| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 05.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 23.05.00 |
| PATENT TITLE |
Electroactive inorganic hybrid materials |
| PATENT ABSTRACT |
Hybrid materials are formed having a homogeneous distribution of a conductive organic polymer or copolymer in an inorganic matrix. The conductive organic polymer may be electronically conductive, e.g., polyaniline, or may be ionically conductive, e.g., sulfonated polystyrene. The inorganic matrix is formed as a result of sol-gel chemistry, e.g., by the hydrolysis and condensation of tetraethyl orthosilicate and trialkoxysilyl groups in the organic polymers. A homogeneous distribution of organic polymer in the inorganic matrix is achieved by preparing separate solutions of organic polymer and sol-gel monomer, and then combining those solutions with a catalyst and stirring, to form a homogeneous clear solution. Upon evaporation of the solvent and other volatiles, a monolithic hybrid material may be formed. The combination of conductive organic polymer in an inorganic matrix provides desirable adhesion properties to an inorganic substrate while maintaining the conductivity of the organic polymer. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 16.10.98 |
| PATENT REFERENCES CITED |
Harreld et al "Design & Synthesis of Varadium Pentoxide/Polypyrrole" Mater. Res. Soc. Symp. Proc. 519, 191-200 1998 (Abstract Only). Yen Wei et al., "Synthesis, Characterization, and Properties of New Polystyrene-SiO.sub.2 Hybrid Sol-Gel Materials," J. Mater. Res., 8-5:1143-1152 (1993). No Month. Yen Wei et al., "Synthesis of Water-Soluble Polyacrylics Modified Silica Sol-Gel Materials", Chem. Mater., 6-10:1737-1741 (1994). No Month. E. Pope et al., "Transparent Silica Gel--PMMA Composites," J. Mater. Res., vol. 4, No. 4 (Jul./Aug. 1989), pp. 1018-1026. G. Wilkes et al., "New Inorganic--Organic Hybrid Materials Through the Sol-Gel Approach," from Silicon-Based Polymer Science: A Comprehensive Resource, (1990) pp. 207-225. No Month. Yen Wei et al., "Polymerization of Aniline and Alkyl Ring-Substituted Anilines in the Presence of Aromatic Additives," J. Phys. Chem., (1990) pp. 7716-7721. No Month. M. Ellsworth and B. Novak, "Mutually Interpenetrating Inorganic-Organic Networks. New Routes into Nonshrinking Sol-Gel Composite Materials," J. Am. Chem. Soc., vol. 113, No. 7 (1991), pp. 2756-2758. No Month. J. Mark et al., "Stimultaneous Curing and Filling of Elastomers, " Macromolecules, vol. 17 (1984) pp. 2613-2616. No Month. H. Huang et al., "Structure--Property Behavior of New Hybrid Materials Incorporating Oligomeric Species into Sol-Gel Glasses. 3. Effect Acid Content, Tetraethoxysilane Content, and Molecular Weight of Poly(dimethylsiloxane)," Macromolecules, vol. 20 (1987) pp. 1322-1330. No Month. Y. Chujo et al., "A Novel Silane Coupling Agent. 1. Synthesis of Trimethoxysilyl-Terminated Poly(N-acetylethylenimine)," Macromolecules, vol. 22 (1989) pp. 2040-2043. No Month. B. Wang et al., "New High Refractive Index Organic/Inorganic Hybrid Materials from Sol-Gel Processing," Macromolecules, vol. 24 (1991) pp. 3449-3450. No Month. G. Wilkes et al., "`Ceramers`: Hybrid Materials Incorporating Polymeric/Oligomeric Species Into Inorganic Glasses Utilizing a Sol-Gel Approach," Polymer Preprints, vol. 26 (1985) p. 300-301. No Month. H. Huang and G. Wilkes, "Structure-Property Behavior of a TEOS-Poly(Tetamethylene Oxide) Hybrid System Prepared by the Sol-Gel Process 1. Effect of PTMO Molecular Weight," Polymer Preprints, vol. 28(2) (1987) pp. 244-245. No Month. Y. Chujo et al., "Block Copolymer of 2-Methyl-2-Oxazoline with Silica Gel. An Organic-Inorganic Hybrid Polymer," Polymer Preprints, vol. 31, No. 1 (1990) pp. 59-60. No Month. C. Landry and B. Coltrain, "Organic-Inorganic Composites Prepared Via the Sol-Gel Method: Some Insights Into Morphology Control and Physical Properties," Polymer Preprints, vol. 32, No. 3 (1991) pp. 514-515. No Month. A. Morikawa et al., "Preparation of a New Class of Polyimide--Silica Hybrid Films by Sol-Gel Process," Polymer Journal, vol. 24, No. 1, (1992) pp. 107-113. No Month. Yen Wei et al., "An Open-Circuit-Potential Study of the Chemical Plymerization on Aniline and Effect of Additives" Polymer Preprints, vol. 35(1) (1994) pp. 242-243. No Month. J. Mark et al., "Electron Microscopy of Elastomers Containing In-Situ Precipitated Silica," Polymer, vol. 26 (1985) p. 2069. No Month. Yen Wei et al., "A Study of the Mechanism of Aniline Polymerization," Journal of Polymer Science: Part A: Polymer Chemistry, vol. 27, (1989) pp. 2385-2396. No Month. Yen Wei et al., "A New Method for Preparation of Electrically Conductive Polythiophenes," Journal of Polymer Science: Part C: Polymer Letters, vol. 28 (1990) pp. 219-225. No Month. M.S. Metwally et al., "Synthesis Of A New Sulphonated Cation Exchange Resin And Its Application In Catalysed Hydrolysis Of Esters," Journal of Materials Science, vol. 25 (1990) pp. 4223-4225. No Month. P. Calvert, "Vegetable and mineral," Nature, vol. 353 (Oct. 10, 1991) pp. 501-502. Y. Haruvy and S. Webber, "Supported Sol-Gel Thin-Film Glasses Embodying Laser Dyes. 1. A New Fast Method for the Preparation of Optically Clear Polysiloxane Thin-Film Glasses," Chem. Mater., vol. 3, No. 3 (1991) pp. 501-507. No Month. K. Rajamani et al., "Kinetics of the Hydrolysis of Ethyl Acetate Catalysed by Cation-exchange Resin," J. Appl. Chem. Biotechnol. vol. 28 (1978) pp. 699-707. No Month. M. Nandi et al., "Molecular Level Ceramic/Polymer Composites. 2. Synthesis of Polymer-Trapped Silica and Titania Nanoclusters," A. Chem. Mater., vol. 3, (1990) pp. 201-206. No Month. B. Novak, "Hybrid Nanocomposite Materials--Between Inorganic Glasses and Organic Polymers," Adv. Mater, vol. 5, pp. 422-433. No Month. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. An electronically conductive inorganic organic hybrid material produced according to a process comprising: (a) preparing a solution comprising (i) solvent, and (ii) an electronically conductive organic polymer or a polymeric precursor thereof; (b) preparing a solution comprising (i) solvent, (ii) monomers that can form an inorganic matrix according to sol-gel chemistry, (iii) a catalyst, and (iv) water; (c) combining the solutions of steps (a) and (b) and allowing a sol-gel reaction to proceed to form a homogeneous gel; and (d) removing components having a molecular weight of less than about 300 daltons from the homogeneous gel of step (c) to provide an electronically conductive inorganic organic hybrid which comprises an electronically conductive polymer and an inorganic matrix. 2. The inorganic organic hybrid according to claim 1, wherein said electronically conductive polymer is selected from the group consisting of unsubstituted or substituted polyphenylene, polyphenylvinylene, polyaniline, polythiophene, polypyrrole, polyacetylene, poly(phenylene sulfide), polydiacetylene, and copolymers thereof which include at least one of said polymers in the backbone or in a side chain. 