NOVEL TETRACYANOANTHRAQUINODIMETHANE POLYMERS AND USE THEREOF

Abstract

Novel tetracyanoanthraquinodimethane polymers and use thereof. The problem addressed was that of providing novel polymers which are preparable with a low level of complexity, with the possibility of controlled influence on the physicochemical properties thereof within wide limits in the course of synthesis, and which are usable as active media in electrical charge storage elements for high storage capacity, long lifetime and stable charging/discharging plateaus. Tetracyanoanthraquinodimethane polymers consisting of an oligomeric or polymeric compound of the general formula I have been found.

##STR00001##

Claims

1-5. (canceled)

6. A tetracyanoanthraquinodimethane polymer comprising an oligomeric or polymeric compound of the general formula I: ##STR00029## where R.sub.1 to R.sub.7: are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, X: is an organic group which is formed by polymerization reaction from a group consisting of an organic double bond, an organic triple bond, an oxirane or an aziridine, or is an organic group which is formed by a polymer-analogous reaction, n: is an integer greater than or equal to 2.

7. The tetracyanoanthraquinodimethane polymer according to claim 6, wherein at least five of R.sub.1 to R.sub.7 are hydrogen and zero to two of R.sub.1 to R.sub.7 are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen substituents.

8. The tetracyanoanthraquinodimethane polymer according to claim 6, wherein X is an organic group of one of the general formulae II-XIV: ##STR00030## ##STR00031## wherein R.sub.8 to R.sub.24: are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, R.sub.26 to R.sub.28: are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, R.sub.30 to R.sub.32: are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, halogen atoms or a combination of these groups or atoms, R.sub.33 to R.sub.35: are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, A: is an oxygen atom, a sulphur atom or an N(R.sub.29) group, where R.sub.29 is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, alkylthio group, haloalkyl group, haloalkoxy group, cycloalkyl group, cycloalkoxy group, aryl group, heteroaryl group, aryloxy group, aralkyl group, carboxylic acid group, sulphonic acid group, nitro group, alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, carboxylic ester group, carboxamide group, or sulphonic ester group, A.sub.1 and A.sub.2: are each independently a covalent bond, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a monoalkylamino group, a dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, alkynylcarbonyl group, a carboxylic ester group, a carboxamide group, or a sulphonic ester group, A.sub.3 and A.sub.4: are each independently a covalent bond, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic ester group, a carboxamide group,or a sulphonic ester group, A.sub.5 and A.sub.6: are each independently a covalent bond, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a monoalkylamino group, a dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic ester group, a carboxamide group, a sulphonic ester group, Ar: is an independently substituted cycloalkyl group, cycloalkoxy group, aryl group, heteroaryl group, aryloxy group, or aralkyl group.

9. The tetracyanoanthraquinodimethane polymer according to claim 8, wherein at least two of the R.sub.8 to R.sub.10 substituents are hydrogen atoms and zero to two of the R.sub.8 to R.sub.10 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein at least two of the R.sub.11 to R.sub.13 substituents are hydrogen atoms and zero to two of the R.sub.11 to R.sub.13 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein R.sub.14 is a hydrogen atom, and/or wherein at least two of the R.sub.15 to R.sub.17 substituents are hydrogen atoms and zero to two of the R.sub.8 to R.sub.10 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein at least two of the R.sub.18 to R.sub.20 substituents are hydrogen atoms and zero to two of the R.sub.18 to R.sub.20 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein R.sub.21 is a hydrogen atom, and/or wherein at least two of the R.sub.22 to R.sub.24 substituents are hydrogen atoms and zero to two of the R.sub.22 to R.sub.24 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein at least two of the R.sub.26 to R.sub.28 substituents are hydrogen atoms and zero to two of the R.sub.26 to R.sub.28 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein at least two of the R.sub.30 to R.sub.32 substituents are hydrogen atoms and zero to two of the R.sub.30 to R.sub.32 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents, and/or wherein at least two of the R.sub.33 to R.sub.35 substituents are hydrogen atoms and zero to two of the R.sub.33 to R.sub.35 substituents are halogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atom substituents.

