USE OF CERTAIN POLYMERS AS A CHARGE STORE

Abstract

The present invention relates to polymers and to the use thereof in the form of active electrode material or in an electrode slurry as electrical charge storage means, the electrical charge storage means especially being secondary batteries. These secondary batteries are especially notable for high cell voltages, and simple and scalable processing and production methods (for example by means of screen printing).

Claims

1: A polymer, comprising n.sup.1 mutually linked repeat units of the following chemical structure (I) or n.sup.2 mutually linked repeat units of the following chemical structure (II): ##STR00024## wherein n.sup.1 and n.sup.2 are each independently an integer 4, m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0, the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (I) within the polymer are joined to one another in such a way that the bond identified by ## in a particular repeat unit is joined by the bond identified by # in the adjacent repeat unit and the bond identified by in a particular repeat unit is joined by the bond identified by in the adjacent repeat unit, the repeat units of the chemical structure (II) within the polymer are joined to one another in such a way that the bond identified by * in a particular repeat unit is joined by the bond identified by ** in the adjacent repeat unit, the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals are each independently selected from the group consisting of hydrogen, (hetero)aromatic radical, aliphatic radical optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, at least two of A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, A.sup.6 are each an oxygen or sulphur atom and the others of A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, A.sup.6 are each a direct bond, at least two of A.sup.7, A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.12 are each an oxygen or sulphur atom and the others of A.sup.7, A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.12 are each a direct bond, at least two radicals in ortho positions to one another among the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals and/or at least two radicals in ortho positions to one another among the R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23 radicals may each also be bridged by at least one (hetero)aromatic ring or aliphatic ring optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen, alkyl group and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, the R.sup.1 radical in the case that A.sup.1=direct bond, the R.sup.2 radical in the case that A.sup.2=direct bond, the R.sup.3 radical in the case that A.sup.3=direct bond, the R.sup.4 radical in the case that A.sup.4=direct bond, the R.sup.19 radical in the case that A.sup.12=direct bond, the R.sup.20 radical in the case that A.sup.8=direct bond, the R.sup.21 radical in the case that A.sup.9=direct bond, the R.sup.22 radical in the case that A.sup.10=direct bond, the R.sup.23 radical in the case that A.sup.11=direct bond and the R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals may each also be selected from the group consisting of nitro group, CN, F, Cl, Br, I, COOR.sup.36, C(O)NHR.sup.37, NR.sup.38R.sup.39, where R.sup.36, R.sup.37, R.sup.38, R.sup.39 are each independently selected from the group consisting of hydrogen, (hetero)aromatic radical, aliphatic radical optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, and wherein the R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals may independently also be a radical of the formula OR.sup.40 where R.sup.40 is an aliphatic radical optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, B.sup.1, B.sup.2, B.sup.3 are each independently selected from the group consisting of &(CH.sub.2).sub.p1&& where p1 is an integer from 1 to 4, and where at least one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.r1B.sup.5(CH.sub.2).sub.r2&& where B.sup.5 is a (hetero)aromatic divalent 6-membered ring, 3-membered ring or 5-membered ring and r1, r2 are each 0 or 1, where r1+r21, &(CH.sub.2).sub.q1B.sup.6(CH.sub.2).sub.q2&& with B.sup.6O, S, NH; q1=0, 1, 2 and q2=1, 2, 3 where q1+q23 and where one CH.sub.2 group may also be replaced by C(O), &OC(O)NHCH.sub.2&&, B.sup.1, in the case that A.sup.5=direct bond, B.sup.2 in the case that A.sup.6=direct bond, B.sup.3 in the case that A.sup.7=direct bond, may each independently also selected from the group consisting of &(CH.sub.2).sub.5&& where at least one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.v1B.sup.7(CH.sub.2).sub.v2&& with B.sup.7O, S, NH; v1=0, 1, 2, 3 and v2=1, 2, 3, 4, where v1+v2=4 and where one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.t1B.sup.8(CH.sub.2).sub.t2&& where B.sup.8 is a (hetero)aromatic divalent 3-membered ring, 5-membered ring or 6-membered ring and t1, t2 are each 0 or 2, where t1+t22, &CH.sub.2OC(O)NHCH.sub.2&&, &OC(O)NH&&, &CH.sub.2OC(O)NH&&, &CH.sub.2CH.sub.2OC(O)NH&&, &OC(O)NHCH.sub.2CH.sub.2&&, wherein B.sup.1, in the case that A.sup.5=O or S, B.sup.2 in the case that A.sup.6=O or S, B.sup.3 in the case that A.sup.7 O or S, may in each case also be a direct bond, in the B.sup.1, B.sup.2, B.sup.3 radicals, at least one hydrogen atom bonded to a carbon atom or nitrogen atom may be replaced by a halogen atom or an alkyl group, && for B.sup.1 denotes the bond pointing toward A.sup.5, for B.sup.2 the bond pointing toward A.sup.6, and for B.sup.3 the bond pointing toward A.sup.7, and & for B.sup.1 denotes the bond pointing toward R.sup.5, for B.sup.2 the bond pointing toward R.sup.8, and for B.sup.3 the bond pointing toward R.sup.24.