3. The inorganic organic hybrid according to claim 2, wherein said electronically conductive polymer is substituted with a substituent selected from the group consisting of alkyl groups of from 1 to about 22 carbon atoms, and alkoxy groups of from 1 to about 22 carbon atoms. 4. The inorganic organic hybrid according to claim 1, wherein said electronically conductive polymer is selected from the group consisting of polytoluidine, poly(o-ethoxyaniline), and poly(3-n-pentylthiophene). 5. The inorganic organic hybrid according to claim 1, wherein the polymeric precursor to the electronically conductive polymer is a polymer or copolymer that can be converted to an electronically conductive polymer either by altering the oxidation state of the precursor or by elimination reaction. 6. The inorganic organic hybrid according to claim 1, wherein the electronically conductive organic polymer comprises at least one functional group capable of covalently bonding to the inorganic matrix. 7. The inorganic organic hybrid according to claim 6, wherein the at least one functional group has a formula (I): --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) (I) wherein R.sup.2 is selected from the group consisting of H, halide, and OR.sup.9 ; R.sup.3 is R.sup.2 or R.sup.9 ; R.sup.9 is selected from the group consisting of H, and an organic moiety having from 1 to about 22 carbon atoms and from 0 to about 6 atoms selected from the group consisting of O, S, N, and P; M is a single metal atom selected from the group of elements having atomic numbers of 13-14, 21-32, 39-51, 57-84, and 89-107; and c is the valence of M such that 3.ltoreq.c.ltoreq.6, a=1, 1.ltoreq.b.ltoreq.5. 8. An inorganic organic hybrid material according to claim 1, wherein said monomers of step (b) have the formula (II): M(R.sup.1).sub.a (R.sup.2).sub.b (R.sup.3).sub.(c-b-a) (II) wherein R.sup.1 is R.sup.2 ; R.sup.2 is selected from the group consisting of H, halide, and OR.sup.9 ; R.sup.3 is selected from the group consisting of R.sup.2, and R.sup.9 ; R.sup.9 is selected from group consisting of H, and an organic moiety having from 1 to about 22 carbon atoms and from 0 to about 6 atoms selected from the group consisting of O, S, N, and P; M is a single metal atom selected from the group of elements having atomic numbers of 13-14, 21-32, 39-51, 57-84, and 89-107; and c is the valence of M such that 3.ltoreq.c.ltoreq.6, a=1, and 1.ltoreq.b.ltoreq.5. 9. The inorganic organic hybrid material according to claim 1, wherein the monomer of step (b) is selected from the group consisting of tetraethyl orthosilicate, titanium tetraisopropoxide, and aluminum tri-sec-butoxide. 10. The inorganic organic hybrid material according to claim 1, wherein the catalyst of step (b) is camphor sulfonic acid. 11. The inorganic organic hybrid material according to claim 1, wherein said catalyst of step (b) is selected from the group consisting of proton donors, and proton acceptors. 12. The inorganic organic hybrid material according to claim 11, wherein the proton donor is hydrochloric acid. 13. The inorganic organic hybrid material according to claim 11, wherein the proton donor is formed by ultraviolet irradiation of a photoacid. 14. The inorganic organic hybrid material according to claim 13, wherein the photoacid is selected from the group consisting of diphenyliodonium chloride, and triphenylsulfonium hexafluoroantimonate, and step (c) further comprises directing ultraviolet radiation at the solution of step (c) to generate hydrochloric acid from the photoacid. 15. The inorganic organic hybrid material according claim 1, wherein the solvent of step (a) is selected from the group consisting of tetrahydrofuran, m-cresol, N-methylpyrrolidone, and isopropanol. 16. An electronically conductive inorganic organic hybrid material produced according to a process comprising: (a) preparing a solution comprising (i) solvent, and (ii) an electronically conductive organic polymer or a polymeric precursor thereof; (b) preparing a solution comprising (i) solvent, (ii) monomers that can form an inorganic matrix according to sol-gel chemistry, (iii) a catalyst, and (iv) water; (c) combining the solutions of steps (a) and (b) and allowing a sol-gel reaction to proceed to form a homogeneous gel; and (d) removing components having a molecular weight of less than about 300 daltons from the homogeneous gel of step (c) to provide an electronically conductive inorganic organic hybrid, wherein said electronically conductive polymer is selected from the group consisting of unsubstituted or substituted polytoluidine, poly(o-ethoxyaniline), poly(3-n-pentylthiophene), polyphenylene, polyphenylvinylene, polyaniline, polythiophene, polypyrrole, polyacetylene, poly(phenylene sulfide), polydiacetylene, and copolymers thereof which include at least one of said polymers in the backbone or in a side chain. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION The invention is directed to hybrid materials comprising organic polymers and an inorganic matrix, and more particularly to organic polymers that are homogeneously distributed throughout, and in covalent bonding with, an inorganic matrix, and methodology for preparing same. BACKGROUND OF THE INVENTION As recognized today, organic compounds are the compounds formed primarily of carbon, hydrogen and oxygen, although other atoms such as nitrogen, sulfur and phosphorus may also be present. Inorganic chemistry essentially embraces all the compounds that are not organic compounds. In the natural world, organic compounds are found predominately in animal and vegetable matter, while minerals contain predominantly inorganic compounds. Over 90% of the earth's crust is composed of minerals, with silicate minerals, i.e., minerals having silicon-oxygen bonds, being by far the most prevalent. While the natural world, and the historical development of chemistry, has tended to separate inorganic and organic compounds, modern researchers have become increasingly interested in preparing organic inorganic hybrid materials. As used herein, the term organic inorganic hybrid materials embraces two types of hybrids. In the first, covalent bonding occurs between an organic polymer and an inorganic matrix, and such hybrids will be referred to as covalent hybrids. An oxygen atom, which is commonly found in both organic polymers and inorganic matrices, is typically employed to link the organic and inorganic components of a covalent hybrid. In a second type of hybrid, the organic polymer and inorganic matrix are intimately mixed together, i.e., the organic polymer is uniformly dispersed throughout an inorganic matrix, or vice versa. This second type of hybrid, which does not contain a covalent bond between organic and inorganic components, will