10. The tetracyanoanthraquinodimethane polymer according to claim 8, wherein A is an oxygen atom.

11. The tetracyanoanthraquinodimethane polymer according to claim 8, wherein A.sub.1 and A.sub.2 and A.sub.3 and A.sub.4, are a covalent bond or an alkyl group and A.sub.5 and A.sub.6 are a covalent bond, aryl group or an alkyl group.

12. An active electrode material for a secondary battery or other electrical charge storage device comprising the tetracyanoanthraquinodimethane polymer according to claim 6.

13. A full or partial surface coating of electrode elements for a secondary battery or other electrical charge storage device comprising the tetracyanoanthraquinodimethane polymer according to claim 6.

14. An electrode slurry for a secondary battery or an electrical charge storage device, comprising the tetracyanoanthraquinodimethane polymer according to claim 6.

Description

[0141] The drawings show:

[0142] FIG. 1: Cyclic voltammograms of a monomer prepared according to Example 2 (broken line) and of an electrode produced therefrom according to Example 4 (solid line)

[0143] FIG. 2: Charge/discharge curves of the first (solid line) and five hundredth (broken line) charging/discharging cycle of a secondary battery produced according to Example 5

[0144] FIG. 3: Charging/discharging behaviour of the secondary battery produced according to Example 5

[0145] FIG. 4: Coulomb efficiency of the secondary battery produced according to Example 5

[0146] .sup.1H and .sup.13C NMR spectra were recorded with a Broker AC 300 (300 MHz) spectrometer at 298 K. Elemental analyses were conducted with a Vario ELIII-Elementar Euro instrument and an EA-HekaTech instrument. For cyclic voltammetry and galvanostatic experiments, a Biologic VMP 3 potentiostat was available. Size exclusion chromatography was conducted on an Agilent 1200 series system (degasser: PSS, pump: G1310A, autosampler: G1329A, oven: Techlab, DAD detector: G1315D, RI detector: G1362A, eluent: DMAc+0.21% LiCl, 1 ml/min, temperature: 40 C., column: PSS GRAM guard/1000/30 ).

##STR00028##

EXAMPLE 1

Synthesis of 2-vinylanthraquinone (3)

[0147] 2-Bromoanthraquinone (1.5 g, 5.22 mmol), bis(dibenzylideneacetone)palladium(0) (0.060 g, 0.104 mmol), biphenyl-2-yldi-tert-butylphosphine (0.062 g, 0.209 mmol) are dissolved in a 0.3 M solution of tetrabutylammonium fluoride in tetrahydrofuran. The solution is purged with argon, and 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-1,3,5,7,2,4,6,8-tetraoxatetrasiloxane (0.902 nil, 2.61 mmol) is added dropwise. The mixture is stirred at 80 C. under an argon atmosphere for 8 hours. The reaction mixture is cooled to room temperature and added to 250 ml of ethanol. The precipitate is filtered off and washed twice with n-hexane. After drying under reduced pressure, almost pure 2-vinylanthraquinone (3) (1.175 g, 5.02 mmol, 96%) is obtained as a yellowish solid, the purity of which is sufficient for the next reaction step.

[0148] Anal. Calcd for C.sub.16H.sub.10O.sub.2: C, 81.90; H, 4.30. Found: C, 81.85; H, 4.31. .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 5.54 (d, 1H), 6.05 (d, 1H), 6.87 (dd, 1H), 7.80 (m, 3H), 8.32 (m, 4H). .sup.13C NMR (CDCl.sub.3, 75 MHz, ppm): 183.2, 182.6, 143.2, 135.4, 134.1, 134.0, 133.8, 133.6, 133.5, 132.5, 131.4, 128.3, 127.8, 127.2, 124.8, 118.4.