2: The polymer according to claim 1, comprising n.sup.1 mutually linked repeat units of the chemical structure (I) or n.sup.2 mutually linked repeat units of the chemical structure (II) ##STR00025## wherein n.sup.1 and n.sup.2 are each independently an integer 4, m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0, the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (I) within the polymer are joined to one another in such a way that the bond identified by ## in a particular repeat unit is joined by the bond identified by # in the adjacent repeat unit and the bond identified by in a particular repeat unit is joined by the bond identified by in the adjacent repeat unit, the repeat units of the chemical structure (II) within the polymer are joined to one another in such a way that the bond identified by * in a particular repeat unit is joined by the bond identified by ** in the adjacent repeat unit, the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals are each independently selected from the group consisting of hydrogen, phenyl, benzyl, aliphatic radical optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, R.sup.11, R.sup.13, R.sup.15, R.sup.17 radicals may each independently also be a group of the general structure (III): ##STR00026## wherein the R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35 radicals may independently be as defined for R.sup.1, at least two of A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, A.sup.6 are each an oxygen or sulphur atom and the others of A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, A.sup.6 are each a direct bond, at least two of A.sup.7, A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.12 are each an oxygen or sulphur atom and the others of A.sup.7, A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.12 are each a direct bond, at least two of A.sup.13, A.sup.14, A.sup.15, A.sup.16, A.sup.17, A.sup.18 are each an oxygen or sulphur atom and the others of A.sup.13, A.sup.14, A.sup.15, A.sup.16, A.sup.17, A.sup.18 are each a direct bond, and wherein at least two radicals in ortho positions to one another among the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals and/or at least two radicals in ortho positions to one another among the R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23 radicals and/or at least two radicals in ortho positions to one another among the R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35 radicals may each also be bridged by at least one (hetero)aromatic ring or aliphatic ring optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen, alkyl group and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, the R.sup.1 radical in the case that A.sup.1=direct bond, the R.sup.2 radical in the case that A.sup.2=direct bond, the R.sup.3 radical in the case that A.sup.3=direct bond, the R.sup.4 radical in the case that A.sup.4=direct bond, the R.sup.19 radical in the case that A.sup.12=direct bond, the R.sup.20 radical in the case that A.sup.8=direct bond, the R.sup.21 radical in the case that A.sup.9=direct bond, the R.sup.22 radical in the case that A.sup.10=direct bond, the R.sup.23 radical in the case that A.sup.11=direct bond, the R.sup.31 radical in the case that A.sup.14=direct bond, the R.sup.32 radical in the case that A.sup.15=direct bond, the R.sup.33 radical in the case that A.sup.16=direct bond, the R.sup.34 radical in the case that A.sup.17=direct bond, the R.sup.35 radical in the case that A.sup.18=direct bond and the R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals may each also be selected from the group consisting of nitro group, CN, F, Cl, Br, I, COOR.sup.36, C(O)NHR.sup.37, NR.sup.38R.sup.39, where R.sup.36, R.sup.37, R.sup.38, R.sup.39 are each independently selected from the group consisting of hydrogen, (hetero)aromatic radical, aliphatic radical optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, wherein the R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals may independently also be a radical of the formula OR.sup.40 where R.sup.40 is an aliphatic radical optionally substituted by at least one group selected from nitro group, NH.sub.2, CN, SH, OH, halogen and optionally having at least one group selected from ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, phosphoric ester, B.sup.1, B.sup.2, B.sup.3, B.sup.4 are each independently selected from the group consisting of &(CH.sub.2).sub.p1&& where p1 is an integer from 1 to 4, and where at least one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.r1B.sup.5(CH.sub.2).sub.r2&& where B.sup.5 is a (hetero)aromatic divalent 6-membered ring, 3-membered ring or 5-membered ring and r1, r2 are each 0 or 1, where r1+r21, &(CH.sub.2).sub.q1B.sup.6(CH.sub.2).sub.q2&& with B.sup.6O, S, NH; q1=0, 1, 2 and q2=1, 2, 3 where q1+q23 and where one CH.sub.2 group may also be replaced by C(O), &OC(O)NHCH.sub.2&&, B.sup.1, in the case that A.sup.5=direct bond, B.sup.2 in the case that A.sup.6=direct bond, B.sup.3 in the case that A.sup.7=direct bond, B.sup.4 in the case that A.sup.13=direct bond, may each independently also be selected from the group consisting of &(CH.sub.2).sub.5&& where at least one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.v1B.sup.7(CH.sub.2).sub.v2&& with B.sup.7O, S, NH; v1=0, 1, 2, 3 and v2=1, 2, 3, 4, where v1+v2=4 and where one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.t1B.sup.8(CH.sub.2).sub.t2&& where B.sup.8 is a (hetero)aromatic divalent 3-membered ring, 5-membered ring or 6-membered ring and t1, t2 are each 0 or 2, where t1+t22, &CH.sub.2OC(O)NHCH.sub.2&&, &OC(O)NH&&, &CH.sub.2OC(O)NH&&, &CH.sub.2CH.sub.2OC(O)NH&&, &OC(O)NHCH.sub.2CH.sub.2&&, B.sup.1, in the case that A.sup.5=O or S, B.sup.2 in the case that A.sup.6=O or S, B.sup.3 in the case that A.sup.7=O or S, B.sup.4 in the case that A.sup.13=O or S, may in each case also be a direct bond, in the B.sup.1, B.sup.2, B.sup.3, B.sup.4 radicals, at least one hydrogen atom bonded to a carbon atom or nitrogen atom may be replaced by a halogen atom or an alkyl group, && for B.sup.1 denotes the bond pointing toward A.sup.5, for B.sup.2 the bond pointing toward A.sup.6, for B.sup.3 the bond pointing toward A.sup.7, and for B.sup.4 the bond pointing toward A.sup.13, and & for B.sup.1 denotes the bond pointing toward R.sup.5, for B.sup.2 the bond pointing toward R.sup.8, for B.sup.3 the bond pointing toward R.sup.24, and for B.sup.4 the bond pointing toward R.sup.12 or R.sup.14 or R.sup.16 or R.sup.18.