be referred to as dispersion hybrids. Covalent and dispersion hybrids are to be distinguished from conventional composite materials formed from organic and inorganic materials, where conventional composite materials have macroscopic interfaces. The development of sol-gel chemistry, which occurred during the past two decades, has provided a convenient entry to the inorganic matrices of hybrid materials according to the invention. For leading references to sol-gel chemistry, which was initially developed for the preparation of ceramics, see, e.g., C. J. Brinker et al. Sol-Gel Science, The Physics and Chemistry of Sol-Gel Processing, Academic Press, San Diego (1990); D. R. Ulrich J. Non-Cryst. Solids (1990) 121:419; G. L. Wilkes et al., Silicon-Based Polymer Science, Advances in Chemistry Series 224, J. M. Ziegler and F. W. Fearon, Eds. Am. Chem. Soc., Wash., D.C. (1990), pp. 207-226; R. Dagani, Chemical & Engineering News (1991) 69-21:30; P. Calvert, Nature (1991) 353:501; and B. M. Novak, Adv. Mater. (1993) 5:422. A number of organic polymers have been incorporated into SiO.sub.2 and/or TiO.sub.2 matrices. See, e.g., G. L. Wilkes et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) (1985) 26:300; H. Huang et al., Macromolecules (1987) 20:1322; J. E. Mark et al., Macromolecules (1984) 17:2613; J. E. Mark et al., Polymer (1985) 26:2069; S. B. Wang et al., Macromol. Reports (1991) A28:185; and Y. Haruvy et al., Chem. Mater. (1991) 3:501, using polydimethylsiloxane; H. Huang et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) (1985) 28:244, using poly(tetramethylene oxide); Nandi, et al., A. Chem. Mater. (1991) 3:201), using polyimides; B. Wang et al., Macromolecules (1991) 24:3449; and A. Morikawa et al., Polym. J. (1992) 24:107), using poly(arylene ether ketone) and poly(arylene ether sulfone); E. J. A. Pope et al., J. Mater. Res. (1989) 4:1018; C. J. T. Landry et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) (1991) 32:514; and N. W. Ellsworth et al., J. Am. Chem. Soc. (1991) 113:2756, using polymethacrylates; Y. Chujo et al., Macromolecules (1989) 22:2040; Y. Chujo et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) (1990) 31:59; and Y. Chujo et al., Makromol. Chem., Macromol. Symp. (1991) 42/43:303), using polyoxazolines. For reviews on specific applications of hybrid materials, see, e.g., M. G. Kanatzidls et al., Chem. & Eng. News (1990) 36; Handbook of Conducting Polymers, T. A. Skotheim, Ed. Marcel Dekker, New York (1986) 1 & 2; and ACS Symposium on Conducting Polymers: Polym. Prepr. (1994) 35-1. Simultaneous with the development of sol-gel chemistry, and hybrid materials based on sol-gel chemistry, has been the development of conductive organic polymers, where that conductivity includes ionic and electronic conductivity. For representative reports describing electronically conductive organic polymers, see, e.g., Y. Wei et al., J. Polym Sci., Part A, Polym. Chem. (1989) 27: 2385-2396; Y. Wei et al., J. Polym Sci, Part-C (1990) 28:219-226; Y. Wei et al., J. Phys. Chem. (1990) 94:7716-7721; Y. Wei et al., Polym Prep. (1994) 35-1:242-243; Y. Wei et al., U.S. Pat. No. 4,940,517 (1990); Y. Wei et al., U.S. Pat. No. 4,986,886 (1991); and Y. Wei et al., U.S. Pat. No. 5,120,807 (1992). For representative reports describing ionically conductive polymers, many of which are also used as ion exchange resins, see, e.g., Albright, R. L. and Yarnell, P. A., "Ion-Exchange Polymers" Encyclopedia of Polymer Science and Engineering, 2nd edition, 8:341-393 (1987); Inaba, M., et al., Chem. Lett. (1993) 10:1779; Rajamani, K., et al., J. Appl. Chem. Biotechnol. (1978) 28:699; Metwally, M. S., et al ., J. Material Sci. (1990) 35:4993; Small, H., Ion Chromatography, Plenum Press, New York, (1989) pp. 41-55; Snyder, L. R., et al., Introduction to Modern Liquid Chromatography, 2nd edition, John Wiley & Sons, New York (1974); and Done, J. N., et al., Applications of High-Speed Liquid Chromatography, John Wiley & Sons, New York (1974). Conductive polymers are being increasingly investigated for various commercial applications. For example, polyaniline has been studied as an electroactive coating that changes the corrosion behavior of stainless steel. See, e.g., DeBerry, D. W. J Electrochem. Soc., (1985) 132:1027. Designs for items containing conductive organic polymer often call for the polymer to adhere to inorganic materials, e.g., metal or ceramic. Achieving intimate and stable contact between a conductive organic polymer and an inorganic material has been problematic, and there remains a need in the art for methodology to achieve this goal. SUMMARY OF THE INVENTION The invention provides for an inorganic organic hybrid that may be produced according to a process comprising the steps: (a) preparing a solution comprising i) solvent and ii) conductive organic polymer or a polymeric precursor thereof; (b) preparing a solution comprising i) solvent ii) monomers that can form an inorganic matrix according to sol-gel chemistry iii) a catalyst and iv) water; (c) combining the solutions of steps (a) and (b) to allow a sol-gel reaction to proceed and form a homogeneous gel; and (d) removing components having a molecular weight of less than about 300 daltons from the homogeneous gel of step (c) to provide an inorganic organic hybrid. Another aspect of the invention is a process to prepare an inorganic organic hybrid material as described above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The inorganic organic hybrids of the invention, also referred to herein as hybrid materials, are the reaction product of hybrid forming components including organic polymer, sol-gel monomer, catalyst and solvent, where the solvent is preferably aqueous. The solvent provides for a homogeneous distribution of organic polymer and sol-gel monomer in a solution, and thus the resulting hybrid material will likewise have a homogeneous distribution of organic polymer in the inorganic matrix that forms from the sol-gel monomer. The catalyst is present to promote the hydrolysis and condensation chemistry that is necessary to convert the sol-gel monomer into an inorganic matrix. The sol-gel monomer reacts with itself to form an inorganic matrix, which because it typically has a high glass transition temperature, is also referred to as a glass or an inorganic glass. The organic polymer either has functionality that imbues it with conductive properties, for example electronically or ionically conductive properties, or has a structure that may react and thereby be converted to an organic polymer having conductive properties. In a preferred embodiment, the organic polymer comprises functional groups that react with the sol-gel monomer, so that covalent bonding is formed between the organic polymer and the inorganic matrix. The inorganic matrix of the inorganic organic hybrid materials of the invention is prepared using sol-gel