Electroactive polymers

• US 4,519,938 A
• Filed: 11/17/1982
• Issued: 05/28/1985
• Est. Priority Date: 11/17/1982
• Status: Expired due to Fees

• Current Assignee: Chevron Research Company (Chevron Corp.)
• Original Assignee: Chevron Research Company (Chevron Corp.)
• Inventors: Papir, Yoram S.
• Primary Examiner(s): LEE, LESTER
• Application Number:
  US06/442,531
• Time in Patent Office: 923 Days
• Field of Search: 252/500, 252/510, 252/514, 252/518
• US Class Current: 252/500
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/141 comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Tractable doped electroactive polymers, comprising recurring units of a heterocyclic ring system and a sufficient concentration of charge compensating ionic dopants associated therewith.

Claims

1. A tractable electroactive polymer comprising:

a linear charged polymer backbone and a sufficient concentration of charge compensating ionic dopant(s) associated therewith, wherein said linear polymer backbone is capable of undergoing reversible oxidation or reversible reduction or both to form said linear charged polymer backbone, said linear polymer backbone comprises diradical repeat units selected from the group consisting of a heterocyclic ring system including at least one Group 5B or Group 6B atom, wherein none of the ring carbon atoms is saturated, a heterocyclic ring system including at least one Group 5B or Group 6B atom wherein none of the ring carbon atoms is saturated and a connecting unit, and mixtures thereof, wherein said diradical repeat unit contains no exocyclic double bonds and said diradical unit in the form of a monomeric repeat unit is capable of undergoing reversible oxidation or reversible reduction or both to form a stable ionic species, wherein said ionic species is a charged atomic or molecular species in the condensed phase which maintains said ionic species chemical integrity throughout the course of the chemical process of undergoing reversible oxidation or reversible reduction or both, and wherein said connecting unit is a conjugated system or atom or group of atoms which maintain π

orbital overlap with the heterocyclic ring system without adversely affecting the reversible oxidation or reversible reduction or both of said linear polymer backbone, said connecting unit is selected from the group consisting of;

##STR36## and atoms, groups of atoms and conjugated molecules which maintain π

orbital overlap with said heterocyclic ring system wherein R^v, R^vi and R^vii are H or methyl and mixtures thereof and R^viii is lower alkyl C₁ -C₄, or P-substituted phenyl, Ar is phenylene, or biphenylene, with the proviso that the heterocyclic ring system excludes fused 5,6-membered heterocyclic ring systems wherein two heteroatoms are in the 5-membered ring.

2. The electroactive polymer according to claim 1 wherein said Group 5B or 6B heteroatom is selected from the group consisting of N, P, As, O, S, Se, Te or mixtures thereof.

3. The electroactive polymer according to claim 2 wherein none of the heteroatoms occupy the ring fusion positions.

4. The electroactive polymer according to claim 3 wherein said heteroatom is selected from the group consisting of N, S, O, or mixtures thereof.

5. The electroactive polymer according to claim 4 wherein the heteroatoms are nitrogen and no more than two nitrogen atoms are bonded sequentially within the heterocyclic ring system.

6. The electroactive polymer according to claim 4 wherein the heteroatoms consisting of the group P, As, O, S, Se, Te do not occupy adjacent ring positions.

7. The electroactive polymer according to claim 3, 4, 5 or 6 wherein said linear charged polymer backbone is a polycation and said charge compensating ionic dopants are anions selected from the group consisting of AsF₄^-, AsF₆^-, ClO₄^-, PF₆^-, Cl^-, F^-, Br^-, I^-, I₃^-, SO₃ CF₃^-, BF₄^-, NO₃^-, POF₄^-, CN^-, SiF₅^-, SbCl₆^-, SbF₆^-, HSO₄^-, acetate, benoate, tosylate, or mixtures thereof.

8. The electroactive polymer according to claim 3, 4, 5 or 6 wherein the linear charged polymer backbone is a polyanion and the said charge compensating ionic dopants are cations selected from the group consisting of the alkali metal ions, alkali earth metal ions, Group III metal ions, ##STR37## wherein R^xi is a straight or branched chain alkyl of C₁ -C₆ groups, or mixtures of said cations.

9. The electroactive polymer according to claim 4 wherein the charge compensating ionic dopant is a cation selected from the group consisting of the alkali metal ions, alkali earth metal ions, Group III metal ions, ##STR38## wherein R^xi is a straight or branched chain alkyl of C₁ -C₆ groups, or mixtures of said cations.

