WO2006076016A2 - Conducting polymers - Google Patents

Abstract

Embodiments of the present invention are directed at the preparation of conducting polymeric material comprising a phase separable segmented (co)polymer wherein at least one segment of the copolymer comprises a donor segment that forms a complex with an added conducting polymer, or a conducting polymer precursor, wherein the self assembly characteristics of the resulting phase separable segmented copolymer comprising the conducting polymer complex templates the nanostructure of the final conducting material. The phase separable segmented copolymers can comprise any structural topology including linear block copolymers, star copolymers, graft copolymers or brush copolymers such that one phase of the final nanostructure of the conducting material comprising a conducting polymer complex form a spherical, cylindrical. gyroidal or lamellar morphology.

Description

TITLE: Conducting Polymers

INVENTORS

Bruno Dufour and Krzysztof Matyjaszewski

TECHNICAL FIELD OF THE INVENTION The invention is directed towards the preparation of conducting polymeric materials by utilizing the self assembly characteristics of a strongly phase separating precursor segmented (co)polymer comprising at least one non-donor segment and at least one donor segment wherein the donor segment forms a complex with, and thereafter templates the organization of, the conductive polymer complex; thereby forming the final stable nano- structured conducting material.

BACKGROUND OF THE INVENTION

Since their discovery, conducting polymers have been widely studied because they can combine the ease of processing and the lightness of plastics with the electrical properties of metals. Among conducting polymers polyaniline, (Pani) is of great interest because of its simple preparation and good environmental stability. Moreover, by using an appropriate selection of dopant and solvent, it can be processed in the doped state and after solvent evaporation provides materials exhibiting good electrical conductivity, up to 400 S/cm [Y. Cao, P. Smith, AJ. Heeger, Synth. Met., 48, 91 (1992)]. However, these materials are usually very brittle. In order to obtain conducting materials with improved mechanical properties, doped polyaniline can be mixed, or physically blended, with an insulating polymer such as poly(methyl methacrylate). [J. Anand, S. Palaniappan, D.N. Sathyanarayana, Prog. Polym. Sci., 23, 993 (1998)] However, such blends are not environmentally stable.

Polyaniline blends with controlled and stable morphology have been prepared by Mezzenga et al., using the self-assembly of colloids and block copolymers to force the doped conductive polymer into a three dimensionally continuous minor phase [R. Mezzenga, etal.; Science, 299, 1872 (2003)]. Such conducting polymer nanostructures can be useful for many applications, for instance sensors, energy conversion and storage, catalysis and electronics [A.G. MacDiarmid, Rev. Mod. Phys., 73, 701 (2001)]. However, in this example provided by Mezzenga the preparation of the conducting nano structures requires a complex four component system, forming a triphasic system in which a crosslinked homopolymer diluent is present at high-volume fraction. As a result of the final low volume fraction of the conducing polymer in the material only low conductivities were obtained (10^"3 S/cm) which could be further exacerbated by the weak interaction between the donor and the acceptor group.

One of the present inventors has examined the use of counterion induced processability for the formation of a stretchable polyaniline. See US Patent Application 2003/0091845 and Chem. Mater. 2003 15, 1587-1592 both of which are incorporated herein by reference to provide examples of prior art and definitions of some terms. U.S. Patent

Application, 2003/0091845, disclosed use of low molecular weight dopants where selection of the substituents on the doping agent provides a method for supramolecular organization and tuning of the properties of the resulting material. However, there are limitations to independently developing both strength and conductivity in the films. In the polyaniline/sulfosuccinate system, the plasticizing effect originates from the long alkyl or alkoxy group present on the dopant. Stretchability and flexibility can be improved by using a longer alkyl group, but this causes a decrease in the electrical properties. The properties cannot be controlled independently.

Within the discussion of prior art in US Patent Application 2003/0091845 there is a reference to a paper in J. Phys.: Condens. Matter, 10, 1998, pp 8293-8303 which discusses the use of 2-acrylamido-2-methyl-l-propanesulphonic acid, known as AMPSA, as the dopant for polyaniline in an acidic solvent such as 2,2-dichloroacetic acid. However, although the temperature at which the transition between nonmetallic behavior and metallic behavior occurs is lower than for the above Pani-CSA system the film remained brittle and the structure is not well defined.

Pani is not the only conducting polymeric material and a partial list is given below. Conductive oligo-polymeric materials can comprise substituted and unsubstituted poly(para- phenylene)s, poly(para-phenylenevinylene)s, polyphenyleneethynylene such as poly(p- phenylenepentadienylene), poly anilines, polyazines, polythiophenes, polythienylenevinylene, poly(para-phenylene sulfide) s, polyfurans, polypyrroles, polyfluorene, polyselenophene, polyacetylenes, polynaphthalenes and polyethylene dioxythiophene. These materials have been examined in the search for a stable conductive polymeric material.

Reghu [Reghu, M.; etal., Physical Review B: Condensed Matter and Materials Physics 1991, 43, 4236-4243)] discussed the case of a percolating conducting phase of fibrillar morphology when polypyrrole was dispersed in the insulating matrix. But once again, even with this other conductive material the morphology of the blend is not stable upon annealing or ageing.

Another approach to preparing conductive polymers, which should provide a more stable structure, is to prepare a block copolymer wherein one of the segments is the conductive polymer. ATRP is one example of a controlled radical polymerization (CRP) process that has been used to prepare the non-conductive segment in such segmented copolymers. [Su Lu, Qu-Li Fan, Shao-Yong Liu, and Soo-Jin Chua, Wei Huang, Macromolecules, 2002, 55, 9875-9881; J. Liu, E. Sheina, T. Kowalewski, R.D. McCullough, Angew. Chem. Int. Ed., 41, 329, (2002); PJ. Costanzo, K.K. Stokes, Macromolecules, 35, 6804, (2003); CA. Breen.T. Deng, T. Breiner, E.L. Thomas, T.M. Swager, J. Am. Chem. Soc, 125, 9942 (2003)]. However in these materials aggregation of the conjugated polymer chain is decreased, therefore quenching of fluorescence, or electrical conductivity, is decreased in the solid state. While conducting polymer nanowires can be obtained from the materials prepared by McCullough et al, the polymer solubility and stability in the doped state remains a topic for further research.

It remains very desirable to prepare polymers with conductivities exceeding 10^"3 S/cm, indeed above 1 S/cm, which are also stable in air and sufficiently elastic to resist mechanical stresses induced during use, e.g. they are inherently cohesive materials that can be bent, rolled, dropped, pierced etc. As noted above several approaches have been evaluated to enhance the supramolecular organization and mechanical properties of conducting polymers while attempting to preserve conductivity. They include blending of the conducting polymers, such as polyaniline, with insulating polymers and a surfactant, or with polymer colloids. In these blends, conductivity is achieved by percolation of the dispersed doped pi- conjugated polymer phase hosted in an insulating polymer matrix. Another approach is the preparation of block copolymers wherein one of the segments is the conducting polymer. However as noted above the properties of the final materials prepared by both approaches remain deficient in stability of the material at elevated temperature or over extended time periods or in conductivity or physical properties. A need therefore exists for a procedure to independently tune the physical and electrical properties of conjugated conducting polymers and provide highly conducting tough durable materials. BRIEF DESCRIPTION OF THE FIGURES

The features and advantages of the present invention may be better understood by reference to the accompanying figures, in which:

Figure 1. Schematic of conducting polyaniline nanostructures templated via self- assembly of a block copolymer.

Figure 2. AFM images of (AMPSA)₂₃(MA)₂₉O (top) and 4EBn₁₅Z(AMPSA)₂₃(MA)₂₉₀ (bottom).

Figure 3. Schematic of incorporation of doped polyaniline into the phase separable block copolymer Figure 4. AFM image of (Pani(AMPSA)i)₂.₃/(AMPSA)23(MA)29o.