3: The polymer according to claim 2, comprising n.sup.1 mutually linked repeat units of the chemical structure (I) or n.sup.2 mutually linked repeat units of the chemical structure (II) ##STR00027## wherein n.sup.1 and n.sup.2 are each independently an integer 4 and 5000, m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0 and 5000, the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (I) within the polymer are joined to one another in such a way that the bond identified by ## in a particular repeat unit is joined by the bond identified by # in the adjacent repeat unit and the bond identified by in a particular repeat unit is joined by the bond identified by in the adjacent repeat unit, the repeat units of the chemical structure (II) within the polymer are joined to one another in such a way that the bond identified by * in a particular repeat unit is joined by the bond identified by ** in the adjacent repeat unit, the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals are each independently selected from the group consisting of hydrogen, alkyl group having 1 to 30 carbon atoms, R.sup.22 is an alkyl group having 1 to 30 carbon atoms, the R.sup.11, R.sup.13, R.sup.15, R.sup.17 radicals may each independently also be a group of the general structure (III): ##STR00028## wherein the R.sup.31, R.sup.32, R.sup.34, R.sup.35 radicals are each independently selected from the group consisting of hydrogen, alkyl group having 1 to 30 carbon atoms, R.sup.33 is an alkyl group having 1 to 30 carbon atoms, and wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 may each also be selected from the group consisting of nitro group, CN, F, Cl, Br, I, OR.sup.40 where R.sup.40 is an alkyl group having 1 to 30 carbon atoms, B.sup.1, B.sup.2, B.sup.3, B.sup.4 are each independently selected from the group consisting of direct bond, &(CH.sub.2).sub.p1&& where p1 is an integer from 1 to 4, and where at least one CH.sub.2 group may also be replaced by C(O), &(CH.sub.2).sub.r1B.sup.5(CH.sub.2).sub.r2&& where B.sup.5 is a (hetero)aromatic divalent 6-membered ring, 3-membered ring or 5-membered ring and r1, r2 are each 0 or 1, where r1+r21, &(CH.sub.2).sub.q1B.sup.6(CH.sub.2).sub.q2&& with B.sup.6O, S, NH; q1=0, 1, 2 and q2=1, 2, 3 where q1+q23 and where one CH.sub.2 group may also be replaced by C(O), &OC(O)NHCH.sub.2&&.

4: The polymer according to claim 3, comprising n.sup.1 mutually linked repeat units of the chemical structure (I) or n.sup.2 mutually linked repeat units of the chemical structure (II) ##STR00029## wherein n.sup.1 and n.sup.2 are each independently an integer 10 and 1000, m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0 and 1000, the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, the repeat units of the chemical structure (I) within the polymer are joined to one another in such a way that the bond identified by ## in a particular repeat unit is joined by the bond identified by # in the adjacent repeat unit and the bond identified by in a particular repeat unit is joined by the bond identified by in the adjacent repeat unit, the repeat units of the chemical structure (II) within the polymer are joined to one another in such a way that the bond identified by * in a particular repeat unit is joined by the bond identified by ** in the adjacent repeat unit, the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 radicals are each independently selected from the group consisting of hydrogen, alkyl group having 1 to 8 carbon atoms, R.sup.22 is an alkyl group having 1 to 8 carbon atoms, the R.sup.11, R.sup.13, R.sup.15, R.sup.17 radicals may each independently also be a group of the general structure (III): ##STR00030## wherein the R.sup.31, R.sup.32, R.sup.34, R.sup.35 radicals are each independently selected from the group consisting of hydrogen, alkyl group having 1 to 8 carbon atoms, R.sup.33 is an alkyl group having 1 to 8 carbon atoms, and wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 may each also be selected from the group consisting of nitro group, CN, F, Cl, Br, I, OR.sup.40 where R.sup.40 is an alkyl group having 1 to 8 carbon atoms, B.sup.1, B.sup.2, B.sup.3, B.sup.4 are each independently selected from the group consisting of direct bond, &(CH.sub.2).sub.p1&& where p1 is an integer from 1 to 3, &B.sup.5CH.sub.2&& where B.sup.5=phenylene, &(CH.sub.2).sub.q1B.sup.6(CH.sub.2).sub.q2&& with B.sup.6O, S; q1=0, 1, 2 and q2=1, 2, 3 where q1+q23, &OC(O)NHCH.sub.2&&.