chemistry. Monomers that may be employed in sol-gel chemistry are numerous and well-known in the art, and are referred to herein as sol-gel monomers. Any of the monomers that are conventionally employed to prepare an inorganic matrix by way of sol-gel chemistry, may also be employed to prepare the inorganic matrix of the inorganic organic hybrid materials of the invention. Exemplary sol-gel monomers include, without limitation, tetraethyl orthosilicate (TEOS), titanium tetraisopropoxide (TIPO), aluminum tri-sec-butoxide (ASBO), silicon tetrachloride, titanium tetrabutoxide, titanium (IV) bis(ethyl acetate), silicon(IV) chloride, silicon(IV) bromide, silicon(IV) acetate, silicon(IV) acetylacetonate, triethoxyhydrosilane, hexachlorodisiloxane, titanium(IV) ethoxide, titanium(IV) butoxide, titanium(IV) chloride, titanium(IV) 2-ethylhexoxide, titanium(IV) oxide acetylacetonate, titanium diisopropoxide bis(2,4-pentanedionate), titanium(IV) (triethanolaminato)isopropoxide, zirconium(IV) tert-butoxide, zirconium (IV) acetylacetonate, zirconium (IV) ethoxide, rubidium acetylacetonate, ruthenium(III) acetylacetonate, niobium(IV) ethoxide, vanadium(IV) oxytriethoxide, tungsten hexaethoxide, etc. Essentially any monomer useful in sol-gel chemistry as described in J. Livage, M. Henry and C. Sanchez, Prog. Solid State Chem. (1988) 18:259-341, where this article is incorported herein by reference, may be used in the instant invention. Sol-gel chemistry, and exemplary monomers used to prepare inorganic matrices by sol-gel chemistry, are disclosed in the following references, where each of the following references is hereby incorporated herein by reference: C. J. Brinker et al. Sol-Gel Science, The Physics and Chemistry of Sol-Gel Processing, Academic Press, San Diego (1990); D. R. Ulrich J. Non-Cryst. Solids (1990) 121:419; G. L. Wilkes et al., Silicon-Based Polymer Science, Advances in Chemistry Series 224, J. M. Ziegler and F. W. Fearon, Eds. Am. Chem. Soc., Wash., D.C. (1990), pp. 207-226; R. Dagani, Chemical & Engineering News (1991) 69-21:30; P. Calvert, Nature (1991) 353:501; and B. M. Novak, Adv. Mater. (1993) 5:422. A general formula for sol-gel monomers is M (R.sup.1).sub.a (R.sup.2).sub.b (R.sup.3).sub.(c-a-b). R.sup.1 may be either R.sup.2 or a polymer ligand, where polymer ligand is defined herein as an organic polymer having at least one pendant M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group. Pendant groups, i.e., groups that are appended to an organic polymer, are defined as groups that are covalently bound to, but not part of, the backbone of an organic polymer. The preferred organic polymer of the polymer ligand is a long chain of carbon atoms, having various substitutions as described below. Thus, polymer ligands are organic polymers wherein at least one hydrogen of the organic polymer is replaced with a M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group. Sol-gel monomers incorporating a polymer ligand may be prepared by the polymerization or copolymerization reaction of monomers that are functionalized with a group of the formula M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b), and that undergo, for example, free radical, ionic, Ziegler-Natta, or group transfer polymerization. Exemplary monomers are methylidene monomers, i.e., monomers containing the .dbd.CH.sub.2 group. Exemplary methylidene monomers include, without limitation, acrylates, methacrylates, styrene and styrene derivatives, 1-olefins and vinyl molecules. When acrylate and/or methacrylate, i.e., CH.sub.2 .dbd.CR.sup.4 --CO.sub.2 --R.sup.5, is used as a monomer to prepare the polymer ligand, at least some of said monomer may contain the --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group, which may be covalently bound to the monomer as one or both of R.sup.4 or R.sup.5. Thus, R.sup.4 may be --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) or --H for acrylate monomers, and --CH.sub.3 or R.sup.6 --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) for methacrylate monomers, where R.sup.6 is a C.sub.1 -C.sub.12 organic moiety. For either acrylate or methacrylate monomers, R.sup.5 may be H, C.sub.1 -C.sub.22 organic moiety or R.sup.6 --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b). Exemplary acrylate and methacrylate monomers that may be used to prepare the organic ligand of the invention include, without limitation, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate (ESMA), methacryloxypropyltris(pentamethyldisiloxanyl)silane, 3-acryloxypropyldimethylmethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 3-acryloxpropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane, 2-methacryloxyethyldimethyl[3-trimethoxysilyl propyl]ammonium chloride, 3-methacryloxypropyltris(methoxyethoxy)silane, methacryloxypropenyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and methacryloxypropylmethyldichlorosilane. Styrene and styrene derivatives may also be used to prepare the organic ligand of the sol-gel monomer. Preferably, at least some styrene or styrene derivative is covalently bonded to the M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group, where the covalent bond is achieved by substituting at least one hydrogen of styrene or the styrene derivative with the M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group. The term styrene derivative is intended to include all molecules having the styrene formula, i.e., CH.sub.2 .dbd.CH--Ph, but wherein one or more of the styrene hydrogen atoms, other than the CH.sub.2 .dbd. hydrogen atoms, may be replaced with halide, sulfonic acid, or an organic moiety having 1 to about 22 carbon atoms and 0 to about 4 oxygen, sulfur, nitrogen and/or phosphorus atoms. Exemplary, non-limiting examples of styrene derivatives include, .alpha.-methylstyrene, .alpha.-halostyrene, .alpha.-phenylstyrene, as well as styrene derivatives substituted on the phenyl ring at one or more of the o-, m- or p-positions with an alkyl, alkoxy, aryl, or halo group, such as o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-(n-butyl)styrene, p-(tert-butyl)styrene, p-(n-hexyl)styrene, p-(n-octyl)styrene, p-(n-nonyl)styrene, p-(n-decyl)styrene and p-(n-dodecyl)styrene. Exemplary styrene and styrene derivatives that may be employed to prepare the polymer ligand of the invention include, without limitation, styrylethyltrimethoxysilane (STMS), styrylethyltriethoxysilane, styrylethyltrichlorosilane, styrylpropyltrimethoxysilane and styrylpropyldimethylethoxysilane. STMS is a preferred styrene derivative according to the invention. The 1-olefin monomers that may be used as a monomer to prepare the organic ligand have the formula CH.sub.2 .dbd.CHR.sup.7, wherein R.sup.7 has the formula --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) or R.sup.8 --M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b), wherein R.sup.8 is a hydrocarbon group having 1 to about 10 carbon atoms. Exemplary 1-olefin monomers that may be employed to prepare the polymer ligands of the invention include, without limitation, vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, vinyltriphenoxysilane, vinyl-tert-butoxysilane, vinyltrichlorosilane, vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltris(methylethylketoximine)silane, 1-vinyl-1-methylsila-17-crown-6,1-vinylsilatrane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinyldiethylchlorosilane, N-(3-trimethoxysilylpropyl)-N-methyl-N,N-diallylammonium chloride, tetraallyloxysilane and diisopropenoxydimethylsilane. Vinyltriethoxysilane and vinyltrimethoxysilane are preferred 1-olefin monomers according to the invention. The polymer ligand can also be prepared by copolymerization of one or more of the methylidene monomers that contain at least one sol-gel reactive --M(R.sup.2).sub.b (R.sup.3).sub.