Figure 5. UV-Vis-NIR spectra of doped polyaniline in dichloroacetic acid Figure 6. UV-Vis-NIR spectra of doped polyaniline in dichloroacetic acid for samples 151 and 152

Figure 7. Conductivity vs polyaniline content. Figure 8. UV- Vis results for Pani/AMPSA₂ complexed with AMPSA₇₂MA₄₆O

Figure 9. UV-Vis-NIR spectra of dispersed PEDOT/(AMPSA)₂3-b-(MA)₂₉o in water (1% wt)

Figure 10. Dynamic Light Scattering of PEDOTZ(AMPS A) ₂₃-b-(M A)₂₉₀ dispersion in water (1 wt %). Figure 11. UV- Vis spectrum of film from polypyrrole prepared within a donor triblock copolymer micelle (Example 6.1)

Figure 12. AFM image of sample prepared in example 6.1 (deposited from 100 mg/ml solution in NMP)

Figure 13. UV- Vis spectrum of film from polypyrrole prepared within a donor triblock copolymer micelle (Comparison of Examples 6.1 and 6.2)

DISCUSSION OF THE INVENTION

We herein provide a new approach to conductive polymeric materials which yields stable conductive polymer films, fibers, coatings, articles, or whatever, with adjustable as formed conductivities that can exceed 10^"3 S/cm, 1 S/cm or even 10 S/cm under ambient conditions. These exemplary conducting materials are not brittle and can be shaped into many different forms that can be bent, rolled, dropped, pierced etc. This exemplary approach employs the nanostructured morphology of a strongly phase separating copolymer, initially exemplified in one embodiment of the invention by an amphiphilic block copolymer to interact with and thereby confine and organize the added conducting material, or precursor of the conducting material, within the phase separated strongly acidic dopant segment of the amphiphilic block copolymer by forming a complex with the added material thereby incorporating the newly formed conductive complex into the phase separable material. The incorporation of the conducting polymer within the dopant phase, by complexation with the tethered donor functionality, can change the volume fraction of the dopant phase of the copolymer complex and the new supramolecular complex containing phase can form a dispersed, co-continuous or a continuous conductive phase based on the final volume fraction of the phases. It is the volume fraction of the final complexed segment that predominately dictates final nanostructure of the conductive material. The first conducting precursor material can be a monomer, an oligomer or a (co)polymer and can be added to the first phase separable copolymer as the sole reactive additive, a partially doped additive or as one component of a mixture of additives. The formed conducting complex is a stable composition and not a blend. However, if desired, the conductive properties can be modified by postprocessing doping by addition of a low molecular weight dopant.

As noted above one embodiment of the invention will be exemplified by using a segment of an amphiphilic block copolymer to dope a conductive oligomer or polymer precursor and thereby confine the resulting complex into its own modified nanostructured morphology. The concept is shown schematically in Figure 1 for incorporation of a small mole fraction of conductive material into a spherical domain. Further we will demonstrate that the final morphologies of the doped structure can be continuous or discontinuous and can be (reversibly) converted from one to another state by the mole fraction of added conductive material or by external stimuli: including solvent, vapors, temperature (T), pH, mechanical stresses, etc. This results in the preparation of stable processable conductive polymers with conductivities from below 10^"3 S/cm to 100 S/cm that can additionally find application as inherent conductive materials or as components of sensors, actuators, etc.

In this first exemplifying use of an amphiphylic block copolymer to prepare these stable structures the second block of the block copolymer can be selected to be the dominant phase and thereby provide a matrix, either continuous or co-continuous, to enhance mechanical properties and processability of the polymer complex or alloy or can be selected to be the minor phase which provides a toughening of the conductive matrix. The non-donor, non-conductive segment(s) can be used to provide further functionality to the conducting material such as provision of ionic conductivity to the material thereby providing a material suitable for use as a membrane in a battery. The morphology of this second ionic conducting phase can additionally be modified by the addition of a removable solvent thereby providing greater free volume for transmission of ions or other molecules, or after removal, form pores of known dimensions within the formed electrically conducting structure. Indeed this second block does not have to be a pure homopolymeric block but can comprise a copolymer or a block copolymer, forming a third block, where the additional monomer units or segments provide additional functionality. Additional doping agents, added prior to complex formation or post-complex formation, can be used to adjust conductivity of the nanostructured composite and optionally the volume fraction of the conducting phase, or the volume fraction of the conducting phase can be selected such that the presence of an additional agent in the contacting environment causes a change in the conductivity of the nanostructured composite. Such a material thereby acts as a sensor.

Conductive oligo-polymeric materials that can interact with the dopant segment of a block copolymer can comprise precursors for substituted and unsubstituted poly(para- phenylene)s, poly(para-ρhenylenevinylene)s, polyphenyleneethynylene such as ρoly(p- phenylenepentadienylene), poly anilines, polyazines, polythiophenes, polythienylenevinylene, poly(para-phenylene sulfide) s, polyfurans, polypyrroles, polyfluorene, polyselenophene, polyacetylenes, polynaphthalenes and polyethylene dioxythiophene.

The obtained conductive nanostructured materials can be formed as a film, foil, fiber, pipe or other three dimensional structure, or can form a coating etc... and find application as materials suitable for, or suitable as constituents in, semiconductors, flexible photovoltaic diodes, flexible electroluminescent diodes or plastic field-effect transistors or when present in the fully conducting state, as materials that can be dispersed in a further material to provide antistatic protection, electromagnetic shielding, or act as modified electrodes or sensors. Indeed with the level of control attainable by appropriate selection of the non-donor segments it is possible to prepare conducting materials with elastic properties, plastic properties or rigid properties and therefore provide materials that would find application in plastic electronics and nano-electronics. Further, as noted above, the materials can be selected to respond to respond to the environment and act as remote sensors.

As noted above the embodiments of this invention are directed to the preparation of stable conducting processable polymeric materials where the conductivity of the material could be controlled over a wide spectrum of conductivity and the material would be robust enough to fulfill the needs of several applications that had long been the target for conductive polymers. The limitations of prior art were resolved by using the self organizing properties of a phase separable segmented copolymer [S. Forster and T. Plantenberg, Angew. Chem. Int. Ed. 2002, 41, 688-714; F.S. Bates and G.H. Fredrickson, Physics Today, February 1999] comprising one or more segment(s) designed to form a complex with and subsequently organize the morphology of the conducting nanostructured materials. The phase separable segmented copolymer of the present invention comprise block copolymers, star copolymers, graft copolymers, brush copolymers or core shell copolymers having a portion or segment capable of donating a proton to a conductive polymer, or conductive polymer precursor, and a segment or portion that acts to organize the phase separable segmented copolymer and provide desired physical properties to the final conducting polymer complex. Block and graft copolymers that undergo phase separation are well known to those skilled in the art. They are polymers comprised of two or more attached polymeric chains, segments or blocks, each containing different (co)monomers. Each segment of the phase separable copolymers can be prepared by the same polymerization process or by a different polymerization process wherein the first block is used as a macroinitiator or a macromonomer for the preparation of the next block or segment. All known polymerization processes can be used but a controlled, living or "living" polymerization process is preferred since the nanostructure of phase separated copolymers is partially dependent on the molecular weight distribution (MWD) of each segment and controlled polymerization processes provide narrower MWD. Therefore the segments in the first segmented copolymer can comprise any desired (co)monomer and each segment of the copolymer is synthesized by appropriate selection of the polymerization process for the selected monomer(s). Monomers that undergo radical polymerization processes, including controlled radical polymerization processes utilized as exemplary processes for the preparation of the segmented copolymers discussed herein, are disclosed in various review articles and books. [Moad, G; The Chemistry of Free Radical Polymerisation 1995: Odian, G; Principles of Polymerisation 1991] Atom transfer radical polymerization (ATRP), nitroxide mediated polymerization (NMP) and reversible addition fragmentation transfer (RAFT) are the three most commonly used Controlled Radical Polymerization (CRP) processes and are suitable for the preparation of block copolymers with functional groups on the monomer units. ATRP has been thoroughly described in a series of U.S Patents and Applications, such as U. S. Patent Nos. 5,763,548; 5,807,937; 5,789,487; 5,945,491; 6,111,022; 6,121,371; 6,124,411; 6,162,882; 6,407,187; 6,512,060; 6,538,091; 6,541,580; 6,624,262; 6,624,263; 6,627,314; 6,759,491; and U.S. Patent Applications 09/534,827; 09/972,056; 10/034,908; 10/269,556; 10/289,545; 10/638,584; 10/860,807; 10/684,137; 10/781,061 and 10/992,249 all of which are assigned to Carnegie Mellon University and these patents and applications are herein incorporated by reference as they thereby provide a list of monomers that can be polymerized by CRP processes and elucidate some of the benefits of preparing materials by a CRP. The definitions included in these cited references will be used in this application in addition to definitions provided in other cited prior art and those given below.

