations in the manufacturing process of the composition and led

only a slight weakening of the manifestation of the delamination effect.

The aim of the invention is a new substance as a component for electrochromic composition and the creation of

electrochromic composition having a constant relaxation time of the induced absorption during prolonged exposure to electric voltage, and simplification of its manufacturing process.

The specified goal is achieved by 1,1-dimethyl-4, 4-dipyridylidicarboxone decaborate of the above formula and the creation of an electrochromic composition containing the quaternary dipyridylate salt,

ferrocene i) A 6 butyrolactone, which contains 1; 1-dimethyl-4,4-dipyridyl dicarboundecaborate as the quaternary salt in the following ratio, May. %:

1,1-Dimethyl-4,4-dipyridylidene dicarboundecaborate 2-10

Ferrocene derivative 1-4 y-Butyrolactone

The proposed salt, 1,1-dimethyl-4,4-dipyridylidicarboundecarborate, has a combination of an electrochromic active cation and an inactive dicarboundecaborate anion, which is a new ion combination

And it leads to a significant difference in the properties of the proposed compound from the properties of the known quaternary dipyridyl salts with other anions.

The proposed compound is obtained at

reaction

3Q-NQ-) +

(НЗС-нО-) 2 (CgVeN, g) g1-2KE

those. by the exchange interaction of aqueous solutions of 1,1-dimethyl-4.4-dipyridylidium iodide and potassium dicarboundecaborate. The precipitated hardly soluble 55 in water product is filtered off, washed with water and recrystallized from an organic solvent.

Method for determining the relaxation time of the induced absorption of compounds in

depending on the time of exposure to electric voltage was as follows. Electrochromic compositions were tested in devices consisting of two glass plates 40x60 mm in size with layers 1n20z coated with 5 dopants with dopants. The glass plates overlap each other with a shift in one of the directions, which made it possible to attach the contacts 10 conductive coatings. The distance between the plates was fixed by a Teflon frame measuring 30x30 mm and a side width of 5 mm. The thickness of the frame was 60-200 microns. The space limited by the plates and the Teflon frame was filled with a non-aqueous solution of the Quaternary salt of Dig1iridil with an additive showing the resource of repainting the composition with ferrocene derivative. 20 For sealing, the device was clamped with clamps. The electrodes of the device were supplied with a constant electric voltage for a certain time (s). Then the voltage was turned off, the electrodes of the circuit were short-circuited. In this case, the relaxation time (ti) was measured at the initial unpainted state, characterized by a certain absorption spectrum.

P. primer 1. Synthesis of 1,1-dimethyl-4.4-30 dipyridylidicarboundecarborate.

A solution of 4.4 g (10 mmol) of 1,1-dimethyl-4,4-dipyridyl iodide ft 50 35 ml of water is added to a solution of 3.4 g (2 b mmol) of potassium dicarboundecaborate in 100 ml of water. The precipitate of 1,1, -dimethyl4, 4-dipyridylidicarboxone decarborate was filtered off, washed with water and dried in air. The target product is recrystallized from a mixture of acetone with 40 alcohol. Yield 3.81 g (84% of theory), T.P. 242-244 ° C.

Found,%: C 42.09; H 8.37; N, 6.33.

Cl6H38Bl8N2

Calculated,%: C 42.41; H 8.45; W 6.18. 45 The electrochromic properties of the proposed substance were evaluated by the electrochromic characteristics of the compositions made on its basis.

Known solution (prototype). In a 0.5% -50% solution of polymethylmethacrylate in ubutyrolactone, 1,1-dimethyl-4,4-dipyridyl di-chlorate in 2% concentration and a mixture of mono-, di-, three tert-butylferrocene in 3% concentration are dissolved. 55 The electrochromic device is filled with the resulting composition with a distance between the electrodes of 200 µl. In the initial state, the solution is not colored. When a voltage of 1.05 V is applied, an induced

absorption with a long wavelength band having a maximum at λ-608 nm, and the color of the composition turns blue. The steady-state optical density during the first 2 minutes of exposure to the electrical voltage at Lox is 2, and Bpei of relaxation is 5 s. However, after 10 minutes of exposure, it increases to 120 s due to the manifestation of the delamination effect associated with a change in the concentration of the colored form in the volume of the composition. The upper part of the volume of the composition during the relaxation process is colored, while its lower part is not colored. The delamination effect increases with increasing time of exposure to voltage, which leads to an increase in relaxation time (see table, prototype), which after 180 minutes of exposure to electric voltage increases by about two orders of magnitude.

