USE OF PARTICULAR POLYMERS AS CHARGE STORAGE MEANS

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. The secondary batteries are especially notable for high cell voltages, and high capacities after undergoing several charging and discharging cycles, and simple and scalable processing and production methods (for example by means of screen printing).

Claims

1. Polymer 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) with ##STR00019## where n.sup.1 and n.sup.2 are each independently an integer4, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer0, where the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, where the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, where 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, where 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, where H.sup.1, H.sup.2, H.sup.3, H.sup.4, H.sup.5, H.sup.6 are independently selected from O, S, NR, CRR, where the R, R, R, 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, where 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, where 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, and where 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, and where 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.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.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 where the R, 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, where 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, are each independently selected from the group consisting of direct bond, &(X.sup.1).sub.p1[CX.sup.2].sub.p2(X.sup.3).sub.p3B.sup.5(Y.sup.2).sub.q2[CY.sup.1].sub.q1&&, &(Y.sup.3).sub.q3(CY.sup.4)&&, and where 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, are independently selected from the group consisting of &(X.sup.4).sub.p4[CX.sup.5].sub.p5 (X.sup.6).sub.p6B.sup.6(Y.sup.7).sub.q6[CY.sup.6].sub.q5(Y.sup.5).sub.q4&&, &(Y.sup.10).sub.q9(CY.sup.9).sub.q8(Y.sup.8).sub.q7&&, where p1, p2, p3 are each 0 or 1, with the proviso that it is not simultaneously true that p1=p3=1 and p2=0, where p4, p5, p6 are each 0 or 1, with the proviso that it is not simultaneously true that p4=p6=1 and p5=0, where q1, q2 are each 0 or 1, where, when q1=0, then q2=0, where q3=0 or 1, where q4, q5, q6 are each 0 or 1, with the proviso that it is not simultaneously true that q4=q6=1 and q5=0, where q7, q8, q9 are each 0 or 1, with the proviso that it is not simultaneously true that q7=q9=1 and q8=0, and that, when q7=1 and q8=0, then q9=0, where X.sup.2, X.sup.5, Y.sup.1, Y.sup.4, Y.sup.6, Y.sup.9 are independently selected from the group consisting of oxygen, sulphur, where X.sup.1, X.sup.3, X.sup.4, X.sup.6, Y.sup.2, Y.sup.3, Y.sup.7, Y.sup.10 are independently selected from the group consisting of O, S, NH, N-alkyl, where Y.sup.5, Y.sup.8 is selected from NH, N-alkyl, where B.sup.5, B.sup.6 are independently selected from the group consisting of divalent (hetero)aromatic radical, divalent 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 where && 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 where & 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. 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) with ##STR00020## where n.sup.1 and n.sup.2 are each independently an integer4, especially 4 and 5000, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer0, especially 0 and 5000, where the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, where the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, where 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, where 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, where H.sup.1, H.sup.2, H.sup.3, H.sup.4, H.sup.5, H.sup.6 are independently selected from O, CRR, where the R, R, 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, and where 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) with ##STR00021## in which 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, where 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, especially an oxygen atom, and the others of A, A2, A3, A4, A.sup.5, A.sup.6 are each a direct bond, where 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, especially an oxygen 