5: The polymer according to claim 4, wherein R.sup.1R.sup.3, R.sup.2R.sup.4, R.sup.19R.sup.21, R.sup.20R.sup.23, R.sup.31R.sup.34, R.sup.32R.sup.35.

6: The polymer according to claim 5, wherein R.sup.1R.sup.3H, R.sup.2R.sup.4=alkyl group having 1 to 8 carbon atoms, R.sup.19 R.sup.21H, R.sup.20R.sup.23=alkyl group having 1 to 8 carbon atoms, R.sup.31R.sup.34H, R.sup.32R.sup.35=alkyl group having 1 to 8 carbon atoms, and B.sup.1, B.sup.2, B.sup.3, B.sup.4 are each independently selected from the group consisting of direct bond, methylene, ethylene, n-propylene, &B.sup.5CH.sub.2&& where B.sup.5=1,4-phenylene.

7: The polymer according to claim 6, wherein R.sup.1R.sup.3H, R.sup.2R.sup.4=alkyl group having 1 to 6 carbon atoms, R.sup.19 R.sup.21H, R.sup.20R.sup.23=alkyl group having 1 to 6 carbon atoms, and R.sup.31 R.sup.34H, R.sup.32R.sup.35=alkyl group having 1 to 6 carbon atoms.

8: The polymer according to claim 7, wherein R.sup.1R.sup.3H, R.sup.2R.sup.4=tert-butyl group, R.sup.19 R.sup.21H, R.sup.20R.sup.23=tert-butyl group, R.sup.31 R.sup.34H, and R.sup.32R.sup.35=tert-butyl group.

9: An electrical charge storage method, comprising employing the polymer according to claim 1 as redox-active electrode material for electrical charge storage.

10: An electrical charge storage method, comprising adding the polymer according to claim 1 in an electrode slurry for electrical charge storage.

Description

FIGURES

[0232] FIG. 1 (=FIG. 1) shows the cyclic voltammogram of 2 (1 mmolar in CH.sub.2Cl.sub.2 with 0.1 M TBAPF.sub.6) at various scan rates (reported in mV/s). The x axis indicates the potential V, the y axis the current in mA.

[0233] FIG. 2 (=FIG. 2) shows the cyclic voltammogram of 5 in CH.sub.2Cl.sub.2 (1 mmolar in CH.sub.2Cl.sub.2 with 0.1 M TBAClO.sub.4) at various scan rates (reported in mV/s). The x axis indicates the potential V, the y axis the current in mA.

[0234] FIG. 3 (=FIG. 3) indicates the measured voltages V (y axis) against the capacity (x axis) of an electrode according to the invention produced with 6 after 1 or 2 or 10 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes; section 4.1). The filled boxes in the diagram correspond to the charging cycles, the empty boxes to the discharging cycles.

[0235] FIG. 4 (=FIG. 4) indicates the measured voltages V (y axis) against the capacity (x axis) of an electrode not according to the invention produced with 13 after 1 or 2 or 10 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes; section 4.2). The filled boxes in the diagram correspond to the charging cycles, the empty boxes to the discharging cycles.

[0236] FIG. 5 (=FIG. 5) indicates the measured voltages V (y axis) against the capacity (x axis) of an electrode not according to the invention produced with 16 after 1 or 2 or 10 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes; section 4.3). The filled boxes in the diagram correspond to the charging cycles, the empty boxes to the discharging cycles.

[0237] The examples which follow are intended to elucidate the present invention without limiting said invention in any way.

EXAMPLES

1. General Remarks

1.1 Abbreviations

[0238] AIBNazobis(isobutyronitrile); DMAPdimethylaminopyridine; DMFdimethylformamide; NEt.sub.3triethylamine; TBAClO.sub.4tetrabutylammonium perchlorate; TBAPF.sub.6tetrabutylammonium hexafluorophosphate; THFtetrahydrofuran; Tol.toluene.

[0239] The numbers in brackets given in the reaction schemes which follow relate to the respective section in which the synthesis has been described.