EXAMPLE 2. B) -butyrolacto is dissolved 1,1-dimethyl 4,4-dipyridyl dicarboundecaborate in a 2% concentration and a mixture of MONO-, DI-, tri-tret-butylferrocene in a 1% concentration. The resulting solution is filled into an electrox (X) device with a distance between the electrodes of 200 microns. In the original cocoa, the composition is not colored. When a voltage of 1.00 V is applied, induced absorption is formed with a long-wavelength band having a maximum at A - 608 nm, and the color of the composition turns blue. The stationary optical density 3 during the action of the electric voltage at ax is equal to 2, and the relaxation time of the induced absorption is 10 s, it remained almost constant after more time intervals, equal to 10, 30, 60, 180 and 360 minutes (see table, sample 1).

Example 3, 1,1-dimethyl 4,4-dipyridyl dicarboundecaborate is dissolved in y-5-butyrolactone in a 4% concentration and a mixture of MONO-, DI-, tri-tert-butylferrocene in a 2% concentration. The electrochromic device was filled with the resulting solution with a distance between the electrodes of 200 µm. In the initial state, the composition is not. When a voltage of 0.9 V is applied, induced absorption forms with a long-wavelength band having a maximum at A of 608 nm, and the color of the composition turns blue. The stationary optical density during exposure to electric voltage at Lmax is 3, and the relaxation time of the induced absorption after 2 min of exposure to voltage, equal to 10 s, remained almost constant after 10, 30, and 60 min of exposure

voltage, varying within acceptable limits after 180 and 360 minutes (see table, sample 2).

Example 4 1,1-dimethyl 4,4-dipyridyl dicarboundecaborate was dissolved in y-butyrolactone in a 10% concentration and a mixture of MONO-, di-tri-tert-butylferrocycium in a 4% concentration. An electrochromic device was filled with the resulting solution with a distance between the electrodes of 60 microns. In the initial state, the composition is not colored. When a voltage of 1.05 V is applied, an induced absorption is generated with a long-wavelength band having a maximum at L 608 nm, and the color of the composition turns blue. The stationary optical density during exposure to electric voltage at LikS is 2.3, and the relaxation time of the induced absorption after 2 minutes of exposure to voltage for 3 s. it remained practically constant after longer periods of time equal to 10, 30, 60, and 180 min (see table, sample 3).,

As can be seen (see table) from a comparison of the relaxation time of the induced absorption of the compositions based on

of a known substance (prototype) and of the proposed one (e.g., sample 1), the relaxation time of the induced absorption of the latter does not depend on the time of exposure to a constant electric voltage, whereas in the case of the known BeatecTsa this time increases by two orders of magnitude after 3 hours of exposure to voltage.

In addition, when using the inventive substance, the process for producing an electrochromic composition is simplified, since it does not need to introduce a viscosity increasing substance. The proposed composition has a new combination of properties; the constant relaxation time of the induced absorption h and the possibility of obtaining an optical density of 3 at the maximum of the long-wavelength band of this absorption.

Electrochromic devices made on the basis of the proposed composition will have a controlled time re; stroke from painted to unpainted state.

(56) Copyright certificate of the USSR hfe 722219, cl. S 09 K 11 / V, 1978.

Note, and is the value of the electric voltage applied to the device: D is the initial stationary optical density of the induced absorption at Liax 608 nm and the effect of electric voltage; . thickness of samples;

tt is the relaxation time of the induced absorption to the initial state: t2 is the time of exposure to electric voltage.