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, where 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, especially an oxygen 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 where 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, and where 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, R, 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 where the R, 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, where 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, are independently selected from the group consisting of direct bond, &(X.sup.1).sub.p1[CX.sup.2].sub.p2(X.sup.3).sub.p3B.sup.5(Y.sup.2).sub.q2[CY.sup.1].sub.q1 &&, &(Y.sup.3).sub.q3(CY.sup.4)&&, and where 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, are independently selected from the group consisting of &(X.sup.4).sub.p4[CX.sup.5].sub.p5(X.sup.6).sub.p6B.sup.6(Y.sup.7).sub.q6[CY.sup.6].sub.q5(Y.sup.5).sub.q4&&, &(Y.sup.10).sub.q9(CY.sup.9).sub.q8(Y.sup.8).sub.q7&&, where p1, p2, p3 are each 0 or 1, with the proviso that it is not simultaneously true that p1=p3=1 and p2=0, where p4, p5, p6 are each 0 or 1, with the proviso that it is not simultaneously true that p4=p6=1 and p5=0, where q1, q2 are each 0 or 1, where, when q1=0, then q2=0, where q3=0 or 1, where q4, q5, q6 are each 0 or 1, with the proviso that it is not simultaneously true that q4=q6=1 and q5=0, where q7, q8, q9 are each 0 or 1, with the proviso that it is not simultaneously true that q7=q9=1 and q8=0, and that, when q7=1 and q8=0, then q9=0, where X.sup.2, X.sup.5, Y.sup.1, Y.sup.4, Y.sup.6, Y.sup.9 are independently selected from the group consisting of oxygen, sulphur, where X.sup.1, X.sup.3, X.sup.4, X.sup.6, Y.sup.2, Y.sup.3, Y.sup.7, Y.sup.10 are independently selected from the group consisting of O, S, NH, N-alkyl, where the alkyl group especially has 1 to 10 carbon atoms, where Y.sup.5, Y.sup.8 is selected from NH, N-alkyl, where the alkyl group especially has 1 to 10 carbon atoms, where B.sup.5, B.sup.6 are independently selected from the group consisting of divalent (hetero)aromatic radical, divalent 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 especially a divalent aliphatic radical optionally having at least one group selected from ether, thioether, amino ether, and where && 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 where & 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. 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) with ##STR00022## where n.sup.1 and n.sup.2 are each independently an integer4 and 5000, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer0 and 5000, where the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, where the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, where 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, where 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, where H.sup.1, H.sup.2, H.sup.3, H.sup.4, H.sup.5, H.sup.6 are independently selected from O, CH.sub.2, where 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, and where R.sup.22 is an alkyl group having 1 to 30 carbon atoms, and where 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) with ##STR00023## where 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, and where R.sup.33 is an alkyl group having 1 to 30 carbon atoms, and where 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, where B.sup.1, B.sup.2, B.sup.3, B.sup.4 are independently selected from the group consisting of direct bond, &(X.sup.1).sub.p1[CX.sup.9].sub.p2(X.sup.3).sub.p3B.sup.5(Y.sup.2).sub.q2[CY.sup.1].sub.q1&&, &(Y.sup.3).sub.q3(CY.sup.4)&&, where p1, p2, p3 are each 0 or 1, with the proviso that it is not simultaneously true that p1=p3=1 and p2=0, where q1, q2 are each 0 or 1, where, when q1=0, then q2=0, where q3=0 or 1, where X.sup.2, Y.sup.1, Y.sup.4 are independently selected from the group consisting of oxygen, sulphur, where X.sup.1, X.sup.3, Y.sup.2, Y.sup.3 are independently selected from the group consisting of O, S, and where B.sup.5 is selected from the group consisting of &-phenylene-CH.sub.2&&, a divalent aliphatic radical optionally having at least one group selected from ether, thioether, amino ether.