Donor monomers include various acids (including salts or anhydrides of acids), unsubstituted amides, N-hydrocarbyl-substituted amides including N-vinyl amides, sulfoalkyl esters, or sulfoalkyl amides. Such monomers, for ease of polymerization, would normally include an ethylenically unsaturated group such as a vinyl group. Typical acids include carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acidic half esters of maleic and fumaric acids where the alcohol-derived moiety contains 1 to 8 carbon atoms, and maleamic acids. Preferred acids contain 3 to 10 carbon atoms, preferably 3 to 5 carbon atoms. Also included are salts or anhydrides of such acids. While such monomers can be incorporated into homopolymeric donor blocks they can also be incorporated into copolymer donor blocks, an example would be an alternating copolymer of styrene and maleic anhydride. The preparation of an alternating copolymer with a donor monomer unit provides a method of controlling the distribution of the donor groups at the molecular level to accommodate bulkier conducting units or conducting materials comprising a second, non-tethered donor.

Salts include ammonium salts, amine salts, and metal salts such as alkali metal salts and alkaline earth metal salts. Specific preferred metals include lithium, sodium, and potassium salts. In some cases it may be convenient to initially prepare the polymer containing the donor monomer in a protected form or in its acid or anhydride form, and thereafter deprotect the functional group prior to neutralizing the acid functionality of the polymer. The salts may be substantially completely neutralized, that is, about 100% of the acid groups being in the salt form, or incompletely neutralized. Fully neutralized and partially neutralized salts are prepared by known methods of reacting an acid with a base supplying the desired cation.

Alternatively, the donor monomer can be a sulfonic acid or a salt thereof. Suitable polymerizable sulfonic acids include acrylamidoalkane sulfonic acids such as 2-acrylamido- 2-methylpropanesulfonic acid, as well as such monomers such as 2-sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, and methallylsulfonic acid. The monomer can also be a sulfoalkyl ester such as 2-sulfoefhylmethacrylate, 3-sulfopropyl acrylate, or 3-sulfopropylmethacrylate.

The donor monomer can also be a phosphonic acid or a salt or anhydride thereof, such as phosphonomethylacrylate, phosphonomethyl methacrylate, vinyl phosphonic acid, vinyl phosphate and allyl phosphonic acid.

The donor monomer can also be an amide, either unsubstituted such as acrylamide, or methacrylamide, or a N-substituted derivative thereof such as an N-hydrocarbyl-substituted amide derivative. It will be recognized that as the number and length of such hydrocarbyl substituents increases, the hydrophilic nature of the monomer and the resulting polymer block will decrease. Accordingly, each such hydrocarbyl group will preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Preferably, also, each nitrogen atom of the amide will contain only one such substituent and among the suitable amides are N-methyl acrylamide, N,N-dimethyl acrylamide, N-methylmethacrylamide, N,N-dimethyl- or diethylmethacrylamide, as well as such materials as t-butylacrylamide. Other substituted amides include those having N- substituents with polar functional groups such as hydroxy or carbonyl groups, such as CH.sub.2 .dbd.CHC(O)NH~CH.sub.2 CH(OH)CH.sub.3 or CH.sub.2 .dbd.CHC(O)NH- C(CH.sub.3).sub.2 CH.sub.2 C(O)CH.sub.3 or CH.sub.2 .dbd.CHC(O)NH~CH.sub.2 CO.sub.2 H.

Sulfoalkyl amides include sulfomethyl acrylamide and related materials. The donor polymer segment can be prepared from a mixture of monomers. Thus, if one of the less strongly donor monomers, or indeed if a non-donor comonomer, is used, it may advantageously be used in combination with one of the more strongly acidic monomers. Typical mixtures of monomers in the donor block include an acrylamidoalklanesulfonic acid with various acrylamides such as acrylamide, N,N-dimethylacrylamide, or N-t- butylacrylamide. Preferably the acrylamidoalkanesulfonic acid monomer and the acrylamide monomer (if such is used) are present in a mole ratio of 5:1 or 2:1 to 1:5 or even 1:15. In an exemplified embodiment, the hydrophilic block is a copolymer containing 2-acrylamido-2- methylpropanesulfonic acid (or a salt thereof), or a homopolymer of 2-acrylamido-2- methylpropanesulfonic acid (or a salt thereof).

It is also possible that a donor monomer precursor may be employed which, after incorporation into the polymer, can be converted into a donor monomer. For instance, certain esters, such as vinyl acetate or t-butyl acrylate, are normally considered neutral monomers and would be incorporated into a polymer using techniques for polymerizing normal monomers. After polymerization, the polymer can be subjected to hydrolysis to convert the monomer units into donor alcohol or acid units. In another approach an incorporated monomer is functionalized in a post polymerization reaction which can be exemplified by preparation of a block copolymer with a polystyrene segment that can be sulfonated to provide a donor block or by procedures discussed in the patent application based on provisional application 60/550,413.

There are several processes known for the preparation of segmented copolymers but preferred process for the preparation of the present block, star or graft copolymers with donor segment or bottle-brush copolymers or dendrimers with donor units on the periphery of the molecule, however, involves free radical, rather than ionic, polymerization processes since they can be used directly for the polymerization of ionic monomers but dual polymerization processes can be used and are exemplified herein.

As noted above the donor block can also be formed by function alization of an existing block in a preformed block copolymer such as sulfonation of an aromatic ring in an aryl based segment of a block copolymer or by other post-polymerization functionalization reactions such as hydrolysis of a protected functionality in one or more of the segments of a copolymer.

The conducting material selected for initial evaluation to exemplify one embodiment of the process was based on polyaniline as the conductive material since it is a conductive polymer that is easy to prepare and is quite stable. The polyaniline was incorporated into the ^■ block copolymer as the emeraldine base or as an emeraldine salt or as a tetramer. The preparation and use of this first specific exemplary stable conductive material is based on the preparation of an amphiphylic block copolymer that interacts with semi-oxidized polyaniline, forms a donor/acceptor complex with the semi-oxidized polyaniline and directs the organization of the final conductive material within the final phase separated material. The success of this approach provides a path for the identification of the parameters desired for synthesis of a suitable phase separable segmented copolymers. Other examples are provided to show me broad utility of this approach to use a broad spectrum of phase separable multi- segmented copolymers that additionally allow for further functionality in the final material including materials that display ionic conductivity or materials that can be selected to provide other functions such as water solubility.

The organization and size of the nano-dimensions of each phase can be modified by the molecular weight of each segment and the topology or architecture of the copolymer or by the presence of selected solvents or diluents. One embodiment that takes the effect of added solvents into account is that if one desired larger pores for ionic conductivity in a tri- block copolymer then water could be added to the composite structure. Other phase selective solvents could also be employed to provide porosity to a final membrane after the conductive material is fabricated into a film. For example the phase diagram of the native segmented material comprising the conductive polymer could be modified by the addition of solvents to provide gyroidal structure. After fabrication under suitable conditions the solvent could be removed thereby providing a three dimensional structure with uniform co-continuous domains, one conductive and one supportive or biphasic forming a conductive material with a network of continuous pores throughout the structure. A specific example that demonstrates both aspects of the concept would be the preparation of a phase-separated, amphiphilic block copolymer which displayed a gyroidal phase separation when the hydrophilic phase is selectively swollen with water above the T_s of the hydrophobic phase followed by lowering the temperature below the T_g of the hydrophobic phase and freeze drying to leave hydrophilic pores.

If the porous membrane was to be used in a fuel cell then a suitable hydrophobic phase would be a perfluroalkyl (meth)acrylate. If it was to be used for drug delivery then additional functionality on the hydrophilic segments could be selected so that the pore walls could interact with or bind the selected drug to the pore with a degradable link. Suitable functional groups would be -OH and -NHR.

