Polymers, method of producing the same and use of the same

• US 6,197,923 B1
• Filed: 04/20/1998
• Issued: 03/06/2001
• Est. Priority Date: 10/27/1995
• Status: Expired due to Fees

• Current Assignee: Nissan Chemical Industries Limited (Shin-Etsu Chemical Company Limited)
• Original Assignee: Nissan Chemical Industries Limited (Shin-Etsu Chemical Company Limited)
• Inventors: Yamamoto, Takakazu
• Primary Examiner(s): Truong, Duc
• Application Number:
  US09/051,754
• Time in Patent Office: 1,051 Days
• Field of Search: 528/424, 528/423, 528/422, 526/259, 526/265
• US Class Current: 528/424
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: D01F 6/58 from homopolycondensation products
• CPC Class Codes: G02F 1/15165 Polymers
• 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: H01M 4/606 containing aromatic main chain polymers
• CPC Class Codes: H01M 4/608 containing heterocyclic rings
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

N-Oxides of nitrogenous heterocycle or nitrogenous fused heterocycle polymers of general formula (1) or (7) (wherein any two of a, b, c, d, e, f, g and h are carbon atoms participating in the bonding between repeating units; at least one of them is N→O; the rest are each CH, N or N→O; and the degree of polymerization “n” is at least 5). These polymers have excellent heat resistance, are soluble in aqueous or organic solvents and controllable in the degree of depolarization and electrochemical redox potential, exhibit clear color changes by chemical or electrochemical oxidation or reduction, and are conductive per se . They can be used as moldings such as fibers and films; electrochromic elements; active materials and electrodes of cells; semiconductors including n-type semiconductors; and so on.

Claims

1. N-oxidated poly(nitrogen-containing heterocyclic ring) containing a polymer chain represented by the formula (1):

wherein any two of a, b, c, d, e, and f represent carbon atoms that are involved in binding between repeating units, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, d, e, and f is 2, the maximum total number of the nitrogen atoms is 3, and the degree of polymerization n is at least 5.

3. The N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 1, wherein said formula (1) is the formula (1a), (1b), (1c), or (1d):

wherein the degree of polymerization n₁, n₂, n₃, and n₄ represent at least 5 and α

₁, β

₁, and γ

₁ represent 0 or 1.

11. A fiber or film which is made of the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 1.

12. An electrochromic element which is made of the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 1.

13. An active material or electrode for a battery, which is made of the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 1.

14. A semiconductor which is made of the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 1.

15. An n-type semiconductor prepared by reducing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 1 with a reducing agent or by electrochemical doping.

2. N-oxidated poly(nitrogen-containing heterocyclic ring) containing a polymer chain represented by the formula (2):

wherein any two of a, b, c, d, e, and f represent carbon atoms that are involved in binding between repeating units, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, d, e, and f is 2, the maximum total number of the nitrogen atoms is 3, any two of o, p, q, r, s, and t represent carbon atoms that are involved in binding between repeating units, the remainings independently represents a CH group or a nitrogen atom, the maximum total number of the nitrogen atoms contained in o, p, q, r, s, and t is 3, and the degree of polymerization 1+m is at least 5.

4. The N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 2, wherein said formula (2) is the formula (2a), (2b), (2c), or (2d):

wherein the degree of polymerization 1₁+m₁, 1₂+m₂, 1₃+m₃, and 1₄+m₄ represent at least 5 and α

₂, β

₂, and γ

₂ represent 0 or 1.

5. A method of producing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 4, which comprises reacting poly(nitrogen-containing heterocyclic ring) containing a polymer chain represented by the formula (3):

wherein o, p, q, r, s, and t have the same meaning as described above and the degree of polymerization x represents at least 5, with peroxide to N-oxidate the nitrogen atom in the ring.

6. A method of producing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 4, which comprises reacting a dihalide derivative represented by the formula (4)

wherein X and Y represent a halogen atom, any two of a, b, c, d, e, and f represent carbon atoms that bind to said halogen atoms, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, d, e, and f is 2, and the maximum total number of the nitrogen atoms is 3, with a zerovalent nickel compound.

7. A method of producing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 4, which comprises subjecting a dihalide derivative represented by the formula (4):

wherein X and Y represent a halogen atom, any two of a, b, c, d, e, and f represent carbon atoms that bind to said halogen atoms, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, d, e, and f is 2, and the maximum total number of the nitrogen atoms is 3, to electrolytic reduction in the presence of a nickel compound.

8. The method of producing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 5, wherein said formula (3) is the formula (3a), (3b), (3c), or (3d):

wherein the degree of polymerization x₁, x₂, x₃, and x₄ represent at least 5.