(c-b-a) group with one or more of methylidene monomers that do not contain the reactive group. Exemplary methylidene monomers that do not contain --M(R.sup.2).sub.b (R.sup.3).sub.(c-b-a) group include, without limitation, acrylonitrile, vinylhalides, acrylates, methacrylates, acrylic acid, acrylamine, tetrafluoroethylene, 1,1-dihaloethylene, butadiene, 2-halobutadiene, isoprene, ethylene, .alpha.-olefins, vinylethers, vinyl acetate, vinyl carbazole, arylethylenes, vinylketones, 2-methylene-1,3-dioxepane and vinyl butyral. R.sup.2 in the sol-gel monomer or polymer ligand of the invention is a reactive leaving group, i.e., a group that may be displaced during the inorganic organic hybrid forming reaction, and allow the position formerly occupied by the R.sup.2 group to be occupied by a bond to either another molecule of sol-gel monomer or a molecule of organic polymer. Representative R.sup.2 groups are hydrogen, halide and OR.sup.9, where R.sup.9 is hydrogen or an organic moiety having from 1 to 22 carbon atoms and 0 to about 6 oxygen, sulfur, nitrogen, and/or phosphorus atoms. C.sub.1 -C.sub.5 alkoxy groups are a preferred R.sup.2 group. R.sup.3 may be an R.sup.2 group, e.g., hydrogen, halide or OR.sub.9, or R.sub.3 may be an R.sup.9 group, i.e., R.sub.3 may be an organic moiety having from 1 to 22 carbon atoms and 0 to about 6 oxygen, sulfur, nitrogen, and/or phosphorus atoms. Preferably, R.sup.3 is identical to R.sup.2. M in the sol-gel monomer or polymer ligand of the invention is a metal, and specifically a transition metal, a post-transition metal, a lanthanide, an actinide or silicon. That is, M has an atomic number of 13-14, 21-32, 39-51, 57-84 and 89-107. Preferred metals are Al, Si, Ti, Zr and Hf. Furthermore, M is capable of forming stable bonds to at least three atoms. Thus, "c" is at least equal to 3, and is not larger than the maximum number of atoms to which M may be bonded. For example, when M is Si, where Si ordinarily forms bonds to four atoms, then c is 4, however when M is Al, where Al ordinarily forms bonds to three atoms, then c is 3. Typically, "c" is a number including 3 to 6. The number "a" is fixed at 1. Therefore, the number "b" is at least 1 and may be as high as c-1. The organic polymer of the inorganic organic hybrid forming components is a conductive organic polymer, where electronically or ionically conductive polymers and precursors thereof are specifically included within the term conductive organic polymer. The organic polymers have a backbone composed primarily of carbon, that may optionally incorporate other atoms, such as nitrogen and oxygen. As the name implies, electronically conductive polymers are capable of conducting electrons upon doping. In general, electronically conductive polymers have a chain of pi orbitals that extend along the entire length of the polymer. Electronically conductive polymers are sometimes referred to in the art as electrically conductive polymers or electroactive polymers. Examples of electronically conductive polymers include polyphenylene, polyphenylvinylene, polyaniline, polythiophene polypyrrole, polyacetylene, poly(phenylene sulfide), and polydiacetylene and copolymers thereof which include at least one of said polymers in the backbone or in a side chain, as well as substituted derivatives thereof that are electrically conductive upon doping. Exemplary substitutents on an electronically conductive polymer include alkyl groups having 1 to about 22 carbon atoms, an alkoxy groups having 1 to about 22 carbon atoms. Polytoluidine, poly(o-ethoxyaniline) and poly(3-n-pentylthiophene) are exemplary substituted derivatives of electronically conductive polymers. Exemplary electronically conductive polyanilines and derivatives thereof that may be employed in the practice of this invention are disclosed in, for example, U.S. Pat. No. 4,940,517, the entire disclosure of which is hereby incorporated herein by reference. Exemplary electronically conductive polypyrroles and derivatives thereof that may be employed in the practice of this invention are also disclosed in, for example, U.S. Pat. No. 5,120,807, the entire disclosure of which is hereby incorporated herein by reference. Exemplary electronically conductive polythiophenes and derivatives thereof that may be employed in the practice of this invention are further disclosed in, for example, U.S. Pat. No. 4,986,886, the entire disclosure of which is hereby incorporated by reference. While the organic polymer may be an electronically conductive polymer, the organic polymer may also be a precursor to an electronically conductive polymer. Examples include (1) polymers that can be converted to electronically conductive polymers by altering the oxidation state of the precursor polymers, e.g., polyaniline in its fully reduced or fully oxidized forms, and (2) polymers that can be converted to electronically conductive polymers from soluble and processible non-conjugated precursor polymers by a simple elimination reaction, e.g., polyphenylenechloroethylene and poly(p-xylene-2-dimethylsulfonium chloride), both of which are precursors to conductive polyphenylenevinylene, where they form polyphenylenevinylene upon simple heating to achieve elimination of, e.g., HCl. Ionically conductive polymers, as the name implies, are capable of transferring ionic groups along a polymer chain. The ionically conductive polymers of the invention have pendant charged groups, i.e., groups having a positive and/or negative charge are substituted for any hydrogen atom otherwise present on the ionically conductive polymer. Exemplary charged groups that may be incorporated into the ionically conductive polymer include, without limitation, negatively charged groups such as carboxylate, sulfate, sulfonate, phosphate, phenolate, hydroxide, alkoxylate, ketonate, enolate, borate, silicate and titanate, as well as positively charged groups such as ammonium, sulfonium, oxonium, iodonium, pyridinium, phosphenium, metallocenes and organometallic groups. The organic polymer to which the charged groups are appended is a polymer or copolymer having a structure provided by polymerization of a monomer of the formula CH.sub.2 .dbd.C(R.sup.a)(R.sup.b), wherein R.sup.a is H or CH.sub.3, R.sup.b is R.sup.c or CO.sub.2 R.sup.3, and R.sup.c is C.sub.1-C.sub.22 hydrocarbyl. Associated with the charged group will be a counterion, where the counterion is the actual species being conducted in the ionically conductive polymers of the invention. Exemplary counterions for negatively charged groups include proton, ammonium, sulfonium, oxonium, iodonium, phosphenium, and all metal ions including, without limitation, Na.sup.