Indeed when one considers the requirements of the final product it is only in this final fabricated state that the material has to display a desired controlled nanostructure. The first block copolymers can be selected such that added materials may induce the phase separation in the first segmented (co) polymer and then the first segmented copolymer can function to organize the phase separated complexed structure. Further the phase separation can occur during processing of the first block copolymer comprising a donor segment, or polymer with more complex architecture with site specific donor units, and the added conductive precursor material as temperature or composition (e.g. by removal of solvent or other additive) is changed. Known fabrication technologies, including solution deposition or zone casting or mechanical means for orientation such as stretching the fabricated material, can be utilized to further modify the organization of the bi-phasic materials and hence the conductivity of the article. DISCUSSION OF EXAMPLES

We will first exemplify the invention by a description of the preparation of nanostructured conducting polyaniline or oligoaniline-based materials templated by the self- assembly of a diblock copolymer, poly(acrylamido-2-methyl-N-ρropanesulfonic acid)-block- poly(methyl acrylate), P(AMPSA-b-MA), as illustrated in Figure 1 for a case that would provide a low conducting spherical morphology (this is purely for simplicity of the schematic). The initial diblock copolymer, was prepared by a RAFT polymerization process and exhibits microphase separation because of the incompatibility between the hard hydrophilic PAMPSA block and the soft hydrophobic PMA block. Oligo- or polyaniline molecules are protonated by the sulfonic acid group on the PAMPSA block and therefore are forced into this phase of the block copolymer through complex formation. I.e. the first phase separable morphology of the block copolymer templates the organization of the conductive added oligo/polymer by forming a complex with the added agent thereby incorporating the complexed conductive material into this phase of the bi-phasic copolymer thereby modifying the bulk morphology of the first bi-phasic copolymer forming a conductive supramolecular complex.

The morphology of these composite conductive materials has been studied by atomic force microscopy (AFM) which shows that the final morphology is dependent on the final volume fraction of the phases thereby demonstrating that by controlling the molecular weight of the segments and the final ratio of the two phases one can control the degree and topology of phase separation between the incompatible blocks and hence the aggregation of the conjugated polymer chain and the solubility/processability of the material. This level of control over the synthesis of the first segmented copolymer provided by controlled polymerization processes results in the capability to control mechanical properties, electrical properties, optical properties and provide inherent stability to environmental conditions. The following examples exemplify this approach to stable nano-composite materials with unique chemical properties, enhanced mechanical, optical and electrical properties that can find use in nanoelectronics, such as preparation of nanowires or nanofibers and in energy conversion and storage, and as materials for biological and chemical sensing applications. In the first example the level of control provided by this approach to conductive materials is demonstrated by the fact that in our present exemplifying system, high conductivity, up to 31 S/cm with good mechanical properties are obtained with low incorporated polyaniline content (11 wt%). In the earlier system disclosed by one of the present inventors, polyaniline/alkyl sulfo succinate, the required polyaniline content was about 30-40 wt% and conductivity is reduced as flexibility is increased whereas in the present disclosed system, the electrical properties are controlled by the overall volume fraction or molar ratio of the doped polyaniline and the acidic segment content in the templating, or complex forming donor segment, of the phase separable copolymer. The mechanical properties can be tuned independently of the desired level of conductivity by changing the composition and mole fraction of the non acidic segment of the block copolymer. Flexible and stretchable films are obtained using soft blocks with a Tg below use temperature such as poly (methyl acrylate), poly (butyl aery late), etc.. Whereas a rigid material would be formed if the non-donor block had a Tg above room temperature, such as exemplified below by preparation of a styrene based block copolymer. The topology of the segmented copolymer is not limited to an AB block copolymer and one can also use an ABA copolymer, a star copolymer, a graft copolymer or a bottle brush copolymer or a brush copolymer tethered to a substrate. This control of the mechanical, and indeed chemical, properties by the polymer matrix also induces better mechanical stability at high temperature since as noted above in the discussion of present art conductive polymer blends depend on surfactants that can decompose at high temperature, or the plasticizing group can migrate inducing rigidity and brittleness to the system. The morphology of our disclosed system is defined by the final composition of the complex, the conducting phase can be continuous or discontinuous and while the morphology of the final material is inherently stable the material can be designed to change from discontinuous to continuous on stimulation by physical or chemical processes.

In the first example the process chosen for the preparation of the dopant block was RAFT since this controlled radical polymerization process was expected to be able to polymerize acrylamido-2-methyl-N-propanesulphonic acid directly forming a suitable macroinitiator for chain extension. However other controlled radical polymerization procedures would also be suitable for use in this task of directly preparing the dopant block or segment in a phase separable copolymer. Indeed another controlled radical polymerization process (ATRP), which was disclosed by one of the present inventors in a series of referenced and incorporated applications and disclosures and patents that teach conditions for directly polymerizing ionic monomers forming suitable donor blocks associated with a wide range of non-donor assembly directing blocks, is also exemplified for the preparation of a similar material. The references to these procedures have been disclosed and incorporated in the above list. Indeed a precursor block can be prepared by any controlled polymerization process, if one is willing to conduct a post polymerization functionalization reaction such as neutralization, hydrolysis or substitution.

Applications for the materials disclosed include flexible photovoltaic diodes, flexible electroluminescent diodes, plastic field transistors, as semiconductors, antistatic protection, electromagnetic shielding, modified electrodes or sensors.

EXAMPLES

Atomic Force Microscopy. Tapping mode atomic force microscopy (TMAFM) studies were carried out with a NanoScope III-M system (Digital Instruments, Santa Barbara, CA), equipped with the J-type vertical engage scanner. The AFM observations were performed at room temperature in air using silicon cantilevers with nominal spring constant of 40 N/m and nominal resonance frequency of 300 kHz (standard silicon TESP probes.

EXAMPLE 1.

Preparation and use of P(AMPSA-b-MA) copolymers for complexation with, and organization of, Pani. Example 1.1. Synthesis of poly(acrylamido-2-methyl-N-propanesulfonic acid) by RAFT. The process is summarized in scheme 1.

AMPSA poly(AMPSA)

Scheme 1. Synthesis of poly(acrylamido-2-methyl-N-propanesulfonic acid)

Acrylamido-2-methyl-N-propanesulfonic acid, 5 g, and cumyl-dithiobenzoate, 35.2 mg, were dispersed in 20 ml distilled methanol and azoisobutyronitrile, 4 mg, was added under nitrogen flow. The reaction mixture was heated at 60 ⁰C. The mixture remained homogeneous during the polymerization. The reaction was stopped at 50 % conversion (measured by ¹H NMR). The polymer was separated from unreacted monomer using dialysis versus distilled water, and subsequent evaporation of water. Molecular weights and molecular weight distributions were determined respectively by ¹H NMR and SEC using a mixture of water/methanol/NaNO₃ as the eϊuerifahd poly (ethylene oxide) as standards. (DP 23, polydispersity index (PDI) 1.20).

Solvents other than methanol can be employed and different RAFT agents can be employed. E.g. the reaction was run in DMF using 3-benzylsulfanylthiocarbonylsulfanyl propionic acid as the transfer agent. When DMF was used as the solvent it was found to be advantageous to continuously add AMPSA to the reaction to control the concentration of free AMPSA in solution since the monomer interacted with the acidic transfer agent.

A further examples based on his example can target reducing the PDI of the formed PAMPSA macroinitiator by employing continuous addition of the AMPSA to a RAFT polymerization using cumyl dithiobenzoate as transfer agent and running the reaction in purified/distilled methanol.

Example 1.2. Chain extension to form a poly(methyl acrylate) block. (Scheme 2)

methanol, 60 ⁰C

Scheme 2. Chain extension to form a block copolymer

PoIy(AMPSA) (250 mg) and azoisobutyronitrile (1 mg) were dissolved in distilled methanol (5 ml); degassed meihyl acrylate (4 ml) and degassed anisole (0.2 ml) were then added and the reaction mixture was heated at 60 ⁰C. The reaction was stopped after 18 h. Solvents were then removed by evaporation under vacuum until constant weight.

Composition and molecular weight distribution were measured by elemental analysis and SEC using DMF/LiBr as eluent and polystyrene standards, respectively. The composition of the block copolymer was (AMPSA)₂₃(MA)₂₉₀ (16% wt PAMPSA), PDI 1.16.

Example 1.3. Other Block copolymers

Several block copolymers were prepared using slight variations of the above conditions, all producing well defined block copolymers. (Table 1.) Therefore successful preparation of well-defined PAMPS A-b -PMA block copolymers was demonstrated in methanol using cumyl-dithiobenzoate as the transfer agent since both the AMPSA polymerization and the PMA block extension exhibited rather linear kinetic plots, showing the controlled/living nature of the polymerization process.

Table 1. Composition of PAMPSA-b-PMA block copolymers

The molecular weight distributions of the macro-transfer agent and the final block copolymer were clearly unimodal. Despite methanol being a poor solvent for poly(methyl acrylate), the block copolymer does not precipitate due to the presence of the PAMPSA block resulting in a controlled polymerization.

Example 1.4. Preparation of polyaniline.

Polyaniline was synthesized as follows: distilled aniline (30 ml) was added to a solution of LiCl (48 g) in a mixture of ethanol (285 ml) and 3 M HCl (255 ml). This solution was cooled to -25 ⁰C and then a solution of ammonium persulfate (18.75 g) and LiCl (24 g) in 2 M HCl (180 ml) previously cooled to -25 ⁰C was added. The reaction mixture was stirred overnight at -25 ⁰C. It was then filtered, washed 5 times with 200 ml 1 M HCl, followed by 5 times with 200 ml water. The HCl doped polyaniline powder was then dedoped in 2 L 0.1 M NH₄OH for 2 days. The polyaniline powder was filtered, washed with a large amount of water, methanol and ether, and dried until constant weight. The yield was 95% with respect to ammonium persulfate.

Example 1.5. Preparation of tetra-aniline. The amino terminated aniline tetramer was synthesized according to the following procedure: 7.28 g of N-phenyl-1,4 phenylenediamine hydrochloric salt was dissolved in 600 ml HCl 0.1 M. The solution was coδleS at 0 ⁰C and a solution of 10.705 g FeCl₃ dissolved in 104 ml 0.1 M HCl was then added. The reaction mixture was stirred at 0 ⁰C for 4 h. The mixture was filtered, washed with a large amount of water, deprotonated in 2.5L 0.1 M NH₄OH, filtered, washed with water, and dried until constant mass. The yield was quantitative.

Example 1.6. Preparation of stable poIy(acrylamido-2-methyl-N-propanesuIfonic acid)- block-poly(methyl acrylate) complexes with polyaniline or oligoaniline. (Scheme3)

Tethered donor complexes were prepared by mixing 60 mg of (AMPSA) 23 (MA) 290 and 8.3 mg polyaniline or oligoaniline in 1.2 g dichloroacetic acid. Self -supported films were obtained by casting of the dichloroacetic acid solution onto a polyethylene substrate and subsequent removal of the solvent under vacuum.

acid

tetraaniline : x=2

Scheme 3. Doping of polyaniline by the sulfonic acid group of poly (AMPSA)-poly (methyl acrylate) diblock copolymers

However, when polyaniline or tetraaniline powder was directly mixed with the poly (AMPSA) -poly (methyl acrylate) diblock copolymer in dichloroacetic acid, according to scheme 3, in the ratio's shown in table 2, in most cases, the mixtures were not homogeneous, even after one month stirring. The reason is that the undoped polyaniline has a very low solubility in dichloroacetic acid, therefore the doping reaction, or complex formation by the tethered sulfonic acid groups on the polymer backbone is heterogeneous and very slow. Only in the case of low targeted mole fraction of added polyaniline were clear solutions obtained. In the case of oligoaniline based compositions, the mixtures were homogeneous in every case after a few hours stirring.

Table 2 : Oligoaniline and polyaniline/ poly(AMPSA)-poly(methyl acrylate) diblock copolymers compositions (4EB means tetraaniline unit, Pani means one tetraaniline repeating unit of polyaniline)

As noted above mixtures of PAMPSA-b-PMA with tetra-aniline in dichloroacetic acid were homogeneous. Films were prepared by drop casting. Auto-supported films can be obtained in all cases. The morphology of the phase separated conductive complex cast film was studied by AFM. Examples of AFM images of drop cast films on silicon wafers are presented in figure 2 where the morphology of the un-complexed dispersed phase, 16% hard APMSA phase, is seen to change from a discrete spherical morphology to an extended lamellar morphology, comprising 30% of an APMSA complexed oligo-aniline phase. Protonation of the oligoaniline was demonstrated by UV-Vis-NIR spectroscopy. The morphology of 4EBn,5Z(AMPSA)2₃(MA)₂₉o, corresponding to the maximum degree of doping (2 sulfonic acid groups per 1 tetramer unit) is shown in Figure 2 (lower), in comparison with the morphology of the pure (AMPSA) 23 (MA) 290 diblock copolymer processed under the same conditions which exhibits a spherical morphology (Figure 2, top). In this case, the mole fraction of the hard hydrophilic PAMPSA block was 16 wt%. Upon addition of oligoaniline, assuming its complete incorporation to the PAMPSA phase by complexation with the AMPSA group, the content of this phase was increased to 30 wt% and a lamellar morphology was observed, consistent with the respective molar content of both phases (Figure 2, bottom).

Example 1.7. Improved incorporation of polyaniline into a block copolymer

In order to improve the incorporation of polyaniline inside the poly(AMPSA) block and obtain conducting films, a second strategy can be employed. A solution of polyaniline, fully or partially doped by the AMPSA monomer in dichloro acetic acid was mixed with a 5 wt% solution of diblock copolymer according to the strategy schematically presented in figure 3 and scheme 4.

soluble

homogeneous solutions in dichloroaetic acid Scheme 4. Incorporation of partially doped polyaniline into the hydrophilic block of poly(AMPSA)-poly(methyl acrylate) diblock copolymers

The monomeric AMPSA and tethered AMPSA were expected to re-equilibrate and together complex the polyaniline. Self-supported films were obtained by casting the solution onto a polyethylene substrate and subsequent removal of the solvent under vacuum. However, only a low amount of polyaniline could be incorporated into this system (about 1.2 wt% with respect to the PAMPSA block). Most of the polyaniline remains insoluble. Indeed, undoped polyaniline is not soluble in dichloroacetic acid. The solubilization of doped polyaniline in this solvent is due to the so-called 'doping induced solubility'. Protonation of incorporated polyaniline was evidenced by UV-Vis-NIR spectroscopy. The content of the Pani/P AMPSA phase remained low (about 16 wt%); therefore the bulk morphology of the protonated complex was spherical, (See Figure 1). The obtained material was not conducting.

Example 1.8. Preparation of a complex of poly (acrylamido-Z-methyl-N-propanesuIfonic acid)-block-poly(methyl acrylate) with doped polyaniline.

AMPSA doped polyaniline was obtained by mixing 200 mg polyaniline with 114 mg AMPSA in 10 g dichloroacetic acid. Complexes with tethered AMPSA functionality were prepared by mixing 85 or 415 mg of this solution with 1.2 g of 5 wt% solution of (AMPS A) 23 (MA) ₂90 in dichloroacetic acid. The composition of prepared samples is summarized in table 3.

Table 3 : Composition of poly-protonated complexes of Pani/AMPSA/poly(AMPSA)-b- poly (methyl acrylate) (Pani represents one tetraaniline repeating unit)

The AMPSA doped polyaniline exhibits good solubility in dichloroacetic acid.

Therefore in order to be able to incorporate higher content in polyaniline, and obtain good conductivity in the final self organized material, PAMPSA-b-PMA copolymer was mixed with a solution of polyaniline partially doped with AMPSA. In this case, homogeneous solutions were obtained. An AFM image of (Pani(AMPSA)i)₂.3Z(AMPSA)₂3(MA)₂9o is presented in Figure 4 (For this notation, 1 Pani represents a tetramer repeating unit). In the case of the sample prepared from 10% PAMPSA diblock copolymer the morphology remained spherical since the final content of the hard phase was 13%. However when the final concentration of the hard phase was increased to 20% the morphology turned out to be a complex cylindrical branched morphology and the material was conductive.

Further examples of how the final conductivity of the sample containing the block copolymer can be modified by the conductivity of the first partially doped Pani are shown below: Doped Pani

Pani < 400 SZcm

Pani/AMPSA₂ 153 SZcm + AMPSA₂₃ZMA₂₉₀ 31 SZcm

PaniZAMPSAj.4 121 SZcm + AMPSA₂₃ZMA₂₉₀ 5.5 SZcm

PaniZAMPSA_t 90 SZcm + AMPSA₂₃ZMA₂₉₀ 4.5 SZcm with MA₅₀₀ 2.3 S/cm

DISCUSSION OF INITIAL EXAMPLE

The conductivity of these samples was studied using the four probe method. The conductivity of samples with low polyaniline content could not be measured, as would be expected, since the percolation is expected to be controlled by the morphology of the final diblock copolymer and in these samples the conductive phase was present as discontinuous spheres. The polyaniline containing phase must be continuous inside the material in order to allow the conducting behaviour to be observed at a macroscopic scale. Conductivity values of materials with higher concentration of the conductive complex in the samples are summarized in table 4.

Table 4: Conductivity of Pani/AMPSA/poly(AMPSA)-b-poly(methyl acrylate) complexes

The conductivity of the structures formed by interaction of poly(acrylamido-2- methyl-N-propanesulfonic acid) -block-poly (methyl acrylate) with AMPSA doped polyaniline show that the electrical conductivity of materials with low doped polyaniline content was too low to be measured using the four probe method. However, when the volume fraction of the conductive phase in the block copolymer complex was increased so that there was co- continuous morphology, as in Pani(AMPSA)i)π 5/(AMPSA)23(MA)29o, the material exhibited high conductivity, 4.5 S/cm. Another sample, with higher content of Pani(AMPSA), (Pani(AMPSA)₂)π ₅/(AMPSA)₂₃ (MA) ₂90 had conductivity of 31 S/cm. For comparison, the pure AMPSA doped polyaniline, Pani(AMPSA)2) exhibited a conductivity of 150 S/cm.

In this system, the percolation of the conducting phase is controlled by the morphology of the block copolymer complex. In order for these materials to be conductive, the doped or polymer complexed polyaniline phase needs to be continuous. This condition is not met in materials when the complexed Pani phase is dispersed into isolated spherical domains. Note however that the measured conductivity of the complexes are high considering the low amount of conducting polymer in the sample; this is most probably due to improved ordering of the conducting phase induced by the dopant block copolymer. This phenomenon is discussed below when the results of the UV-Vis-NIR spectra of some doped polyaniline solutions in dichloro acetic acid are interpreted. UV-Vis-NIR spectroscopy is very easily adapted to the study of doping of polyaniline in solution or in solid state.

The film with a conductivity of 31 S/cm was stable at room temperature for at least seven months, that is, there was no change in conductivity within error of the measurement, and the film could be bent through 360 degrees five times without any effect on conductivity.

In solution, the UV-vis-NIR spectrum is strongly dependant on the polyaniline- dopant-solvent interactions. Two extreme spectra can be obtained. In the case of a sample with strong delocalisation of electrons (leading to high conductivity in the solid state), the spectrum exhibits a strong absorption tail in the near infrared, which is usually attributed to an 'extended chain' conformation. On the other hand, in some cases, there is no absorption tail in the NIR, and a strong absorption peak around 800 nm is observed, which is attributed to the localization of polarons due to a coil like conformation of the polymer chain. The UV- Vis-NIR spectra of polyaniline doped with AMPSA (1 AMPSA unit for 4 aniline units), and PAMPSA-b-PMA diblock copolymers (5 sulfonic acid groups for 1 aniline units) in dichloroacetic acid are presented in figure 5. Figure 5 shows that polyaniline doped with

AMPSA exhibits a behaviour intermediate between the two extreme cases, its UV-Vis-NIR spectrum exhibits both a strong absorption peak around 800 nm and an absorption tail in the near infrared. In the case of the polyaniline doped by sulfonic acid groups of a diblock copolymer, localized character is much stronger. This behaviour can be explained by the stiffness of the poly(AMPSA) chain inducing a differing conformation into the poly-doped polyaniline; i.e. the donor segment of the copolymer contributes to the final organization of the complexed conductive polymer.

The UV-Vis-NIR spectra of polyaniline partially doped by AMPSA, and then reacted with poly(AMPSA)-b-poly(MA) to form the polymer doped complex is presented in figure 6 for two examples (sample 151 : (Pani(AMPSA)₂)n.5/(AMPSA)₂3(MA)₂9o and sample 152 : (Pani(AMPSA)2)2.3/(AMPSA)23(MA)29o). As shown in figures 5 and 6, addition of a small amount of diblock poly (AMPSA) -b-poly (methyl acrylate) to partially doped Pani/ AMPSA does not result in a big change in spectroscopic properties, a significant absorption tail in the near infrared remains. In the solid state, after evaporation of the dichloroacetic acid solvent, this sample exhibits high conductivity (31 S/cm). However, when a smaller proportion of Pani/AMPSA with respect to the diblock copolymer is employed, as for sample 152, the intensity of the peak at 800 nm, due to the localized state increases, since the proportion of quinone diimine sites doped by the polymeric dopant is bigger. Further organization, and improved orientation of the conducting phase can be accomplished either during fabrication; where conducting nanostructures using zone-casting system for solution casting would be a means to increase the order of the biphasic conducting material [Tracz, A.; et al. J.Am. Chem.Soc. 2003, 125, 1682-1683], or by physical manipulation such as stretching in one or two directions either during fabrication or post fabrication. When post-fabrication manipulation is conducted under some circumstances it may be desirable to anneal the material above the Tg of the matrix material to realign the conductive domains.

In this initial example it has been demonstrated that by using a combination of self- assembly of strongly acidic/hydrophobic diblock copolymers and acid/base recognition between sulfonic acid groups of a PAMPSA segment in a copolymer and imine groups of polyaniline or oligoaniline that it is possible to obtain a variety of well-defined conducting polymer nanostructures in a soft poly(methyl acrylate) matrix. Doped polyaniline or oligoaniline spheres, cylinders, and lamellae can be observed depending on the final fraction of poly-doped polyaniline in the material. Incorporation of large amounts of polyaniline was achieved using partially doped polyaniline solutions, yielding materials with high electrical conductivity between 5 and 30 S/cm in the as cast alloy. These systems are particularly promising as active components for chemical sensors and various nanoelectronic devices. Other systems can be created using the teachings of this first exemplary example.

EXAMPLE 2 Example 2.1. Samples with higher mole fractions of AMPSA in the block copolymers

A further series of pAMPSA-b-pMA block copolymers was synthesized by RAFT. Their characteristics are summarized in table 5. Well-defined PAMPSA-b-PMA was successfully prepared in methanol using cumyldithiobenzoate as the transfer agent. The molecular weight distributions of the macro-transfer agent and the final block copolymer were clearly unimodal and shifted to higher molecular weight as polymerization progressed. No traces of the pAMPSA macro-transfer agent could be observed in the final block copolymer demonstrating complete end-group functionalization and the efficient cross- propagation between pAMPSA and pMA.

Table 5 : Homopolymerization of AMPSA and chain extension with MA

The morphology of the diblock copolymers was studied by AFM. In most of the cases, i.e. for compositions low in poly(AMPSA), a spherical morphology, or possibly cylindrical morphology with cylinders perpendicular to the surface was observed. For block copolymers with high mole-fraction of poly (AMPSA) (53 wt%), a cylindrical or lamellar morphology was observed. The dependence of the macroscopic electrical conductivity on the composition of the diblock copolymer and the incorporated polyaniline was studied and is presented in figure 7. The evolution of electrical conductivity with incorporated complexed Pani appeared to be strongly dependant on the morphology of the sample induced by the final composition of the resulting diblock copolymer Pani complex. In the case of complexes formed with the block copolymer containing 53% poly(AMPSA) the electrical conductivity decreased slowly with the Pani content. In that case, the poly(AMPSA)/Pani phase should remain continuous for all compositions incorporating different weight fractions of Pani. In the case of the block copolymer containing 16% poly(AMPSA), the morphology of the initial diblock copolymer is spherical, and the morphology becomes continuous upon addition and subsequent complexation of a sufficient amount of doped polyaniline, thus enabling conducting pathways along the sample. A percolation threshold could therefore be observed in this case, as well as for the 27% sample (about 5 wt% Pani). In this system, the percolation of the conducting phase is controlled by the final morphology of the material. In order for these materials to be conductive, the phase incorporating the poly-doped polyaniline needs to be continuous. This condition is not met in materials when Pani is dispersed into isolated spherical domains. Example 2.2. Higher Molecular Weight Samples of Polyaniline reacted with AMPSA copolymers prepared by RAFT