9. The method of producing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 6, wherein said formula (4) is the formula (4a), (4b), (4c), or (4d):

wherein X and Y each represents a halogen atom and α

₃, β

₃, and γ

₃ represent 0 or 1.

10. The method of producing the N-oxidated poly(nitrogen-containing heterocyclic ring) as claimed in claim 7, wherein said formula (4) is the formula (4a), (4b), (4c), or (4d):

wherein X and Y each represents a halogen atom and α

₃, β

₃, and γ

₃ represent 0 or 1.

16. N-oxidated poly(nitrogen-containing condensed heterocyclic ring) containing a polymer chain represented by the formula (7)

wherein any two of a, b, c, d, e, f, g and h represent carbon atoms that are involved in binding between repeating units, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, and d is 2, the maximum total number of the nitrogen atoms is 3, the N→

O groups represented by e, f, g, and h is 2, the maximum total number of the nitrogen atoms is 3, and the degree of polymerization n is at least 5.

18. The N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16, wherein said formula (7) is the formula (7a), (7b-1), (7b-2), (7c-1), or (7c-2):

wherein the degree of polymerization n₁, n₂, n₃, n₄, and n₅ represent at least 5.

20. A method of producing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16, which comprises reacting the poly(nitrogen-containing condensed heterocyclic ring) containing a polymer chain represented by the formula (9):

wherein o, p, q, r, s, t, u, and v have the same meaning as described above and the degree of polymerization x represents at least 5, with peroxide to N-oxidate the nitrogen atom in the ring.

21. A method of producing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed claim 16, which comprises reacting a dihalide derivative represented by the formula (10):

wherein X and Y each represents a halogen atom, any two of a, b, c, d, e, f, g, and h represent carbon atoms that bind to said halogen atoms, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, and d is 2, the maximum total number of the nitrogen atoms is 3, the maximum total number of the N→

O groups represented by e, f, g, and h is 2, and the maximum total number of the nitrogen atoms is 3, with a zerovalent nickel compound.

22. A method of producing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in any of claims 16 to 19, which comprises subjecting a dihalide derivative represented by the formula (10):

wherein X and Y each represents a halogen atom, any two of a, b, c, d, e, f, g, and h represent carbon atoms that bind to said halogen atoms, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, and d is 2, and the maximum total number of the nitrogen atoms is 3, the maximum total number of the N→

O groups represented by e, f, g, and h is 2, and the maximum total number of the nitrogen atoms is 3, to electrolytic reduction in the presence of a nickel compound.

23. The method of producing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 20, wherein said formula (9) is the formula (9a), (9b), or (9c):

wherein the degree of polymerization x₁, x₂, and x₃ represent atleast 5.

24. The method of producing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 21, wherein said formula (10) is the formula (10a), (10b-1), (10b-2), (10c-1), or (10c-2):

wherein X and Y each represents a halogen atom.

25. The method of producing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 22, wherein said formula (10) is the formula (10a), (10b-1), (10b-2), (10c-1), or (10c-2):

wherein X and Y each represents a halogen atom.

26. A fiber or film which is made of the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16.

27. An electrochromic device which is made of the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16.

28. An active material or electrode for a battery, which is made of the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16.

29. A semiconductor which is made of the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16.

30. An n-type semiconductor prepared by reducing the N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 16 with a reducing agent or by electrochemical doping.

17. N-oxidated poly(nitrogen-containing condensed heterocyclic ring) containing a polymer chain represented by the formula (8)

wherein any two of a, b, c, d, e, f, g, and h represent carbon atoms that are involved in binding between repeating units, at least one of them represents an N→

O group, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the N→

O groups represented by a, b, c, and d is 2, the maximum total number of the nitrogen atoms is 3, the maximum total number of the N→

O groups represented by e, f, g, and h is 2, the maximum total number of the nitrogen atoms is 3, any two of o, p, q, r, s, t, u, and v represent carbon atoms that are involved in binding between repeating units, the remainings independently represent a CH group or a nitrogen atom, the maximum total number of the nitrogen atoms represented by o, p, q, and r is 3, the maximum total number of the nitrogen atoms contained in s, t, u, and v is 3, and the degree of polymerization 1+m is at least 5.

19. The N-oxidated poly(nitrogen-containing condensed heterocyclic ring) as claimed in claim 17, wherein said formula (8) is the formula (8a), (8b-1), (8b-2), (8c-1), or (8c-2):

wherein the degree of polymerization 1₁+m₁, 1₂+m₂, 1₃+m₃, 1₄+m₄, and 1₅+m₅ represent at least 5.