10. The electroactive polymer according to claim 9 wherein the recurring diradical units of the linear charged polymer backbone are diradicals of fused nitrogen-containing unsaturated heterocyclic ring system.

11. The electroactive polymer according to claim 10 wherein the diradicals are fused 6,6-membered heterocyclic ring system containing from one to six nitrogen atoms distributed within and among the fused six-member rings wherein no more than two nitrogens are bonded sequentially within said ring system and none of the nitrogens occupies the ring fusion position.

12. The electroactive polymer according to claim 10 wherein the diradicals have one nitrogen atom and second heteroatom selected from the group consisting of O, S, P, Se, Te and N-alkyl substituted N.

13. The electroactive polymer according to claim 1, 4, 11, or 12 wherein the diradical heterocyclic ring system is modified through the addition of substituent groups to a desired reversible oxidation potential or reduction potential or both without effecting the tractable nature of the polymer.

14. An electroactive polymer which comprises a linear charged polymer backbone and charge compensating ionic dopants associated therewith of the formula:

##STR39## wherein a is 0 or 1;

b is 0 or 1;

c is 0 or 1;

n is an integer from 2 to 2000;

d is an integer from 1 to 4000;

S is an integer 1, 2, or 3;

R is a diradical of unsaturated heterocyclic ring system containing at least one Group 5B or 6B heteroatom, wherein none of the ring carbon atoms are saturated;

R'"'"' is the same diradical as R or a different diradical unsaturated heterocyclic ring X is a diradical connecting unit;

Y is the same diradical connecting unit as X or a different diradical connecting unit; and

M is a charge compensating ionic dopant of opposite electrical charge to the charge of the polymer backbone wherein the polymer backbone is capable of undergoing reversible oxidation or reversible reduction or both to form said linear charged polymer backbone, said diradical or diradical-connecting unit in the form of a monomeric repeat unit is capable of undergoing reversible oxidation or reversible reduction or both to form a stable ionic species, wherein said ionic species is a charged atomic or molecular species in the condensed phase which maintains said ionic species chemical integrity throughout the course of the chemical process of undergoing reversible oxidation or reversible reduction or both, and wherein R and R'"'"', contain no exocyclic double bonds, and wherein said connecting unit is a conjugated system or atom or group of atoms which maintain π

orbital overlap with the heterocyclic ring system without adversely affecting the reversible oxidation or reversible reduction or both of said linear polymer backbone, said connecting unit is selected from the group consisting of;

##STR40## and atoms, groups of atoms and conjugated molecules which maintain π

orbital overlap with said heterocyclic ring system wherein R^v, R^vi and R^vii are H or methyl and mixtures thereof and R^viii is lower alkyl C₁ -C₄, or P-substituted phenyl, Ar is phenylene, or biphenylene, with the proviso that the heterocyclic ring system excludes fused 5,6-membered heterocyclic ring systems wherein two heteroatoms are in the 5-member ring.

15. The electroactive polymer according to claim 14 wherein said Group 5B or 6B heteroatom is selected from the group consisting of N, P, As, Sb, Bi, O, S, Se, Te or mixtures thereof.

16. The electroactive polymer according to claim 15 wherein said heteroatom is selected from the group consisting of N, S, O, or mixtures thereof.

17. The electroactive polymer according to claim 16 wherein said linear charged polymer backbone is a polycation and said charge compensating ionic dopants M are anions selected from the group consisting of AsF₄^-, AsF₆^-, ClO₄^-, PF₆^-, SO₃ CF₃^-, BF₄^-, NO₃^-, POF₄^-, CN^-, F^-, Cl^-, Bi^-, I^-, I₃^-, SiF₅^-, SbCl₆^-, SbF₆^-, HSO₄^-, acetate, benzoate, tosylate, or mixtures thereof.

18. The electroactive polymer according to claim 16 wherein the linear charged polymer backbone is a polyanion and the said charge compensating ionic dopants M are cation is selected from the group consisting of alkali metal ions, alkali earth metal ions, Group III metal ions, ##STR41## wherein R^xi is a straight or branched chain alkyl of C₁ -C₆ groups, or mixtures of said cations.