EXAMPLE 2

Synthesis of 2-vinyl-1 2,12-tetracyanoanthraquinodimethane (4)

[0149] 2-Vinylanthraquinone (1 g, 4.27 mmol) and malononitrile (0.85 g, 0.81 ml, 12.81 mmol) are dissolved in 71 ml of chloroform. Pyridine (2.07 ml, 25.6 mmol) and titanium tetrachloride (1.41 ml, 12.81 mmol) are added dropwise to the reaction mixture within five minutes. The mixture is stirred at 80 C. under argon for 15 hours, cooled to room temperature and extracted twice with water and once with brine. The organic phase is dried with sodium sulphate, the desiccant is filtered off and the organic phase is concentrated under reduced pressure. The crude product is purified by column chromatography (silica gel, chloroform). This gives 700 mg of 2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane (4) (2.12 mmol, 50%) as a yellow powder.

[0150] Anal. Calcd for C.sub.22H.sub.10N.sub.4: C, 80.00; H, 3.10, N, 16.90. Found: C, 79.94; H, 3.08. N 16.91. .sup.1H NMR (CD.sub.2Cl.sub.2, 300 MHz, ppm): 5.61 (d, 1H), 6.06 (d, 1H), 6.88 (dd, 1H), 7.77 (m, 3H), 8.27 (m, 4H). .sup.13C NMR (CD.sub.2Cl.sub.2, 75 MHz, ppm): 160.5, 160.0, 141.8, 134.5, 132.4, 130.8, 130.4, 130.2, 129.7, 129.0, 128.01, 127.5, 124.93, 119.3, 113.3, 113.1.

EXAMPLE 3

Synthesis of poly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5)

[0151] 50 mg of 2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane (4) are dissolved in 0.150 ml of N,N-dimethylformamide, and 1.24 mg of AIBN (0.0076 mmol, 5 mol %) are added. The reaction mixture is degassed with argon for five minutes and stirred at 80 C. for 18 hours. Thereafter, the reaction solution is added to 50 ml of dichloromethane, in order to precipitate the product. This forms 42 mg of poly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5) as a yellow solid.

[0152] Anal. Calcd for C.sub.22H.sub.10N.sub.4: C, 80.00; H, 3.10, N, 16.90. Found: C, 79.96; H, 3.13, N 16.95. .sup.1H NMR (DMF-d.sub.7, 300 MHz, ppm): 8.83 to 7.48 (br, 7H), 2.62 to 1.31 (br, 3H). SEC: M.sub.n 2.6710.sup.4 g/mol 1.87.

EXAMPLE 4

Production of an electrode with poly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5), cf. FIG. 1

[0153] A solution consisting of poly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5) in NMP (N1-methyl-2-pyrrolidone) (10 mg/ml) was added to carbon fibres (VGCF; Showa-Denko) and Super P as conductivity additives and poly(vinylidene fluoride) (PVDF; Sigma Aldrich) as binder additives (ratio: 20/30/30/10 wt %). These materials were mixed in a mortar for 10 minutes, and the resulting paste was applied to an aluminium foil using a coating blade method (thickness: 0.015 mm, MTI Corporation). The electrode is dried at 100 C. for 24 hours.

[0154] The electrode is dipped into an electrolyte solution (0.1 M LiClO.sub.4 in propylene carbonate). For the cyclic voltammetry measurement, a half-cell consisting of said electrode as working electrode and an Ag/AgNO.sub.3 electrode as reference electrode, and also a platinum mesh as counterelectrode, is constructed, (FIG. 1)

[0155] The cyclic voltammogram shows a stable redox reaction at 0.71 V.

EXAMPLE 5

[0156] Production of an Li Polymer Battery

[0157] The electrode described in Example 4 is introduced into a secondary battery (Li polymer battery) under an argon atmosphere. The electrolyte used is a 0.1 M solution of LiClO.sub.4 in propylene carbonate; the counterelectrode used is a piece of elemental lithium. The two electrodes are separated from one another by the separator (a porous polypropylene membrane, Celgard). The battery shows a charge plateau at 2.9 V and a discharge plateau at 2.4 V (FIG. 2).

[0158] In the first charge/discharge cycle, the battery shows a capacity of 156 mAh/g (97% of the theoretically possible capacity); after 500 charge/discharge cycles, the battery shows a capacity of 141 mAh/g (FIG. 3) at an average coulomb efficiency of 99%. (FIG. 4) Please amend the claims as follows: