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, even when 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 integer 4, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0, 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.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.25, R.sup.27, R.sup.29 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 A1, 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.2 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.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.25, R.sup.27, R.sup.29 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.sup.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.25, R.sup.27, R.sup.29 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 which joins B.sup.1 to the double bond, for B.sup.2 the bond which joins B.sup.2 to the double bond, and for B.sup.3 the bond which joins B.sup.3 to the double bond.

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 integer 4, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0, 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.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.25, R.sup.27, R.sup.29 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, 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.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, 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, 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.sup.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.25, R.sup.27, R.sup.29 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.sup.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.25, R.sup.27, R.sup.29 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 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, 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 which joins B.sup.1 to the double bond, for B.sup.2 the bond which joins B.sup.2 to the double bond, for B.sup.3 the bond which joins B.sup.3 to the double bond, and for B.sup.4 the bond which joins B.sup.4 to the double bond.

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 integer 4 and 5000, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer 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 the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.19, R.sup.20, R.sup.21, R.sup.23, R.sup.25, R.sup.27, R.sup.29 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 the R.sup.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.25, R.sup.27, R.sup.29 radicals 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.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)-&&, 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 integer 10 and 1000, where m.sup.1, m.sup.2, m.sup.3 are each independently an integer 0 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 4 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.6, R.sup.9, R.sup.13, R.sup.15, R.sup.17, R.sup.19, R.sup.20, R.sup.21, R.sup.23, R.sup.25, R.sup.27, R.sup.29 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.6, R.sup.9, R.sup.11, R.sup.13, R.sup.15, R.sup.17, R.sup.25, R.sup.27, R.sup.29 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 is an 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, methylene, ethylene, n-propylene, &-B.sup.5CH.sub.2-&& where B.sup.5=1,4-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.21H, 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.21H, R.sup.20R.sup.23=tort-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 DRAWINGS

[0254] FIG. 1 indicates the measured voltages V (y axis) against the capacity (x axis) of an electrode according to the invention produced with 3 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.

[0255] FIG. 2 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 or 50 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes; section 4.2). The filled boxes in the diagram denote the charging cycles, the empty boxes the discharging cycles.

[0256] 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.

[0257] 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

[0258] AIBNazobis(isobutyronitrile); Ccarbon particles; Cl-Ph-Chlorobenzene; DMAPdimethylaminopyridine; DMFdimethylformamide; NEt.sub.3triethylamine; ovovernight; RTroom temperature; TBAClO.sub.4tetrabutylammonium perchlorate; TBAPF.sub.6tetrabutylammoniurn hexafluorophosphate; THFtetrahydrofuran; Tol.toluene.

1.2 Test Methods

[0259] .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 ).

2. Inventive Examples

2.1 I1: Synthesis and polymerization of 1,4-di-tert-butyl-2,5-bis(prop-2-yn-1-yloxy)benzene 2

[0260] ##STR00014##

2.1.1 Synthesis of 1,4-di-tertt-butyl-2,5-bis(prop-2-yn-1-yloxy)benzene 2

[0261] A 0.5 M solution of 2,5-di-tert-butylhydroquinone 1 (2.22 g, 10 mmol) in THF was added dropwise to an ice-cooled suspension of NaH (1 g, 25 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 1 hour. Subsequently, propargyl bromide (2.68 ml, 30 mmol, 80 w % in toluene) was added and the reaction mixture was stirred at 40 C. for 16 hours. The reaction was quenched with water and extracted with diethyl ether. The organic phase was dried with MgSO.sub.4, the solvent was removed under reduced pressure and the residue was purified by means of column chromatography (silica gel, CH.sub.2Cl.sub.2/heptane, 1/1). 2.66 g (8.9 mmol, 89%) of 5 were obtained in the form of a pale yellow solid.

[0262] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 7.00 (s, 2H), 4.70 (d, 4H), 2.52 (t, 2H), 1.28 (s, 18H).

2.1.2 Polymerization of 1,4-di-tert-butyl-2,5-bis(prop-2-yn-1-yloxy)benzene 2 in the presence of carbon to give 3

[0263] 1,4-Di-tert-butyl-2,5-bis(prop-2-yn-1-yloxy)benzene 2 (40 mg, 0.13 mmol) and 80 mg of Super P were inertized and dispersed with 4 ml of chlorobenzene. Rhodium norbornadiene tetraphenylborate (5 mol %, 3.4 mg, 6.7 mol) in 50 l of chlorobenzene were inertized by 3 freeze-pump-thaw cycles. Subsequently, the initiator was added to the monomer and the reaction was stirred at room temperature for 16 hours. The gel obtained was transferred directly into a Soxhlet apparatus. It was extracted therein with acetonitrile and diethyl ether and then dried. 109 mg of 3 were obtained in the form of a black powder.

[0264] Elemental analysis: C, 94.29%; H, 2.49%; corresponds to about 28% polymer in composite.