4. 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) with ##STR00024## where n.sup.1 and n.sup.2 are each independently an integer10 and 1000, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer0 and 1000, where the repeat units of the chemical structure (I) within the polymer are the same or at least partly different from one another, where the repeat units of the chemical structure (II) within the polymer are the same or at least partly different from one another, where 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, where 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, where 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, and where R.sup.22 is an alkyl group having 1 to 8 carbon atoms, and where 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) with ##STR00025## where 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, and where R.sup.33 is an alkyl group having 1 to 8 carbon atoms, and where 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, where B.sup.1, B.sup.2, B.sup.3, B.sup.4 are independently selected from the group consisting of direct bond, &(O).sub.p1[CO].sub.p2(O).sub.p3B.sup.5&&, where p1, p2, p3 are each 0 or 1, with the proviso that it is not simultaneously true that p1=p3=1 and p2=0, B.sup.5=alkylene group having 1 to 30 carbon atoms.

5. Polymer according to claim 4, where 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. Polymer according to claim 5, where R.sup.1R.sup.3H, R.sup.2R.sup.4=alkyl group having 1 to 8 carbon atoms, R.sup.19R.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, &[(CO)O].sub.rB.sup.5&& where r=0 or 1 and where B.sup.5=methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene or phenylene.

7. Polymer according to claim 6, where R.sup.1R.sup.3H, R.sup.2R.sup.4=alkyl group having 1 to 6 carbon atoms, R.sup.19R.sup.20H, R.sup.20R.sup.23=alkyl group having 1 to 6 carbon atoms, R.sup.31R.sup.34H, R.sup.32R.sup.35=alkyl group having 1 to 6 carbon atoms.

8. Polymer according to claim 7, where R.sup.1R.sup.3H, R.sup.2R.sup.4=tert-butyl group, R.sup.19R.sup.20H, R.sup.20R.sup.23=tert-butyl group, R.sup.31R.sup.34H, R.sup.32R.sup.35=tert-butyl group.

9. Use of the polymers according to claim 1 as redox-active electrode material for electrical charge storage means.

10. Use of the polymers according to claim 1 in an electrode slurry for electrical charge storage means.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0278] FIG. 1 (=FIG. 1) shows the cyclic voltammogram of 3 (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.

[0279] FIG. 2 (=FIG. 2) shows the cyclic voltammogram of 5 (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.

[0280] 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 4 after 1 or 2 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes; section 4.1). The filled boxes in the diagram denote the charging cycles, the empty boxes the discharging cycles.

[0281] 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.

[0282] 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.

[0283] The invention is to be illustrated in detail hereinafter by the working examples for preparation and use shown in the drawings, without being limited thereto.

[0284] Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.

EXAMPLES

1. General Remarks

1.1 Abbreviations

[0285] AIBNazobis(isobutyronitrile); Ccarbon particles; DMAPdimethylaminopyridine; DMFdimethylformamide; DMSOdimethyl sulphoxide; GGrubbs catalyst (2nd); NEt.sub.3triethylamine; ovovernight; TBAClO.sub.4-tetrabutylammonium perchlorate; TBAPF.sub.6tetrabutylammonium hexafluorophosphate; THFtetrahydrofuran; Tol.toluene; TosCltoluenesulphonyl chloride.

1.2 Test Methods

[0286] .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 5-((2,5-di-tert-butyl-4-methoxyphenoxy)methyl)bicyclo[2.2.1]hept-2-ene 3

[0287] ##STR00014##

2.1.1 Synthesis of bicyclo[2.2.1]hept-5-en-2-ylmethyl 4-methylbenzenesulphonate 2

[0288] 5-Norbornene-2-methanol 1 (4.4 g, 35.5 mmol) and p-toluenesulphonyl chloride (10.1 g, 53 mmol) were dissolved in 20 ml of CH.sub.2Cl.sub.2. The solution was cooled to 0 C. and 7.4 ml (53 mmol) of triethylamine were added dropwise. On completion of addition, the ice bath was removed and the reaction mixture was stirred for 14 hours. The reaction solution was subsequently quenched with water and extracted with CH.sub.2Cl.sub.2. The organic phase was washed with distilled water and dried over magnesium sulphate, the solvent was removed under reduced pressure and the residue was purified by means of column chromatography (silica gel, toluene/n-hexane 3/1). 6.8 g (69%) of a colourless oil 2 were obtained.