+, K.sup.+, Li.sup.+, Mg.sup.++, Ca.sup.++, Fe.sup.++, Cu.sup.++, Zn.sup.++ and Cr.sup.+++. Exemplary counterions for positively charged groups include, without limitation, halides, sulfate, sulfonate, phosphate, carboxylate, hydroxide, alkoxide, halorate, halorite, nitrate, nitrite and sulfite. While the organic polymer may be an ionically conductive polymer, the organic polymer may also be a precursor to an ionically conductive polymer. A precursor to an ionically conductive polymer is any organic polymer that may undergo reaction to form an ionically conductive polymer. An example of a precursor to an ionically conductive polymer is polystyrene, where the term polystyrene is used broadly to include all polymers and copolymers that have pendant phenyl groups as may be derived from, for example, styrene. The term polystyrene as used herein thus encompasses copolymers of styrene and acrylate or methacrylate esters or acid. The organic polymer, in addition to having functionality necessary to give the polymer conductive properties, also desirably contains functionality that allows for covalent bonding between the organic polymer and the inorganic matrix formed by the reaction of the sol-gel monomers. An exemplary functional group is M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b), which upon catalysis will undergo condensation reaction with the sol-gel monomers. The definitions for R.sup.2, R.sup.3, a, b and c in the groups pendant to the preferred polystyrenes are the same as that provided above, in regard to the inorganic component. One convenient approach to preparing an organic polymer, having pendant M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) is to copolymerize at least one of styrene or acrylonitrile with acrylate, where at least some of the acrylate has covalent bonding to the M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group. 3-(trimethoxysilyl)propyl methacrylate is an exemplary acrylate having a covalent bonding to a M(R.sup.2).sub.b (R.sup.3).sub.(c-a-b) group. The copolymerization of 3-(trimethoxysilyl)propyl methacrylate with styrene provides a copolymer identified by the letter P(St-MSMA). Polymerization chemistry suited to prepare such copolymers of styrene and acrylates has been described in, e.g., Rao, V. L., et al., J. Macromol. Sci. Chem. Ed. (1986) A23:1079 and Rao, V. L., et al., Eur. Polym. J., (1989) 25:605, where the two cited references co-authored by Rao, V. L. are incorporated herein by reference. The content of the functional groups in the organic polymer, that are reactive with sol-gel monomer, is generally small in order to afford polymer and copolymers whose properties are substantially the same as the polymers and copolymers not having sol-gel monomer-reactive groups. Although available via free-radical chemistry, poly[methyl methacrylate-co-3-(triethoxysilyl)propyl methacrylate] [P(MMA-ESMA)] may also be prepared through group-transfer polymerization. For example, P(MMA-ESMA) may be prepared by the group-transfer copolymerization of allyl methacrylate and methyl methacrylate, using trimethylsilyl ketene acetal as the initiator and tris(dimethylamino)sulfonium bifluoride (TASHF.sub.2) as catalyst. This preparation of a methacrylate copolymer, may be followed by hydrosilylation of the ester allyl groups in the copolymer, in the presence of the Speier's catalyst (H.sub.2 PtCl.sub.6) . This method offers excellent control of the molecular weight of polymers and copolymers containing alkoxy silyl groups. Exemplary alkoxysilyl-containing monomers that may be employed in the invention as comonomer, to provide organic polymers having functionality that is reactive with sol-gel monomers, includes, without limitation, 3-(trimethoxysilyl)propyl methacrylate (MSMA), 3-(triethoxysilyl)propyl methacrylate (ESMA) and styrylethyltrimethoxysilane (STMS) and vinyltriethoxysilane. Polystyrene is a preferred precursor to an organic polymer that is ionically conductive. Thus, polystyrene may be combined with sol-gel monomers, catalyst and solvent to form an inorganic organic hybrid. After incorporation into a sol-gel derived matrix, polystyrene may be converted to an ionically conductive polymer by exposure to reaction conditions that introduce the ionic functional group onto the phenyl group. Sulfonation chemistry to introduce the sulfonic acid group to the phenyl groups of polystyrene is a preferred method to convert a polystyrene to an anionically conductive sulfonated polystyrene. Suitable sulfonation methodology is described in, e.g., Braun, D., et al., Practical Macromolecular Organic Chemistry, Harwood Academic Publishers, (1984) p. 313. The aforecited Braun, D. reference is incorporated herein by reference. Chloromethylation followed by reaction with a tertiary amine to introduce the positively charged ammonium groups to the phenyl groups of polystyrene is a preferred method to convert polystyrene to a cationically conductive polystyrene. Suitable methodology for chloromethylation followed by reaction with a tertiary amine is described in, e.g., Odian, G., Principles of Polymerization, 3rd edition, Wiley Interscience, (1991), p. 713, which is incorporated by reference herein. The components necessary to form an organic inorganic hybrid of the invention includes at least one catalyst, where the catalyst may be either a proton donor, i.e., an acid, or a proton acceptor, i.e., a base, or a precursor thereof. Thus, the catalyst may be a proton source, where exemplary acids include, without limitation, HCl, HBr, HI, H.sub.2 SO.sub.4, H.sub.3 PO.sub.4, HNO.sub.3, silicic acid, boric acid, methanesulfonic acid, trifluoroacetic acid, tolylsulfonic acid and polyacrylic acid. Alternatively, the catalyst may be a base, where exemplary bases include, without limitation, alkaline metal hydroxides (like NaOH, KOH, CsOH), ammonium hydroxide, ammonia, alkaline metal or ammonium alkoxides (like NaOC.sub.2 H.sub.5, KOC.sub.2 H.sub.5), alkylamine, arylamine, dialkylamine, diarylamine, trialkylamine, imidazole, poly(vinyl imidazole) and polyethylenimine. The catalyst may also be a precursor to an acid or base. Exemplary catalysts that are a precursor to an acid are the so-called photoacids, which upon exposure to specific