Method of making self-doped zwitterionic heterocyclic polymers

• US 5,891,968 A
• Filed: 06/07/1995
• Issued: 04/06/1999
• Est. Priority Date: 03/24/1986
• Status: Expired due to Term

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Wudl, Fred, Heeger, Alan
• Primary Examiner(s): HENDERSON JR, CHRISTOPHER A
• Application Number:
  US08/477,186
• Time in Patent Office: 1,399 Days
• Field of Search: 525/417, 525/410, 528/377, 528/360
• US Class Current: 525/417
• CPC Class Codes: C08F 212/30 Sulfur
• CPC Class Codes: C08G 73/00 Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00 polycarbodiimides prepared from isocyanates C08G18/025, C08G18/797
• CPC Class Codes: C08G 75/00 Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
• CPC Class Codes: H01B 1/122 Ionic conductors

Abstract

A self-doped conducting polymer having along its backbone a π-electron conjugated system which comprises a plurality of monomer units, between about 0.01 and 100 mole % of the units having covalently linked thereto at least one Bronsted acid group. The conductive zwitterionic polymer is also provided. as are monomers useful in the preparation of the polymer and electrodes comprising the polymer.

Claims

1. A method of making a self-doped zwitterionic conducting polymer having along its backbone a π

-electron conjugated system, which method is selected from the following methods (A) or (B);

wherein method (A) which comprises;

(i) providing a polymer having along its backbone a π

-electron conjugated system which comprises a plurality of recurring monomer units, between about 0.01 and 100 mole % of said units having the structure (I);

##STR12## wherein Ht is a heterogroup selected from NH or S;

Y₁ is selected from the group consisting of hydrogen and --R--X--M, wherein

R is a linear or branched alkylene or alkylene ether having between 1 and about 10 carbon atoms;

X is a Bronsted acid anion selected from CO₂ or SO₃ ; and

M is a positive monovalent counterion except H⁺ ; and

(ii) converting at least one --R--X--M group to a --R--X--H group by adding acid, thereby rendering said polymer self-doped, with the proviso that external dopant is not needed and is not present;

or

method (B) which comprises;

(a) providing at least one monomer having the structure;

##STR13## wherein Ht is a heterogroup selected from NH or S;

Y₁ is selected from the group consisting of hydrogen and --R--X--M, wherein

R is a linear or branched alkylene or alkylene ether having between 1 and about 10 carbon atoms;

--X--M is a Bronsted acid alkyl ester group, or X is a Bronsted acid anion selected from CO₂ or SO₃ and then M is a positive monovalent counterion, and

(b) polymerizing said monomers, and if M is not H⁺, then

(c) converting at least one --R--X--M group to a R--X--H group by adding acid, thereby rendering said polymer self-doped, with the proviso that external dopant is not needed and is not present.

2. The method of claim 1, wherein the method (B) comprises the steps of:

providing an electrolyte solution comprising said monomer, immersing in said electrolyte solution, a working electrode and a counter electrode; and

applying a voltage across said working electrode and said counter electrode, whereby polymerization of said monomer at said working electrode is effected to produce a polymer having along its backbone a π

-electron conjugated system which comprises a plurality of recurring monomer units, between about 0.01 and 100 mole % of said units having the structure;

##STR14## wherein Ht is a heterogroup selected from NH or S;

Y₁ is selected from the group consisting of hydrogen and --R--X--M, wherein R is a linear or branched alkylene or alkylene ether having between 1 and about 10 carbon atoms;

--X--M is a Bronsted acid or alkyl ester group, or X is a Bronsted acid anion selected from COO or SO₃ and then M is a positive monovalent counterion alkyl, and

if M is not H⁺, then further comprising the step of converting at least one --R--X--M group to a R--X--H group by adding acid, thereby rendering said polymer self-doped.

3. The method of claim 1 wherein R is linear alkylene.

4. The method of claim 1 wherein R is branched alkylene.

5. The method of claim 1 wherein:

M in method (A) is selected from the group consisting of Li⁺, Na⁺ and K⁺ ; and

M in method (B) is selected from the group consisting of H⁺, Li⁺, Na⁺, K⁺, methyl and ethyl.

6. The method of claim 2 wherein R is branched alkylene ether.

7. The method of claim 2 wherein and R is linear alkylene ether.

8. The method of claim 2 wherein M in method (A) is selected from the group consisting of Li⁺, Na⁺ and K⁺ ;

and M in method (B) is selected from the group consisting of H⁺, Li⁺, Na⁺, K⁺, methyl and ethyl.

9. The method of claim 3 wherein R is branched alkylene ether.

10. The method of claim 9 wherein Ht is NH.

11. The method of claim 1 wherein Ht is S.

12. The method of claim 1 wherein X is CO₂.

13. The method of claim 10 wherein X is SO₃.

14. The method of claim 11 wherein X is CO₂.

15. The method of claim 9 wherein X is SO₃.

16. The method of claim 10 wherein X is SO₃.

17. The method of claim 11 wherein X is SO₃.

18. The method of claim 5 wherein M in method (A) is Na⁺ or K⁺.

19. The method of claim 5 wherein M in method (B) is H⁺, Na⁺ or K⁺.

20. The method of claim 5 wherein M in method (A) is Na⁺ or K⁺, and Ht is S.

21. The method of claim 5 wherein M in method (B) is H⁺, Na⁺ or K⁺, and t is NH or S.

22. The method of claim 1, wherein said monomer is selected from the group consisting of thiophene-3-acetic acid, methyl thiophene-3-(2-ethanesulfonate), and methyl thiophene-3-(4-butanesulfonate).