2.2.1. PoIy(AMPSA) macroinitiator preparation The poly(AMPSA) used in synthesizing the majority of the segmented co-polymers was the result of a RAFT polymerization. The general procedure is as follows: AMPSA (50 g) was added to a Schlenk flask and de-gassed with nitrogen. Degassed methanol (200 mL) was then added, and the mixture was stirred overnight to solubilize the monomer. Methanol (5 mL degassed) was added to the cumyl dithiobenzoate oil (352 mg) and stirred until the oil dissolved. This was then added to the reaction flask by syringe, and stirred until the mixture was a uniform purple color. The solution was degassed for 20 minutes, AIBN (40.3 mg) was then added and the mixture was degassed again, and the flask was lowered into a 60⁰C oil bath. The reaction was stopped when the mixture turned clear

(roughly 48 hours from the start of the reaction). The methanol was removed by rotary evaporation, and the remaining solid was dissolved in 100 mL of water, and purified by dialysis overnight. The water was then removed by rotary evaporation, and the purified polymer analyzed by NMR.

Table 6. PoIy(AMPSA) prepared by RAFT

The poly(AMPSA) produced in these reactions had a fairly high polydispersity (see Table 6). This is not a particularly optimal state of affairs, and may be the result of preparing 'long' chains of AMPSA. (Previously prepared AMPSA had a DP of ~ 23).

Example 2.2.2. Block extension with methyl acrylate or butyl acrylate

The poly(AMPSA) macroinitiators, chiefly either RAFT-2 or RAFT-3, were block- chain extended by RAFT, using either methyl acrylate or butyl acrylate, according to the general following procedure.

PoIy(AMPSA) (500 mg, 0.014 mmol) was added to a 10 mL Schlenk flask and degassed for 30 minutes. Degassed methanol (7.8 mL) was then added, and the mixture was stirred until the PAMPSA dissolved. Degassed butyl acrylate (6.3 mL, 55 mmol) was then added, followed by degassed anisole (1 mL, as internal standard). The mixture was degassed for several minutes, then AIBN (0.5 mg) was added, and the mixture was degassed again. The reaction was then heated to 60⁰C, and monitored by GC. The reaction was stopped after 2 days, with a conversion (according to GC) of 30%. The methanol was removed by rotary evaporation followed by a vacuum pump.

Table 7. Block copolymers from the RAFT block extension of PAMPSA

The polydispersity of these polymers is fairly high (see Table 7), although not markedly higher than the polydispersity of the initial AMPSA blocks (Table 6). It is likely that these polydispersities had some affect on the conductivity of the resultant polyaniline complexes (see below).

Example 2.2.3. Preparation of polyaniline complexes

The above co-polymers were blended in various proportions with polyaniline doped with two equivalents of AMPSA dissolved in dichloro acetic acid to form the poly-complexed structure. The polyaniline was prepared by a fairly standard procedure detailed in example 1.4. The polyaniline/AMPSA₂ was prepared by mixing polyaniline (1 g) and AMPSA (1.144 g) in dichloro acetic acid (100 g), and allowing it to stir until the polyaniline was fully doped (generally 4-6 weeks). This polyaniline/AMPSA₂ was further doped with a solution of the various copolymers (5% by weight in dichloroacetic acid) in different proportions to form polymer doped, or polymer complexed structures, and films were cast from these materials (see Table 8 for example preparation). Table 8. Reaction of Pani/AMPSA₂ with 27 wt.% PAMPSA/PMA block copolymer

The resulting complexes were also characterized by UV- Vis spectroscopy (see figure 8), in order to confirm that the majority of the polyaniline remained doped after reacting with the added segmented copolymer. There seemed to be some loss of low molecular weight dopant upon blending with the segmented copolymer indicating formation of a complex with 27% AMPSA/MA block copolymer. The complexes were then cast as films onto polyethylene sheets, and the solvent was removed slowly (at low heat) in the vacuum oven. Conductivity was measured on a 1 cm² square of the film. The approximate percolation threshold was located (see the sharp drop in conductivity at a 7:1 ratio of sulfonic acid groups to polyaniline). Stable complexes of polyaniline with a di-block P(AMPSA-b-BA) copolymer have also been prepared. Samples of these films were flexile materials and have been sent for mechanical property analysis but data has not yet been returned, however, the films remained coherent and conductive after flexing. Table 9. Conductivities of polyaniline/co-polymer complexes cast from dichloroacetic acid

The methyl acrylate and butyl acrylate-containing copolymers with similar amounts of AMPSA have fairly different conductivities (see Table 9). Given that the AMPSA chain lengths in each case are very different (the methyl acrylate polymer has a much shorter AMPSA length), it is quite likely that some morphological difference between the two polymers, perhaps due to a difference in phase separation, contributes to the lower conductivity of the butyl acrylate polymer.

EXAMPLE 3 Preparation of PS-b-PAMPSA from PAMPSA macroinitiator

Previously prepared poly AMPSA (1 g, DP 72) was added to a Schlenk flask and degassed for 30 minutes. Degassed DMF (6.5 mL) was then added, and the mixture was stirred until the PAMPSA dissolved. Styrene (5.2 mL) was then added, and the mixture was degassed for several minutes. AIBN (1.4 mg) was then added, followed by degassing with stirring for 3 minutes. The reaction mixture was then lowered into a 90⁰C oil bath, and its progress was monitored by GC. The plot of conversion vs. time was fairly linear, as was the plot of ln[M]₀/[M]. From this data, the reaction appeared fairly well controlled.

This successful demonstration that diblock (co)polymers, with different compositions can be prepared in this manner indicates that it will be possible to explore solvent options for blend/complex/film preparation, in order to find something that works as well as dichloroacetic acid, but is easier to remove by evaporation, allowing preparation of good thin films, so that film morphology can be investigated.

EXAMPLE 4 Example 4.1. Polymerization of AMPSA by ATRP

The initial search for optimal ATRP conditions began by trying two different ligand systems, bpy and CuCl in DMF, and HMTETA and CuBr in either DMF or methanol, according to the following general procedure:

AMPSA (5 g, 24.2 mmol) was added to a 25 mL Schlenk flask and degassed for 30 minutes. Degassed tributylamine (5.8 mL, 24.3 mmol) was added to turn the AMPSA into a salt, followed by degassed DMF (8 mL). The mixture was stirred until the AMPSA dissolved, then degassed for 20 minutes. The copper/ligand complex was prepared in a separate Schlenk flask. CuCl (34.2 mg, 0.35 mmol) and bpy (114 mg, 0.73 mmol) were placed in a 10 mL Schlenk flask. The flask was subjected to vacuum for 30 seconds and then flushed with nitrogen. This process was repeated 4 times, in order to remove all the oxygen from the ligand flask. Degassed DMF (3 mL) was then added, and the mixture was stirred for 10 minutes, under nitrogen, in order to make the copper/ligand complex. EBiB (18 microliters) was added to the 25 mL Schlenk flask, and the mixture was degassed. A 1 mL portion of the copper/ligand complex (11.4 mg CuCl, 38 mg bpy) was removed and added to the main reaction flask. The mixture was degassed for 4 minutes, then lowered into a 60⁰C oil bath and heated for 41 hours.

The conversion was monitored by NMR, using the methyl group from TBA (at approx. 1 ppm) as a standard. The reactions with HMTETA turned pale blue early on, indicating a high initial quantity of Cu (II), and no real conversion was observed (percent conversions lower than -10% are fairly well within the error in measuring conversion by NMR). It seems likely that the catalyst complex formed with HMTETA as ligand is too active to successfully polymerize AMPSA. Adding less catalyst or adding some percentage of Cu (II) at the beginning of the reaction might allow for a successful reaction. The CuCl/bpy system exhibited some degree of success, however only with a

CuCl:bpy ratio of 1:0.7. In terms of the CuCl/bpy system, most of the reactions experienced a color change 1 hour into the reaction. This color resulted in a pale brown solution, indicating that oxygen was not a likely culprit. Given that TBA was used to neutralize the acid, it seemed possible that acidity /basicity was affecting the reaction. Differing amounts of the amine were then added, in order to see what effect this had on conversion (and the color change, see Table 10.

