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

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

1998-04-20

2001-03-06

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Nitrogen-containing reactant

C528S423000, C528S422000, C526S259000, C526S265000

Reexamination Certificate

active

06197923

ABSTRACT:

TECHNICAL FIELD
The present invention relates to N-oxidized poly (nitrogen-containing heterocyclic ring) and N-oxidized poly(nitrogen-containing condensed heterocyclic ring) which have excellent heat resistance, which are soluble in aqueous solvents or organic solvents, active in electrochemical oxidation and reduction whose potential can be controlled, color of which clearly changes by chemical or electrochemical oxidation-reduction, and which show conductivity by themselves, a method of producing the same, and use of the same.
BACKGROUND ART
Poly(arylene) having a structure that aromatic rings are serially bound, particularly poly(arylene) having serially &pgr; conjugated system along the main chain (for example, poly(p-phenylene), poly(2,5-thienylene), and poly(1,4-naphthalenediyl)) generally possess excellent heat resistance. Further, it is known that addition products of these poly(arylene) to electron acceptors (e.g., AsF
5
, etc.) or electron donors (e.g., lithium, sodium, etc.) have conductivity and have property to change their color reversibly (electrochromic) by electrochemical oxidation-reduction so as to be available as materials for displays (for example, High polymers, Japan 38, 1080 (1989)). Japanese Patent Application Laid-Open No.Hei 1-210420 discloses conductive substances produced by reducing polymers having serial &pgr; conjugated system along the main chain and groups composed of 6-membered heterocyclic ring units, for example, a 2,5-pyridinediyl group as a repeating constitutive unit. Japanese Patent Application Laid-Open No.Hei 5-70565 discloses poly(quinolinediyl) and poly(isoquinolinediyl), which are composed of condensed heterocyclic ring units and Japanese Patent Application No. Hei 6-56972 discloses quaternary poly(quinolinediyl) and poly(isoquinolinediyl).
However, most of the poly(arylene)s conventionally proposed show low solubility in water or organic solvents and are not melted, which restricts their application and is an obstacle to elicit their characteristic functions. With respect to the above-described poly(arylene)s, it has been desired to modify the molecular structure so as to develop such substances as having properties different from the conventionally known poly(arylene)s. For example, if it is possible to obtain poly(arylene) that has oxidation-reduction potential or changes its color (electrochromic phenomenon), different from the known poly(arylene)s, it would be used as an electrode to provide an electrochromic display which has characteristics different from the conventionally used electrochromic indicative material (for example, “OYO BUTURI”, Vol.56, 1433 (1987)) or it would be used as an active material or an electrode to provide a polymer battery that has characteristics different from the known polymer battery (for example, “Denki Kagaku (Journal of the Electrochemical Society of Japan)” 54, 306 (1986)). In order to confer conductivity on poly(arylene)s, it is necessary to effect oxidation (p-doping) or reduction (n-doping) of poly(arylene)s that are usually in a neutral state (cf. the above-described portions of OYO BUTURI and Denki Kagaku (Journal of the Electrochemical Society of Japan)). This oxidation-reduction is disadvantageous in that a corrosive oxidizing agent such as iodine is used, that the process is complicated, and that dopants such as I
−
, ClO
4
−
, or NR
4
+
may possibly render poly(arylene), which becomes conductive, chemically and physically unstable. Accordingly, it has been desired to develop materials made of poly(arylene)s or its derivatives having no such a dopant and showing conductivity by themselves.
DESCRIPTION OF THE INVENTION
Under these circumstances, the present invention was completed as a result of intensive investigation to screen poly(arylene)s having a novel molecular structure.
An object of the present invention is to provide poly (arylene), particularly N-oxidated (nitrogen-containing heterocyclic ring) polymer and N-oxidated (nitrogen-containing condensed heterocyclic ring) polymer, which have excellent heat resistance, which are soluble in aqueous solvents or organic solvents, depolarization and electrochemical oxidation-reduction potential of which can be controlled, color of which clearly changes by chemical or electrochemical oxidation-reduction, and which show conductivity by themselves.
Another object of the present invention is to apply such a novel N-oxidated poly(nitrogen-containing heterocyclic ring) and N-oxidated poly(nitrogen-containing condensed heterocyclic ring) to moldings such as fiber or film, an electrochromic element, an active material or an electrode for a battery, semiconductor, n-type semiconductor, and the like.
The N-oxidated poly(nitrogen-containing heterocyclic ring) is a polymer containing a polymer chain represented by the formula (1):
wherein two of any 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 resented 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, or a polymer containing a polymer chain represented by the formula (2):
wherein two of any 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, two of any 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 represented by o, p, q, r, s, and t is 3, and the degree of polymerization 1+m is at least 5.
The polymer of the above formula (1) is a polymer mainly containing a repeating unit of a nitrogen-containing heterocyclic ring whose nitrogen atom is oxidated, while the polymer of the above formula (2) is a copolymer containing a repeating unit of a nitrogen-containing heterocyclic ring whose nitrogen atom is oxidated and a repeating unit of a nitrogen-containing heterocyclic ring whose nitrogen atom is not oxidated. These polymers can further have another repeating unit, for example a repeating unit conventionally known as the one forming &pgr; conjugated macromolecule such as a (thiophen-2,5-diyl) unit.
In the copolymer of the above formula (2), the repeating unit of a nitrogen-containing heterocyclic ring whose nitrogen atom is oxidated and the repeating unit of a nitrogen-containing heterocyclic ring whose nitrogen atom is non-oxidated are copolymerized at random.
The subgroup of the N-oxidated poly(nitrogen-containing heterocyclic ring) represented by the above formula (1) include N-oxidated poly(pyridinediyl), poly(pyrazinediyl), poly(pyrimidi nediyl), and poly(pyridazinediyl) represented by the following formula (1a), (1b), (1c), and (1d), respectively:
wherein the degree of polymerization n
1
, n
2
, n
3
, and n
4
represent at least 5 and (&agr;
1
, &bgr;
1
, and &ggr;
1
represent 0 or 1.
The subgroup of the N-oxidated poly(nitrogen-containing heterocyclic ring) represented by the above formula (2) include N-oxidated poly(pyridinediyl), poly(pyrazinediyl), poly (pyrimidinediyl), and poly(pyridazinediyl) copolymers represented by the following formula (2a), (2b), (2c), and (2d), respectively:
wherein the degree of polymerization 1
1
+m
1
, 1
2
+m
2
, 1
3
+m
3
, and 1
4
+m
4
represent at least 5 and &agr;
2
, &bgr;
2
and &ggr;
2
represent 0 or 1.
The N-oxidated poly(nitrogen-containing condensed heterocyclic ring) is a polymer containing a polymer chain represented by the formula (7):
wherein two of any of a, b, c, d, e, f, g and h represent carbon atoms that are involved i

Affiliated with

Also associated with

Rating

Polymers, method of producing the same and use of the same does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Polymers, method of producing the same and use of the same, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Polymers, method of producing the same and use of the same will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2543412