[0289] .sup.1HNMR (CDCl.sub.3, 300 MHz, ppm): 7.77 (d, 2H), 7.34 (d, 2H), 6.00-6.11 (m, 1.3H), 5.57 (in, 0.7H), 3.44-4.10 (m, 2H), 2.75 (in 1.7H), 2.58 (m, 0.311), 2.49 (m, 2H), 2.42 (s, 311), 2.33 (m, 111), 1.52-1.70 (m, 1H), 1.06-1.33 (in, 1.3H), 0.4 (in, 0.7H).

2.1.2 Synthesis of 5-((2,5-di-tert-butyl-4-methoxyphenoxy)methyl)bicyclo[2.2.1]hept-2-ene 3

[0290] KOH (473.5 mg, 8.44 mmol) was suspended in 10 ml of DMSO and degassed with argon. Thereafter, 2,5-di-tert-butyl-4-methoxyphenol (0.5 g, 2.11 mmol) and bicyclo[2.2.1]hept-5-en-2-yl methylbenzenesulphonate 2 (880 mg, 3.17 mmol) were added. The reaction mixture was stirred at 50 C. for 14 hours. Subsequently, the reaction solution was quenched with water and extracted with CH.sub.2Cl.sub.2. The organic phase was washed to neutrality with distilled water and dried over magnesium sulphate. The solvent was removed under reduced pressure and the residue was purified by means of column chromatography (silica gel, chloroform/n-hexane 1/1). 542 mg (75%) of a white solid 3 were isolated.

[0291] .sup.1HNMR (CDCl.sub.3, 300 MHz, ppm): 6.61-6.80 (m, 211), 5.89-6.13 (m, 2H), 3.82-3.94 (m, 0.8H), 3.73 (s, 3H), 3.58-3.65 (in, 0.6H), 3.38-3.47 (m, 0.6H), 3.03 (m, 0.6H), 2.74-2.87 (m, 1.4H), 2.45-2.59 (m, 0.6H), 1.79-1.93 (m, 1H), 1.17-1.47 (m, 20.8H), 0.54-0.62 (0.6H).

2.1.3 Polymerization of 5-((2,5-di-tert-butyl-4-methoxyphenoxy)methyl)bicyclo[2.2.1]hept-2-ene 3 to give 4

[0292] To a 0.5 M solution of 5-((2,5-di-tert-butyl-4-methoxyphenoxy)methyl)bicyclo[2.2.1]hept-2-ene 3 (80 mg, 0.234 mmol) in CH.sub.2Cl.sub.2 was added Grubbs catalyst, 2.sup.nd Generation (3.96 mg, 0.00467 mmol), and the mixture was stirred at room temperature for 14 hours. Thereafter, the mixture was quenched with 50 l of ethyl vinyl ether and the polymer was precipitated in methanol. 62 mg (78%) of a grey-white polymer are obtained.

2.2 I2: Synthesis and polymerization of 5,5-(2,5-di-tert-butyl-1,4-phenylene)bis(oxy)bis(methylene)bis(bicyclo[2.2.1]hept-2-ene) 5

[0293] ##STR00015##

2.2.1 Synthesis of 5,5-(2,5-di-tort-butyl-1,4-phenylene)bis(oxy)bis(methylene)bis(bicyclo[2.2.1]hept-2-ene) 5

[0294] KOH (1 g, 17.98 mmol) was suspended in 15 ml of DMSO and degassed with argon. Thereafter, 2,5-di-tert-butylhydroquinone (0.5 g, 2.25 mmol) and bicyclo[2.2.1]hept-5-en-2-yl methylbenzenesulphonate 2 (1.885 g, 6.75 mmol) were dissolved in 5 ml of DMSO and added. The reaction mixture was stirred at 50 C. for 14 hours. Subsequently, the reaction solution was quenched with water and extracted with CH.sub.2Cl.sub.2. The organic phase was washed to neutrality with distilled water and dried over magnesium sulphate. The solvent was removed under reduced pressure and the residue was purified by means of column chromatography (silica gel, diethyl ether/n-hexane 1/9). 586 mg (60%) of a white solid were isolated.

