Compositions – Electrically conductive or emissive compositions
Reexamination Certificate
1994-01-03
2003-08-12
Mullis, Jeffrey (Department: 1711)
Compositions
Electrically conductive or emissive compositions
C525S088000, C525S09200D, C525S09200D, C525S09200D, C525S09200D, C525S09200D, C525S090000, C525S091000, C525S093000, C525S098000
Reexamination Certificate
active
06605236
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention is generally directed to melt processable, intrinsically conductive and semiconductive polymeric composites useful in preparing electrically conductive films, coatings and articles with controlled conductivity. The conducting polymer composites of this invention can be manipulated in preparative processes to result in materials that are functional in many known applications for intrinsically conducting organic polymers, for example, molecular circuitry, electronic membranes, photovoltaics, light emitting diodes, electrochromic windows, rechargeable batteries, electrolytic capacitors, optical switches, and electromagnetic interference shielding. More specifically, the present invention is directed to conductive polymeric compositions containing therein, known conductive aromatic and heteroaromatic polymers, for example, poly(pyrrole), poly(thiophene) or poly(azulene) and their congeners in intimate admixture with an ionophoric or ionomeric block copolymer, that is, a block copolymer with an ion binding or ion coordinating segment and a nonfunctional segment to control morphology of the structured dispersed phase, and insure solubility and melt processability of the resulting polymeric composite conducting films and and functional articles. The ionophoric or ionomeric character of the block copolymer enables complexation or sequesteration of redox active dipolar molecules or ions in the binding segment of the block copolymer. The redox active ion or dipolar molecule, in embodiments of the present invention, acts as an oxidative coupling agent or redox reagent for the polymerization of heteroaromatic or aromatic monomers, yielding, Intrinsically Conductive organic Polymers (ICPs) which may be physically trapped or matrix polymerized to the ionophoric or ionomeric segment of the block copolymer.
The present invention thus provides soluble, melt processable, electronically conducting or semiconducting thermoplastic composites of intrinsically conducting organic polymers that are matrix polymerized to, or within, the ion-binding segments of ionophoric or ionomeric block copolymers. The present invention further specifies processes for the preparation of these composites and provides processes for making electrically conductive articles therefrom. The ICP composites may be prepared as colloidal solutions or in the solid state, with the material prepared in the solid state generally having higher conductivity.
The composite compositions of this invention are prepared in embodiments by template polymerization of aromatic and heteroaromatic monomers such as thiophene, pyrrole, indole, indene and azulene or a congener, for example, 3-methyl pyrrole, bithiophene, 3-alkylthiophenes, thianapththene, and the like, in the presence of an ionophoric or ionomeric block copolymer to which a suitable redox reagent for the oxidative coupling of the aromatic or heteraromatic monomer reactants, has been specifically bound.
Intrinsically conducting organic polymers, composites thereof, articles thereof, and processes for their preparation, are well known and are extensively documented in numerous prior art patents and publications, the disclosures of which are incorporated by reference herein in their entirety. Thus, for example, Rabek et al.,
Synthetic Metals
, 45 (1991) 335-351, have described the polymerization of pyrrole in solid state FeCl
3
complexes with poly(ethylene oxide), poly(oxy-1,2-ethane diyl), poly(&bgr;-propiolactone), poly(2-oxetanone) or poly(1,5-di-oxepan-2-one). Jasne and Chicklis have described the electrochemical polymerization of pyrrole in latices with covalently bound anionic sites and Bates et al.,
J. Chem. Soc., Chem. Commun
., (1985) 871, have described the preparation of a heat processable composite of poly(pyrrole) in sulfonated styrene (hydrogenated) butadiene triblock copolymer. Armes and Vincent,
J. Chem. Soc., Chem. Commun
., (1987) 288, described the preparation of colloidal poly(pyrrole) in water with agency of poly(vinyl pyrrolidone) or poly(vinyl alcohol-co-acetate). Poly(ethylene oxide), poly(acrylic acid) and block copolymers of poly(ethylene oxide) were specifically reported to be ineffective in stabilizing colloidal dispersions of poly(pyrrole). Similarly, Bjorklund Leidberg
J. Chem. Soc., Chem. Commun
., (1986) 1293, described the preparation of colloidal poly(pyrrole) in water with agency of methylcellulose. The seminal synthesis of poly(pyrrole) involved the electrochemical, oxidative coupling of pyrrole at electrode surfaces to directly yield conducting polymer films as reported by A. F. Diaz, K. K. Kanazawa and G. P. Gardini,
J. Chem. Soc. Chem Comm
., 635 (1979).