1.2 Test Methods

[0240] .sup.1H and .sup.13C NMR spectra were recorded with a Bruker AC 300 (300 MHz) spectrometer at 298 K. 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 A).

2. Inventive Examples

2.1 I1: Synthesis and Polymerization of 4,4-(((2,5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(methylene))bis(vinylbenzene) 2

[0241] ##STR00019##

2.1.1 Synthesis of 4,4-(((2,5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(methylene))bis(vinylbenzene) 2

[0242] A 0.5 M solution of 1 (3 g, 13.5 mmol) in THF was added dropwise to an ice-cooled suspension of NaH (1.35 g, 33.7 mmol, 60% dispersion in mineral oil) in 15 mL of THF and, on completion of addition, the mixture was stirred at room temperature for 1 hour. Subsequently, 4-vinylbenzyl chloride (5.6 ml, 40 mmol) was added and the reaction mixture was stirred at 50 C. for 48 hours. The reaction was quenched with water and extracted with dichloromethane. The organic phase was dried with MgSO.sub.4, the solvent was removed under reduced pressure and the residue was precipitated in hexane/CH.sub.2Cl.sub.2 (4:1). 3.95 g (8.7 mmol, 64%) of 2 were obtained as a white solid.

[0243] FIG. 1 (=FIG. 1) shows the cyclic voltammogram of 2 (1 mmolar in CH.sub.2Cl.sub.2 with 0.1 M TBAPF.sub.6) at various scan rates.

[0244] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 7.42 (8H), 6.90 (s, 2H), 6.72 (dd, 2H), 5.76 (d, 2H), 5.24 (d, 2H), 5.06 (s, 4H), 1.36 (s, 18H).

2.1.2 Polymerization of 4,4-(((2,5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(methylene))bis(vinylbenzene) 2 to Give 3

[0245] A 0.5 M solution of 2 (100 mg, 0.22 mmol) in dry DMF and AIBN (1.80 mg, 0.011 mmol) was degassed with argon for 90 min. The degassed solution was stirred at 80 C. for 16 hours. The polymer was precipitated and washed in methanol. This gave 79 mg (0.17 mmol, 78.3%) of 3 as a white solid.

2.2 I2: Synthesis and Polymerization of 1,4-di-tert-butyl-2-methoxy-5-((4-vinylbenzyl)ox)benzene 5

[0246] ##STR00020##

2.2.1 Synthesis of 1,4-di-tert-butyl-2-methoxy-5-((4-vinylbenzyl)oxy)benzene 5

[0247] A 0.4 M solution of 4 (2 g, 8.5 mmol) in THF was added dropwise to an ice-cooled suspension of NaH (507 mg, 12.7 mmol, 60% dispersion in mineral oil) in 10 mL of THF and, on completion of addition, the mixture was stirred at room temperature for another 2 hours. Subsequently, 4-vinylbenzyl chloride (3.6 ml, 25.4 mmol) was added and the reaction mixture was stirred at 50 C. for 48 hours. The reaction was quenched with water and extracted with dichloromethane. The organic phase was dried with MgSO.sub.4, the solvent and 4-vinylbenzyl chloride were removed under reduced pressure and the residue was purified by means of column chromatography (silica gel, toluene/hexane 1:1). 1.9 g (5.4 mmol, 63.5%) of 5 were obtained as a white solid.

[0248] FIG. 2 (=FIG. 2) shows the cyclic voltammogram of 5 in CH.sub.2Cl.sub.2 (1 mmolar in CH.sub.2Cl.sub.2 with 0.1 M TBAClO.sub.4) at various scan rates.

[0249] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 7.45 (4H), 6.90 (2H), 6.75 (dd, 1H), 5.78 (d, 1H), 5.27 (d, 1H), 5.08 (s, 2H), 3.83 (s, 3H), 1.39 (d, 18H).

2.2.2 Polymerization of 1,4-di-tert-butyl-2-methoxy-5-((4-vinylbenzyl)oxy)benzene 5 to give 6

[0250] A 1.0 M solution of 5 (100 mg, 0.28 mmol) in dry DMF and AIBN (1.32 mg, 0.014 mmol) was degassed with argon for 90 min. The degassed solution was stirred at 80 C. for 16 hours. The polymer was precipitated in methanol. This gave 52 mg (0.15 mmol, 51.7%) of 6 as a white solid.

2.3 I3: Synthesis and Polymerization of 1,4-di-tert-butyl-2-methoxy-5-(ethenyloxy)benzene 7

[0251] ##STR00021##

2.3.1 Synthesis of 1,4-di-tert-butyl-2-methoxy-5-(ethenyloxy)benzene 7

[0252] 2,5-Di-tert-butyl-4-methoxyphenol 4 (591 mg, 2.5 mmol), Na.sub.2CO.sub.3 (318 mg, 3 mmol) and [Ir(cod)Cl].sub.2 (16.8 mg, 0.025 mmol) were freed of traces of water and air in a Schlenk flask. Subsequently, dry toluene (2.5 ml) and vinyl acetate (0.29 ml, 3.125 mmol) were added. The solution was stirred at 90 C. under argon for 24 hours. The reaction solution was purified by column chromatography on silica with toluene as eluent. 202 mg (31%) of 7 were obtained as a yellowish solid.