radiation, will decompose to form a proton. Exemplary photoacids include, without limitation, diphenyliodonium chloride (DIC) and triphenylsulfonium hexafluoroantimonate (TSHF), which decompose to form HCl upon exposure to UV radiation. The catalyst may also be a Lewis acid or a Lewis base. Exemplary Lewis acids include, without limitation, boron trifluoride, aluminum trichloride and iron trichloride. A preferred catalyst is HCl, where the HCl may be used directly as a hybrid forming component, or may be generated from a photoacid. When HCl is used directly as a hybrid forming component, then water is preferably present as a component solvent and hydrolysis agent. It is important to note that under normal conditions, the presence of water is necessary for the sol-gel formation reactions. Water functions as a reagent in the first step of the sol-gel reactions, i.e., hydrolysis of the precursors. In the second step of the sol-gel reactions, i.e., polycondensation, water is partially regenerated as a condensation byproduct. When aqueous acids are used as the catalyst, or m-cresol (which often contains a small amount of water as impurity) was used as solvent in the hybrid forming sol-gel reactions, addition of an extra amount of water may not be needed because water is already present in the acids or m-cresol. Another preferred catalyst is camphor sulfonic acid (CSA). When used as the catalyst to prepare a polyaniline-sol gel hybrid material, CSA is believed to serve three functions in the system: (1) as a dopant to dope polyaniline, (2) to render the resulting doped polyaniline soluble in common organic solvents, and (3) as an acid catalyst for the reactions of the sol-gel monomers, including P(MMA-MSMA). The organic inorganic hybrid forms when the organic polymer and sol-gel monomers are exposed to a catalyst in the presence of a solvent. Other than being inert, a liquid under the reaction conditions, and capable of dissolving both the organic polymer and the sol-gel monomers, there is really no limitation on the identity of the solvent. The term solvent, as used herein, includes combinations of two or more component solvents. The solvent, or component solvents, which may be used in the practice of the invention include N-methylpyrrolidone, m-cresol, tetrahydrofuran, isopropanol, butylalcohol, dimethylsulfoxide, dimethylformamide, ethyl acetate, methylethylketone and acetonitrile. Forming both the organic polymer and the sol-gel monomers as a single solution, prior to forming the inorganic organic hybrid, ensures a uniform distribution of the organic polymer in the inorganic matrix. Thus, there is no macroscopic phase separation between the organic polymers and inorganic matrix in the hybrids of the invention, as evidenced by the facts that (1) the hybrid materials are transparent and therefore the scale of phase separation, if any, should be below the wavelengths of visible light (i.e., <400 nm) and that (2) the glass transition temperature (T.sub.g) of the polymer components is either unmeasurable or significantly altered in comparison with the bulk polymers. In the preparation of polyaniline sol-gel hybrid materials, a preferred solvent is m-cresol. Casting a polyaniline sol-gel monomer film from m-cresol can provide a film having a relatively higher conductivity than may be observed if a solvent other than m-cresol is employed. According to the so-called secondary doping concept (Y. G. Min et al., Polym. Prepr., (1994) 35-1:231 and Y. Xia et al., Macromolecules (1994) 27:7212), the higher conductivity in the presence of m-cresol can be explained as follows: m-cresol (as so-called secondary dopant) promotes the polyaniline molecular conformational change from a more "coil-like" form towards a more "rod-like" form. Since the "rod" conformation is more likely to crystallize than the "coil" conformation, the attainment of a more rod-like conformation frequently increases the crystallinity of the polymer and, therefore, enhances the inter-molecular component of the bulk conductivity. The relative amounts of the components, i.e., the relative amounts of the organic polymer, sol-gel monomers, catalyst and solvent, that may be combined to allow formation of an organic inorganic hybrid of the invention, can vary over a wide range of values. The weight ratio of the organic:inorganic component can range from less than 5:95 to more than 95:5. The choice of this ratio depends on the desired properties of the final hybrid materials. As shown in Example 1, higher organic content (i.e., more polyaniline) in a hybrid material results in better electronic conductivity. On the other hand, higher inorganic content (e.g., less polyaniline) leads to better adhesion properties to an inorganic substrate. The weight percentage of the catalyst with respect to the sol-gel precursors can range from less than 0.01% to more than 500%. Preferred range is about 0.1% to about 200%. In Example 1, the molar ratio of camphor sulfonic acid to polyaniline is 2 to 1. The weight percentage of water with respect to the precursors can range from less than 0.1% to more than 1000%, where a preferred range is from about 1% to about 100%. The temperature range for the sol-gel reactions is only limited by the freezing point and boiling point of the reaction system that contains all the components, i.e., organic component, inorganic component, water, solvent and catalyst. A preferred reaction temperature range is from about 0.degree. C. to about 100.degree. C. The temperature range for post-reaction reaction drying of the hybrid materials is from about 0.degree. C. to more than 300.degree. C., as long as the organic component does not decompose. A preferred range is from about 15.degree. C. to 200.degree. C. The post-reaction drying can also be achieved by other chemical and physical methods or the combination of these methods. Exemplary methods include, without limitation, microwave radiation, infrared radiation, and supercritical fluid extraction. After the solutions of organic polymer and sol-gel monomer are mixed, two distinct phases may be observed, because Water may be substantially the only solvent present to dissolve the sol-gel monomers, and an organic, hydrophobic solvent may be the solvent selected to dissolve the organic polymer. After the formation of the two-phase mixture, the mixture is stirred and condensation reactions will occur as the hybrid material forms. Typically, as the condensation reaction progresses and nears completion, the reaction mixture becomes homogeneous and takes on a gel-like quality, afterwhich stirring is impractical. The gel-like quality is readily discerned simply by gently shaking the reaction vessel containing the forming hybrid material: when the reaction mixture attains a gel-like quality or character, it will not readily flow upon being tilted. As explained previously, solvent is, in most cases, necessarily