19. A process for fabricating a linear electroactive polymer of predetermined and preselected conductivity type, redox potential, work function, and geometric form comprising:

(a) synthesizing a polymer containing diradical repeat units whose monomeric repeat units are capable of undergoing a reversible oxidation and/or reduction process to form a stable ionic species, wherein said ionic species is a charged atomic or molecular species in the condensed phase which maintains said ionic species chemical integrity throughout the course of the chemical process of undergoing reversible oxidation or reversible reduction or both, said monomeric and corresponding diradical repeat units being selected from the group consisting of a heterocyclic ring system including at least one Group 5B or 6B atom, wherein none of the ring system carbon atoms is saturated, a heterocyclic ring system including at least one Group 5B or Group 6B atom wherein none of the ring system carbon atoms is saturated and a connecting unit, and mixtures thereof, said connecting unit is a conjugated system or an atom or a group of atoms which maintain π

orbital overlap with the heterocyclic ring system without adversely affecting the reversible oxidation or reversible reduction or both of said linear polymer backbone, said connecting unit is selected from the group consisting of;

##STR42## and atoms, groups of atoms and conjugated molecules which maintain π

orbital overlap with said heterocyclic ring system wherein R^v, R^vi and R^vii are H or methyl and mixtures thereof and R^viii is lower alkyl C₁ -C₄, or P-substituted phenyl, Ar is phenylene, or biphenylene, wherein said diradical repeat unit is selected such that if a p-type polymeric electrical conductor is desired, the corresponding monomeric repeat unit exhibits a reversible oxidation process, wherein the desired electroactive polymer will exhibit a redox potential which is approximately equal to the redox potential of the monomeric repeat unit, said diradical repeat unit is selected such that if an n-type polymeric electrical conductor is desired, the corresponding monomeric repeat unit exhibits a reversible reduction process, wherein the desired electroactive polymer will exhibit a redox potential which is approximately equal to the redox potential of the monomeric repeat unit, said diradical repeat unit is selected such that if it is desired that the polymeric electrical conductor will exhibit both n- and p-type behavior, the corresponding monomeric repeat unit exhibits both reversible oxidation and reduction processes, wherein the desired electroactive polymer will exhibit redox potentials which are approximately equal to the redox potentials of the monomeric repeat unit;

(b) dissolving the polymer of step (a) in an appropriate solvent or otherwise causing said polymer to become fluids;

(c) processing the polymer of step (b) from the solution or fluid state into an object of desired shape, size, and geometry; and

(d) subjecting the object of step (c) to oxidizing and/or reducing conditions as to cause said polymer to become charged incorporating therewith a sufficient concentration of charge compensating ionic dopants.

20. The process according to claim 19 wherein the heteroatoms are selected from the group consisting of N, P, As, O, S, Se, Te.

21. The process according to claim 20 wherein the heteroatoms are selected from N, O, S.

22. The process according to claim 21 wherein said reducing conditions comprise exposing said polymer to reducing agents selected from the group consisting of alkali naphthalenides, alkali anthracenides, tetraalkylammonium anthracenides and naphthalenides dissolved in a suitable solvent.

23. The process according to claim 21 wherein said reducing conditions comprise contacting said polymer with an inert electrode in the presence of an electrolyte solution containing charge compensating ionic dopants and electrochemically reducing said polymer and associating said polymer with said charge compensating cationic dopants selected from a group consisting of alkali metal ion, alkali earth metal ions, Group III metal ions, ##STR43## wherein R^xi is a straight or branched chain alkyl of C₁ -C₆ groups, or mixtures thereof.

24. The process according to claim 21 wherein said oxidizing conditions comprise exposing said polymer to oxidizing agents selected from the group consisting of AsF₅, SbCl₅, SbF₅, and halogen gases.

25. The process according to claim 21 wherein said oxidizing conditions comprise contacting said polymer with an inert electrode in the presence of an electrolyte solution containing charge compensating ionic dopants and electrochemically oxidizing said polymer and associating said polymer with said charge compensating anionic dopants selected from the group consisting of AsF₄^-, AsF₆^-, ClO₄^-, PF₆^-, SO₃ CF₃^-, BF₄^-, NO₃^-, POF₄^-, CN^-, F^-, Cl^-, Bi^-, I^-, I₃^-, SiF₅^-, SbCl₆^-, SbF₆^-, HSO₄^-, acetate, benzoate, tosylate, or mixtures thereof.