[0253] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.95 (s, 1H), 6.91 (s, 1H), 6.60 (dd, 1H), 4.72 (d, 1H), 4.38 (d, 1H), 3.91 (s, 3H), 1.46 (s, 9H), 1.44 (s, 9H).

2.3.2 Polymerization of 1,4-di-tert-butyl-2-methoxy-5-(ethenyloxy)benzene 7 to give 8

[0254] 1,4-Di-tert-butyl-2-methoxy-5-(ethenyloxy)benzene 7 (65.6 mg, 0.25 mmol) under an argon atmosphere were dissolved in 0.125 ml of dry dichloromethane and cooled to 78C. Subsequently, 5 mol % of BF.sub.3 etherate (1.6 l, 12.5 mol) was added. The reaction mixture was stirred for 24 h, in the course of which it was warmed to room temperature. The gel-like solution was diluted with 1 ml of dichloromethane and precipitated in methanol. The solids were removed by centrifugation, washed with methanol and dried under reduced pressure. 38.8 mg (59% yield) of 8 were obtained in the form of a white powder.

3. Comparative Examples

3.1 C1: Synthesis and Polymerization of ((2,5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(propane-3,1-diyl)bis(2-methyl acrylate) 12

[0255] ##STR00022##

3.1.1 Synthesis of 2-(3-bromopropoxy)tetrahydro-2H-pyran 10

[0256] Stirred into a 0.5 M solution of 1-bromo-3-hydroxypropane 9 (10 g, 72 mmol) in CH.sub.2Cl.sub.2 were p-toluenesulphonic acid hydrate (1.37 g, 7.2 mmol) and dihydropyran (9.8 ml, 107.9 mmol), and the mixture was stirred at room temperature for 16 hours. The reaction was extracted with water. The organic phase was dried with MgSO.sub.4, the solvent was removed under reduced pressure and the residue was purified by means of vacuum distillation. 12.2 g (54.7 mmol, 76%) of 10 were obtained as a colourless oil.

[0257] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 54.52 (s, 1H), 3.78 (m, 2H), 3.46 (m, 4H), 2.05 (m, 2H), 1.68 (m, 2H), 1.46 (m, 4H).

3.1.2 Synthesis of 3,3-((2,5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(propan-1-ol) 11

[0258] To a 0.9 M solution of 1 (1 g, 4.5 mmol) in THF was added dropwise an ice-cooled suspension of NaH (450 mg, 11.2 mmol, 60% dispersion in mineral oil) in 10 mL of THF and, on completion of addition, the mixture was stirred at room temperature for another 2 hours. Subsequently, 10 (5.02 g, 22.5 mmol) was added and the reaction mixture was stirred at 50 C. for 24 hours. The reaction was quenched with water and extracted with dichloromethane. The organic phase was dried with MgSO.sub.4 and the solvent was removed under reduced pressure. Without further purification, the residue was taken up in 50 ml of methanol, and 20 ml of 2 M HCl were added. After detachment of the protecting group (monitoring by TLC), the product was extracted with dichloromethane and dried over MgSO.sub.4, and the solvent was removed under reduced pressure. The residue was purified by means of column chromatography (silica gel, hexane/ethyl acetate, 1:1). 853 mg (2.5 mmol, 56%) of 11 were obtained as a white solid.

[0259] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.85 (s, 2H), 4.10 (t, 4H), 3.92 (t, 4H), 2.09 (m, 4H), 1.37 (s, 18H).

3.1.3 Synthesis of ((2, 5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(propane-3,1-diyl)-bis(2-methyl acrylate) 12

[0260] 11 (505 mg, 1.5 mmol) and DMAP (18 mg, 0.15 mmol) were inertized 10 ml of dry THF, triethylamine (820 l, 5.9 mmol) and methacryloyl chloride (570 l, 5.9 mmol) were added while cooling and the mixture was stirred at room temperature for 16 hours. The reaction was quenched with water and extracted with dichloromethane. The organic phase was dried with MgSO.sub.4 and the solvent was removed under reduced pressure. The residue was purified by means of column chromatography (silica gel, hexane/ethyl acetate, 4:1). 565 mg (1.2 mmol, 80.6%) of 12 were obtained as a white solid.

[0261] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.83 (s, 2H), 6.12 (s, 2H), 5.56 (s, 2H), 4.39 (t, 4H), 4.07 (t, 4H), 2.21 (m, 4H), 1.95 (s, 6H), 1.37 (s, 18H).