2.2 I2: Synthesis and polymerization of 1,4-di-tert-butyl-2-(prop-2-yn-1-yloxy)-5-methoxybenzene 5

[0265] ##STR00015##

2.2.1 Synthesis of 1,4-di-tert-butyl-2-(prop-2-yn-1-yloxy)-5-methoxybenzene 5

[0266] A 0.5 M solution of 2,5-di-tert-butyl-4-methoxyphenol 4 (2.36 g, 10 mmol) in THF was added dropwise to an ice-cooled suspension of NaH (600 mg, 15 mmol, 60% dispersion in mineral oil) in 8 ml of THF and, on completion of addition, the mixture was stirred at room temperature for another 1 hour. Subsequently, propargyl bromide (1.34 ml, 15 mmol, 80% by weight in toluene) was added and the reaction mixture was stirred at 40 C. for 16 hours. The reaction was quenched with water and extracted with diethyl ether. The organic phase was dried with MgSO.sub.4, the solvent was removed under reduced pressure and the residue was obtained by means of column chromatography (silica gel, CH.sub.2Cl.sub.2/heptane, 1/1). 2.17 g (7.9 mmol, 79%) of 5 were obtained in the form of a pale yellow oil.

[0267] .sup.1H NMR (CDCl.sub.1, 300 MHz, ppm): 7.00 (s, 1H), 6.92 (s, 1H), 4.70 (d, 2H), 3.65 (s, 3H), 2.50 (t, 1H), 1.24 (s, 18H).

2.2.2 Polymerization of 1,4-di-tert-butyl-2-(prop-2-yn-1-yloxy)-5-methoxybenzene 5 to give 6

[0268] A 1 M solution of 5 (192 mg, 0.7 mmol) in chlorobenzene and a solution of rhodium norbonadiene tetraphenylborate (3 mol %, 10.8 mg, 21 mol) in 50 l of chlorobenzene was inertized by 3 freeze-pump-thaw cycles. Subsequently, the initiator was added to the monomer and the reaction was stirred at room temperature for 16 hours. The viscous solution obtained was precipitated in acetonitrile. This gave 174.7 mg (91%) of 6 in the form of a red powder.

3. Comparative Examples

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

[0269] ##STR00016## ##STR00017##

[0270] 3.1.1 Synthesis of 2-(3-bromopropoxy)tetrahydro-2H-pyran 10

[0271] 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.

[0272] .sup.1H NMR (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 (m, 4H).

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

[0273] 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.

[0274] .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

[0275] 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.

[0276] .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 in the presence of carbon

[0277] Monomer 12 (40 mg, 0.08 mmol), AIBN (0.7 mg, 0.004 mmol) and 80 mg SuperP (carbon particles, acquired from Sigma Aldrich) were inertized. Subsequently, 2.5 ml of dry toluene were added and the reaction was stirred at 80 C. for 54 hours. The composite was precipitated and washed in methanol. This gave 105 mg of 13 in the form of a black solid.

[0278] Elemental analysis: C, 92.06%; H, 2.38%; corresponds to about 27% polymer in composite.

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

[0279] ##STR00018##

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

[0280] 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.

[0281] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.84 (d, 2H), 4.11 (t, 2H), 3.92 (t, 2H), 3.81 (s, 3H), 2.09 (m, 2H), 1.37 (d, 18H).

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

[0282] 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.

[0283] .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 6.83 (d, 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 (d, 18H).

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

[0284] 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 3 (Inventive Example)

[0285] 3 (prepared as described in section 2.1.2) was processed in a mortar to give a fine powder. Subsequently added to 90 mg of 3 and 10 mg of poly(vinylidene fluoride) (PVDF; Sigma Aldrich as binder additive) was 1 ml of NMP (N-methyl-2-pyrrolidone), and the mixture was mixed in a mortar for five minutes until a homogeneous paste formed. This paste was applied to aluminium foil (15 m, MIT Corporation) using a doctor blade method or with the aid of a coating bar and the 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).

[0286] In the first discharge cycle, the battery shows a capacity of 52 mAh/g (58% of the theoretically possible capacity); after 2 charge/discharge cycles, the battery still shows a capacity of more than 50 mAh/g (FIG. 1=FIG. 1).

4.2 Production of an Electrode Comprising 13 (Comparative Example)

[0287] 13 (prepared as described in section 3.1.4) was processed in a mortar to give a fine powder. Subsequently added to 90 mg of 13 and 10 mg of poly(vinylidene fluoride) (PVDF; Sigma Aldrich as binder additive) was 1 ml of NMP (N-methyl-2-pyrrolidone), and the mixture was mixed in a mortar for five minutes until a homogeneous paste formed. This paste was applied to aluminium foil (15 m, MIT Corporation) using a doctor blade method with the aid of a coating bar and the 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).

[0288] In the first discharge cycle, the battery shows a capacity of 45 mAh/g (80% of the theoretically possible capacity); after 50 charge/discharge cycles the battery shows a capacity of 29 mAh/g (FIG. 2=FIG. 2).

5. Results

[0289] It is clear from the comparison of FIG. 1 with FIG. 2 that the polymer electrodes of the invention have both a higher discharge voltage and discharge capacity and consequently a much higher specific energy compared to those obtained in the prior art. This effect was observed over several charge/discharge cycles. In addition, it was possible to produce the polymers in a much less resource-intensive manner.

[0290] European patent application EP15182453 filed Aug. 26, 2015, is incorporated herein by reference.

[0291] 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.