present as one of the components of the organic inorganic hybrid forming reaction, in order to ensure a homogeneous distribution of organic and inorganic components in the final hybrid. However, the final hybrid material preferably contains little if any water or solvent. Steps may therefore be taken to remove the solvent, and other volatile molecules that are generated and present at the conclusion of the hybrid forming reaction, after or during formation of the hybrid material. The solvents and volatile components typically present in the reaction mixture have a molecular weight of less than about 300 daltons. One approach to forming a solvent-free hybrid material is to cast the solution of hybrid forming components, i.e., the solution formed of organic component, inorganic component, catalyst, and aqueous solvent, onto a surface so as to form a thin film. Assuming the thickness of the film is not too large, the solvent will be readily able to evaporate away from the other hybrid forming components. An alternative approach to preparing a solvent-free hybrid material is to place the solutions of hybrid forming components in a jar with a lid, where the lid has only a few, small orifices through which solvent may pass. The few, small orifices ensure that the solvent will escape slowly from the other hybrid forming components, and therefore that the formed hybrid material will be predominantly monolithic, i.e., a single crack-free piece of material. Differential scanning calorimetry (DSC) analysis of the hybrid materials of the invention shows a general lack of well-defined glass transition temperatures for the polymers in the inorganic matrices, indicating that the polymer chains are uniformly distributed in the hybrid materials. Refractive index analysis also supports the view that the organic polymers of the hybrids of the invention are uniformly distributed throughout the inorganic matrix. Polystyrene-silica hybrid materials were obtained with excellent optical transparency over the entire composition range, and wherein the refractive index changed continuously between the limits of polystyrene and silica glass. This observation is consistent with the conclusion that the polymer chains are uniformly distributed in the inorganic matrices. It is generally the case that with increasing concentration of the conductive organic polymer in the hybrid material, the conductivity of the hybrid will increase. This view is supported, for example, by the data in Table 3, regarding the conductivity of polyaniline containing hybrid materials. The data is Table 3 is consistent with the view that the sol-gel monomers, including P(MMA-MSMA), are not electronically conductive, and that only the polyaniline component contributes to the observed conductivity. This view is also supported, for example, by the data in Table 6, which illustrates that an increase in cation exchange capacity is observed with an increase in the sulfonated polystyrene content of a hybrid material. The invention provides for hybrid materials that serve as conductive coatings having both high conductivity and good adhesive properties. The data in Table 2, which reports the adhesion properties for polyaniline sol-gel hybrid materials, demonstrates that the adhesion of a polyaniline coating to glass increases significantly when the polyaniline is incorporated into a sol-gel matrix. By measuring both adhesion and conductivity as a function of conductive polymer content in a hybrid material, one skilled in the art may determine a hybrid composition that provides both good adhesion and good conductivity properties. The invention will now be illustrated by the following non-limiting examples, which demonstrate the advantageous properties of the present invention. Parts and percentages are by weight unless indicated otherwise. Reagents, Instrumentation and Measuring Techniques Acetonitrile (Fisher, Pittsburgh, Pa.), ammonium persulfate, (NH.sub.4).sub.2 S.sub.2 O.sub.8, (99%, EM Science, Cherry Hill, N.J.), and aluminum tri-sec-butoxide (ASBO) (Aldrich Chemical Company, Milwaukee, Wis.) were all used as received. Aniline (Aldrich) was doubly distilled under a reduced pressure prior to use. Benzene (Aldrich, HPLC grade) was purified by distillation and then stored over 4 .ANG. molecular sieves. Benzoyl peroxide (Fisher) was purified by one or two recrystallizations from methyl alcohol. sec-Butyl methacrylate (SBMA) (Aldrich) was distilled under reduced pressure prior to use. Camphor sulfonic acid (Aldrich), m-cresol (Aldrich) and diphenyliodonium chloride (DIC) (Aldrich and Janssen, New Brunswick, N.J.) were used as received. Ethyl methacrylate (EMA) (Aldrich) was distilled under reduced pressure prior to use. HCl solutions contain water as the solvent. Hexane (Fisher) and LiClO.sub.4 (Johnson Matthey, West Deptford, N.J.) were used as received. Methyl methacrylate (MMA) (Aldrich) was distilled prior to use. 1-Methyl-2-pyrrolidinone (NMP) (Sigma-Aldrich, HPLC grade) was used as received. Styrene (Aldrich) was purified by treating with aqueous KOH or NaOH (to remove hydroquinone), drying over magnesium sulfate or anhydrous calcium chloride, followed by distillation under reduced pressure in a nitrogen atmosphere. Styrylethyltrimethoxysilane (STMS, United Chemical Technologies, Bristol, Pa.) was purified by column chromatography on silica gel. Tetraethyl orthosilicate (TEOS) (Aldrich), tetrahydrofuran (THF) (Aldrich, HPLC grade) and titanium tetraisopropoxide (TIPO) (Aldrich) were used as received. 3-(Trimethoxysilyl)propyl methacrylate (MSMA) (Aldrich) was distilled under reduced pressure in nitrogen. Triphenylsulfonium hexafluoroantimonate (TSHF) was obtained as a 50% solution in propylene carbonate (Pflatz & Bauer, Waterbury, Conn.) and used as received. Electrical conductivity was measured by using a standard four-probe technique. Cyclic voltammetry studies were performed on an EG&G PAR potentiostat/galvanostat (EG&G PAR, Princeton, N.J., Model 173) with a universal programmer (Model 175). Dynamic mechanical analysis was performed on a DuPont 9900 TA thermal analysis system equipped with the DMA 983 module at a programmed heating rate of 50.degree. C./min. Adhesion properties were measured using Scotch tape. Thus, after coating a glass substrate with a solution of the hybrid of interest, the coating was cut with a razor to make grid lines. The total test area was 4 cm.sup.2 with each square dimension of 2.times.2 mm. A strip of Scotch tape (Scotch.TM. Magic.TM. tape with a width of 19.0 mm, by 3M, Minneapolis, Minn.) was applied firmly to cover the grid area at room temperature. After about 1 min, the tape was stripped off with one quick peel. By counting the number of squares peeled off versus the total number of squares covered by the tape, the relative adhesivity of a film could be estimated. |
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