3.1.4 Polymerization of ((2,5-di-tert-butyl-1,4-phenylene)bis(oxy))bis(propane-3,1-diyl)bis(2-methyl acrylate) 12 to Give 13

[0262] A 0.5 M solution of 12 (100 mg, 0.210 mmol) in dry DMF and AIBN (1.72 mg, 0.011 mmol) was degassed with argon for 90 min. The degassed solution was stirred at 80 C. for 16 hours. The polymer was precipitated and washed in methanol. This gave 65 mg (0.178 mmol, 84.3%) of 13 as a white solid.

3.2 C2: Synthesis and Polymerization of 3-(2,5-di-tert-butyl-4-methoxyphenoxy)propyl methacrylate 15

[0263] ##STR00023##

3.2.1 Synthesis of 3-(2,5-di-tert-butyl-4-methoxyphenoxy)propan-1-ol 14

[0264] A 0.8 M solution of 4 (2 g, 8.5 mmol) in THF was added dropwise to an ice-cooled suspension of NaH (507 mg, 12.7 mmol, 60% dispersion in mineral oil) in 10 mL of THF and, on completion of addition, the mixture was stirred at room temperature for another 2 hours. Subsequently, 10 (5.66 g, 25.4 mmol) was added and the reaction mixture was stirred at 50 C. for 48 hours. The reaction was quenched with water and extracted with dichloromethane. The organic phase was dried with MgSO.sub.4 and the solvent was removed under reduced pressure. The residue was taken up in 50 ml of methanol, and 20 ml of 2 M HCl were added. After detachment of the protecting group, the product was extracted with dichloromethane and dried over MgSO.sub.4, and the solvent was removed under reduced pressure. The residue was purified by means of gel filtration (silica gel, hexane/ethyl acetate, 4:1). 1.62 g (5.5 mmol, 65%) of 14 were obtained as a white solid.

[0265] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.84 (2H), 4.11 (t, 2H), 3.92 (t, 2H), 3.81 (s, 3H), 2.09 (m, 2H), 1.37 (18H).

3.2.2 Synthesis of 3-(2,5-di-tert-butyl-4-methoxyphenoxy)propyl methacrylate 15

[0266] 14 (500 mg, 1.7 mmol) and DMAP (20.8 mg, 0.17 mmol) were inertized. 10 ml of dry THF, triethylamine (940 l, 6.8 mmol) and methacryloyl chloride (660 l, 6.8 mmol) were added while cooling and the mixture was stirred at room temperature for 16 hours. The reaction was quenched with water and extracted with dichloromethane. The organic phase was dried with MgSO.sub.4 and the solvent was removed under reduced pressure. The residue was purified by means of column chromatography (silica gel, hexane/ethyl acetate, 4:1). 545 mg (1.5 mmol, 88.5%) of 15 were obtained as a white solid.

[0267] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.83 (2H), 6.12 (s, 1H), 5.56 (s, 1H), 4.39 (t, 2H), 4.07 (t, 2H), 3.80 (s, 3H), 2.21 (m, 2H), 1.95 (s, 3H), 1.36 (18H).

3.2.3 Polymerization of 3-(2,5-di-tert-butyl-4-methoxyphenoxy)propyl methacrylate 15 to give 16

[0268] A 0.5 M solution of 15 (100 mg, 0.275 mmol) in dry toluene and AIBN (1.72 mg, 0.13 mmol) was degassed with argon for 90 min. The degassed solution was stirred at 80 C. for 16 hours. The polymer was precipitated in methanol. This gave 65 mg (0.18 mmol, 64.5%) of 16 as a white solid.

4. Production of the Electrodes

4.1 Production of an Electrode Comprising 6 (Inventive Example)

[0269] 6 (prepared as described in section 2.2.2) was processed in a mortar to give a fine powder. Subsequently added to 5 mg of 6 and 5 mg of poly(vinylidene fluoride) (PVDF; Sigma Aldrich as binder additive) was 0.5 ml of NMP (N-methyl-2-pyrrolidone), and the mixture was stirred for 4 h. This solution was added to 40 mg of Super P (carbon particles from Sigma-Aldrich, as conductivity additive) and the mixture was mixed in a mortar for ten minutes until a homogeneous paste formed. This paste was applied to an aluminium foil (15 m, MIT Corporation). The resultant electrode was dried at 45 C. under reduced pressure for 16 hours. The proportion of the active material on the electrodes was determined on the basis of the masses of dried electrodes. The button cells (2032 type) were constructed under an argon atmosphere. Suitable electrodes were punched out with the aid of an MIT Corporation Precision Disc Cutter (diameter 15 mm). The electrode being used as cathode was positioned at the base of the button cell and separated from the lithium anode with the aid of a porous polypropylene membrane (Celgard, MIT Corporation). Subsequently positioned atop the lithium anode were a stainless steel weight (diameter: 15.5 mm, thickness: 0.3 mm, MIT Corporation) and a stainless steel spring (diameter: 14.5 mm, thickness: 5 mm). The button cell was filled with electrolyte (EC/DMC 3/7, 0.5 M LiClO.sub.4) and covered with the lid before being sealed with an electrical compression machine (MIT Corporation MSK-100D).