[0295] .sup.1HNMR (CDCl.sub.3, 300 MHz, ppm): 7.61-7.72 (m, 2H), 7.34 (d, 2H), 5.89-6.12 (m, 4H), 5.57 (m, 0.7H), 3.38-3.93 (m, 4H), 3.05 (m 0.7H), 2.8 (m, 3.3H), 1.82 (m, 2H), 1.52-1.70 (m, 1H), 1.19-1.40 (m, 25H).

2.2.2 Polymerization of 5,5-(((2,5-di-tert-butyl-1,4-phenylene)bis(oxy)bis(methylene)bis(bicyclo[2.2.1]hept-2-ene 5 to give 6

[0296] To a 0.5 M solution of 5,5-(((2,5-di-tert-butyl-1,4-phenylene)bis(oxy)bis(methylene)bis(bicyclo[2.2.1]hept-2-ene 5 (80 mg, 0.184 mmol) in CH.sub.2Cl.sub.2 was added Grubbs catalyst, 2nd Generation (3.1 mg, 0.00368 mmol), and the mixture was stirred at room temperature for 1 hour. Thereafter, the mixture was quenched with 50 of ethyl vinyl ether and the gel was precipitated in diethyl ether. 73 mg (91%) of a grey-white polymer were obtained.

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-methylacrylate) 12

[0297] ##STR00016## ##STR00017##

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

[0298] 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.

[0299] .sup.1HNMR (CDCl.sub.3, 300 MHz, ppm): 4.52 (s, 1H), 3.78 (m, 2H), 3.46 (m, 4H), 2.05 (m, 2H), 1.68 (m, 2H), 1.46 (in, 4H).

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

[0300] To a 0.9 M solution of 7 (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.

[0301] .sup.1HNMR (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

[0302] 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.

[0303] .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-diyl)bis(2-methyl acrylate) 12 to give 13

[0304] 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 mixture 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.

[0305] 3.2 C2: Synthesis and polymerization of 3-(2,5-di-tert-butyl-4-methoxyphenoxyl)propyl methacrylate 15

##STR00018##

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

[0306] A 0.8 M solution of 8 (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, n-hexane/ethyl acetate, 4:1). 1.62 g (5.5 mmol, 65%) of 14 were obtained as a white solid.

[0307] .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

[0308] 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, n-hexane/ethyl acetate, 4:1). 545 mg (1.5 mmol, 88.5%) of 15 were obtained as a white solid.

[0309] .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 to give 16

[0310] 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 mixture 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 4 (Inventive Example)

[0311] 4 (prepared as described in section 2.1.3) was processed in a mortar to give a fine powder. Subsequently added to 5 mg of 4 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).

[0312] In the first discharge cycle, the battery shows a capacity of 46 mAh/g (59% of the theoretically possible capacity); after 2 charge/discharge cycles, the battery shows a capacity of more than 56 mAh/g (FIG. 3).

4.2 Production of an Electrode Comprising 13 (Comparative Example)

[0313] 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).

[0314] 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)

[0315] 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 mm, 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).

[0316] 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

[0317] The batteries which were obtained with electrodes made from inventive polymers (section 4.1, FIG. 3) show a discharge capacity after the second charge/discharge cycle of 56 mAh/g. This is much higher than the discharge capacity in the second cycle which is achieved with batteries made from electrodes made from prior art polymers, namely less than mAh/g in the 2nd charge/discharge cycle and 24 mAh/g after the 10th charge/discharge cycle with a battery according to section 4.2, and less than 50 mAh/g after the 2nd 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 high discharge capacity after undergoing several charge/discharge cycles. In addition, polymers according to the invention can be produced in a less resource-intensive manner.

[0318] European patent application EP15182454 filed Aug. 26, 2015, is incorporated herein by reference.

[0319] Numerous modifications and variations on the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.