The chemical oxidative coupling polymerization of thiophene to yield conducting polymers is more difficult to effect, and accordingly poly(thiophene) is most often generated electrochemically. Garnier and coworkers reported the electropolymerization of thiophene,
J. Electroanal. Chem
., (1982) 135, 173, and the electropolymerization of thiophene in poly(methylmethacrylate) and poly(vinyl chloride), see
J. Chem. Soc., Chem. Commun
., (1986) 783; and
J. Phys. Chem
., 92 (1988), 833. The chemical synthesis of polythiophene with ferric perchlorate and ferric chloride
itromethane was reported by M. Mermilliod-Thevenin and G. Bidan,
Mol. Cryst. Liq. Cryst
., 118:227 (1985), and S. Hotta, et al.,
Synthetic Metals
, 9 (1984) 381. Ko&bgr;mehl (1986)
Makromol. Chem., Macromol. Symp
, 4:45 and (1982)
Mol. Cryst. Liq. Cryst
., 83:291, reported the chemical synthesis of poly(thiophene) with nitrosonium salts and Yamamoto et al., reported Grignard coupling to yield linear poly(thiophene), see (1981)
Chem. Lett
., 1079; and (1982)
J. Polym. Sci., Polym. Lett. Ed
., 20:365. Similarly, Elsebaumer, et al., reported Grignard coupling to yield poly (3-alkyl thiophenes). Alkylthiophene derivatives can be obtained as soluble polymer solutions, particularly when prepared by coupling of organolithium or organocadmium derivatives,
Synthetic Metals
, 18 (1987) 277.
Environmental instability, lack of mechanical strength and integrity, and difficulties in processing have represented major barriers to commercial application of intrinsically conducting organic polymers. Among ICPs, poly(pyrroles) and poly(thiophenes) are acknowledged to be among the most environmentally stable. Their synthesis is relatively simple. Recent work in leading enterprises seeking to exploit these polymers in the burgeoning commercial applications for intrinsically conducting polymers have focused on improved processing and the development of mechanical integrity in these materials. Poly(thiophenes), obtained by conventional processes are typically intractable, see for example, Advanced Materials, Volume 5, Number 9, September 1993, Part 2, page 646-650. Thus there remains a need for highly conducting, environmentally stable and easily processable polymer composite materials.
The preparative processes and procedures described in the literature fall into four main categories:
Category 1—The electrochemical polymerization of pyrrole or thiophene to directly yield the ICP in film form.
Category 2—The generation of colloidal ICP particles stabilized by selected water soluble polymers.
Category 3—The insitu generation of ICP within the interstices of a preformed polymer host into which a reagent for the oxidative polymerization has been imbibed. Subsequent exposure to the monomer yields a composite of the host polymer and the ICP. Alternatively, monomer (pyrrole or thiophene) may be imbibed into a preformed polymer film on an electrode surface and electrochemically polymerized within the interstices of a preformed polymer host.
Category 4—solublization of the ICP by polymerization of monomers with sufficiently long alkyl substituents. This approach has been particularly popular with poly(thiophene) where soluble polymers can be obtained from 3-alkylthiophene derivatives wherein the alkyl chain is C
4
or longer. The processes of Categories 1 and 3 are generally limited to film geometries, and
Luca David J.
Smith Thomas W.
Thompson Robert F
Xerox Corporation
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