[0270] In the first discharge cycle, the battery showed a capacity of 67 mAh/g (88% of the theoretically possible capacity); after 10 charge/discharge cycles (charging rate 1 C), the battery shows a capacity of 50 mAh/g (FIG. 3=FIG. 3).

4.2 Production of an Electrode Comprising 13 (Comparative Example)

[0271] 13 (prepared as described in section 3.1.4) was processed in a mortar to give a fine powder. Subsequently added to 15 mg of 13 and 5 mg of poly(vinylidene fluoride) (PVDF; Sigma Aldrich as binder additive) was 0.5 ml of NMP (N-methyl-2-pyrrolidone), and the mixture was stirred for 4 h. This solution was added to 30 mg of Super P (Sigma-Aldrich, as conductivity additive) and the mixture was mixed in a mortar for ten minutes until a homogeneous paste formed. This paste was applied to an aluminium foil (15 m, MIT Corporation). The resultant electrode was dried at 45 C. under reduced pressure for 16 hours. The proportion of the active material on the electrodes was determined on the basis of the masses of dried electrodes. The button cells (2032 type) were constructed under an argon atmosphere. Suitable electrodes were punched out with the aid of an MIT Corporation Precision Disc Cutter (diameter 15 mm). The electrode being used as cathode was positioned at the base of the button cell and separated from the lithium anode with the aid of a porous polypropylene membrane (Celgard, MIT Corporation). Subsequently positioned atop the lithium anode were a stainless steel weight (diameter: 15.5 mm, thickness: 0.3 mm, MIT Corporation) and a stainless steel spring (diameter: 14.5 mm, thickness: 5 mm). The button cell was filled with electrolyte (EC/DMC 3/7, 0.5 M LiClO.sub.4) and covered with the lid before being sealed with an electrical compression machine (MIT Corporation MSK-100D).

[0272] In the first discharge cycle, the battery showed a capacity of 34 mAh/g (60% of the theoretically possible capacity); after 10 charge/discharge cycles (charging rate 1 C), the battery shows a capacity of 24 mAh/g (FIG. 4=FIG. 4).

4.3 Production of an Electrode Comprising 16 (Comparative Example)

[0273] 16 (prepared as described in section 3.2.3) was processed in a mortar to give a fine powder. Subsequently added to 5 mg of 16 and 5 mg of poly(vinylidene fluoride) (PVDF; Sigma Aldrich as binder additive) was 0.5 ml of NMP (N-methyl-2-pyrrolidone), and the mixture was stirred for 4 h. This solution was added to 40 mg of Super P (Sigma-Aldrich, as conductivity additive) and the mixture was mixed in a mortar for ten minutes until a homogeneous paste formed. This paste was applied to an aluminium foil (15 m, MIT Corporation). The resultant electrode was dried at 45 C. under reduced pressure for 16 hours. The proportion of the active material on the electrodes was determined on the basis of the masses of dried electrodes. The button cells (2032 type) were constructed under an argon atmosphere. Suitable electrodes were punched out with the aid of an MIT Corporation Precision Disc Cutter (diameter 15 mm). The electrode being used as cathode was positioned at the base of the button cell and separated from the lithium anode with the aid of a porous polypropylene membrane (Celgard, MIT Corporation). Subsequently positioned atop the lithium anode were a stainless steel weight (diameter: 15.5 mm, thickness: 0.3 mm, MIT Corporation) and a stainless steel spring (diameter: 14.5 mm, thickness: 5 mm). The button cell was filled with electrolyte (EC/DMC 3/7, 0.5 M LiClO.sub.4) and covered with the lid before being sealed with an electrical compression machine (MIT Corporation MSK-100D).

[0274] In the first discharge cycle, the battery showed a capacity of 55 mAh/g (81% of the theoretically possible capacity); after 10 charge/discharge cycles (rate 1 C), the battery shows a capacity of 41 mAh/g (FIG. 5=FIG. 5).

5. Results

[0275] The batteries which were obtained with electrodes made from inventive polymers (section 4.1, FIG. 3) show a discharge capacity after the first charge/discharge cycle of 67 mAh/g and a discharge capacity of 50 mAh/g after 10 discharge cycles. This is much higher than the discharge capacity which is achieved with batteries made from electrodes made from prior art polymers, namely 34 mAh/g after the 1st charge/discharge cycle and 24 mAh/g after the 10th charge/discharge cycle with a battery according to section 4.2, and 55 mAh/g after the 1st charge/discharge cycle and 41 mAh/g after the 10th charge/discharge cycle with a battery according to section 4.3. The polymer according to the invention therefore enables batteries having both higher discharge voltage and higher discharge capacity even after several charge/discharge cycles. In addition, it was possible to prepare the polymers according to the invention in a much less resource-intensive manner.