Table 10. Effect of excess acid/base on conversion in the ATRP of AMPSA

Excess acid seemed to be chiefly responsible for the color change, likely by protonating the bpy, and leaving a very minimal amount of ligand available for complexation with the CuCl. The presence of a large excess of amine also inhibits the reaction, which may be the result of preferential complexation of the amine with the copper rather the bpy, resulting in a low active catalyst concentration. A modest excess of amine allowed an acceptable conversion, neutralizing all the acid but not maintaining a high level of amine in the reaction mixture.

These condition were used to synthesize a poly(AMPSA)-b-poly(butyl acrylate)-b- poly (AMPSA) triblock co-polymer, according to the procedure described above, (only with the addition of a polyflbutyl acrylate) macroinitiator (MW 60,000 g/mol) before the addition of AMPSA).

Table 11. Poly (AMPSA) -b-poly (butyl acrylate) -b-poly (AMPSA) triblock co-polymer synthesized by ATRP

The second preparation (see Table 11) contained enough material to be used in the preparation of complexes with polyaniline, and the preparation of films from this material. Control of the reaction seems fairly good, the 'problem' lies in the low conversion, requiring a large excess of AMPSA in order to obtain a reasonable DP for the polymer. One interesting point is that the 1-98 sample forms micelles in water.

Example 4.2.1. Preparation of triblock (AMPSA27BA468AMPSA27) and formation of a complex with Pani/AMPSA

The polymer complexes were prepared by mixing 8 g of the triblock copolymer in dichloroacetic acid solution with decreasing amounts of doped polyaniline in dichloroacetic acid solution, in order to prepare blends with a 1:1 ratio of aniline tetramer to sulfonic acid, and a 1:3 ratio. Films were cast from these complexes and there was evidence from low pressure tapping AFM images that the surface of the film was polybutyl acrylate but higher tapping force indicated the bulk of the film was organized. Samples with a lower molecular weight mid-block would be expected to present a different surface topology. The insulated surface indicates that it should be possible to prepare conductive fibers from such a material. Example 4.3. Preparation of PBA 3-armed stars chain extended with AMPSA

A tri-armed poly (butyl acrylate) (PBA) macro initiator (1 g, MW 210,000 g/mol) was added to a 25 mL Schlenk flask, followed by 2.96 g AMPSA, and the flask was degassed for 30 minutes. Degassed tributylamine (3.4 mL) was then added, followed by degassed DMF (8.6 mL), and this was stirred until the PBA dissolved (generally overnight). The mixture was then degassed for 20 minutes. Bpy (33.5 mg) and CuCl (21.24 mg) were placed in a separate flask which was run through four cycles of vacuum/pumping/flushing with nitrogen. Degassed DMF (3 mL) was then added and the mixture was stirred for 10-20 minutes. A portion of the CuCl/bpy solution (0.5 mL) was then transferred to the main reaction mixture, and this was degassed for several minutes. The flask was then lowered into an oil bath set at 6O⁰C, and the reaction was allowed to run over the weekend (1 day is generally sufficient time for the reaction to stop itself). According to elemental analysis, the resulting polymer contained 25% AMPSA, resulting in a formula of AMPSA350BA1638.

Example 4.4. Iron-catalyzed polymerization of AMPSA

The CuCl/bpy system provides a controlled polymerization of AMPSA, however, the overall conversion in a batch reaction using a single addition of catalyst complex is quite low (<15%). In the incorporated references there are reports of a successful ATRP using Fe(Ac)₂ and PMDETA as catalysts, and so this system was examined. The procedure essentially followed that of CuCl/bpy, except the ratio of metal:ligand was 1:1, and methylbromopropionate (MBP) was used as the initiator instead of EBiB. Polymerization was also attempted using only Fe(Ac)₂, with no ligand, to see if as in the case of vinyl acetate, the Fe(Ac)₂ was acting as something other than an ATRP catalyst, (see Table 12).

Table 12. Maximum conversion for varying conditions in Fe(ac)₂ catalyzed ATRP of AMPSA

A large excess of amine both increases the rate of the reaction, and also increases the maximum conversion that is reached.

Example 4.5. Copolymerization of po!y(AMPSA) and PEO-incorporated using macromonomers and macroinitiators

Several attempts were made to co-polymerize AMPSA and PEO-containing monomers via ATRP, with the goal of having a polymer capable of acting both as a dopant, or complexing agent, for polyaniline but also as an ionic conductor. A PEO macroinitiator (methyl methacrylate backbone, MW 50,000 g/mol) was chain extended with AMPSA. This procedure was the same as that us.ed to synthesize the triblock co-polymer (CuCl/bpy as catalyst). After 26 hours, 10% conversion was observed. However, some unreacted macroinitiator remained, possibly indicating that some bromine functionality had been lost. Contrary to expectations, the polymer was not fully soluble in water, but instead formed micelles. These micelles were analyzed by dynamic light scattering, in both DMF and water, to 'prove' that polymerization had occurred. Polydispersity and size were lower in water, which fits with the hydrophilic nature of the PEO and AMPSA portions of the copolymer.

EXAMPLE 5. Example 5.1. PEDOT based conducting block copolymer

Micelles constituted by phase separation of a poly (AMPSA) -block-poly (methyl acrylate) block copolymers can also be used as template for the preparation of doped poly(ethylenedioxythiophene) (PEDOT) in water according to the scheme 5. The EDOT is polymerized in the presence of the self organizing poly-dopant. EDOT is a commercially available conducting polymer precursor.

doped PEDOT

Scheme 5. Preparation of a conductive Poly-doped PEDOT complex

The synthesis was carried out according to the following procedure: 140 mg (AMPSA)₂3-b-(MA)29o was dissolved in 1 ml DMF. 1 ml water was slowly added with vigorous stirring then 10 ml of additional water was added. The DMF was removed by dialysis versus distilled water. 39 μl ethylenedioxythiophene were then added and the mixture was allowed to stir for 3 hours until the solution became homogeneous. A solution of 183 mg ammonium persulfate in 1 ml water was then added dropwise, and the polymerization was carried out for 24h at 30 ⁰C. The reaction mixture turned dark green after a few hours. No precipitation was observed. The obtained mixture was filtered and purified by dialysis versus distilled water. The UV-Vis-NIR spectrum was recorded using lambda 900 spectrometer. The spectrum is shown in figure 9 and exhibits a peak around 800 nm characteristic of doped polythiophene. The size of micelles before and after polymerization was measured by DLS. Distribution of the size of micelles is presented in figure 10 which shows that there is a clear increase of the size of the micelles after polymerization of ethylenedioxythiophene, from 24 nm to 29 nm. Nevertheless, aggregate formation occurs. Thick films were prepared by casting of 1 wt % dispersion in water onto a polyethylene sheet and removal of the solvent under vacuum at room temperature. Conductivity of these films measured 5 X 10^"3 S/cm. Example 5.2. Preparation of doped PEDOT from molecular brushes:

The reaction was carried as follows: Ethylenedioxythiophene (0.27 ml) was added to 0.5 g of a bottle brush copolymer with poly(butyl acrylate)-b-poly(AMPSA) side chains (BBAAMPS A3), (i.e. the shell of the bottlebrush copolymer comprised the donor monomer units,) in 100 ml water. The mixture was stirred for 6 hours until the EDOT was fully adsorbed. 1.25g of ammonium persulfate in 7 ml water was then added, and the reaction mixture allowed stirred at 30 ⁰C for 20 hours. The color of the reaction mixture turned from colorless to dark green during the course of the reaction. No precipitation was observed. The polymer was purified by dialysis vs. distilled water. Size distribution obtained by Dynamic Light Scattering showed that the size distribution of the molecular brush slightly increased after PEDOT polymerization. No aggregate formation was observed in these cases. UV- visible absorption spectra showed a strong absorption at 790 nm both in DMF and water, characteristic of doped PEDOT. No effect of the solvent was observed. This can be explained by the colloidal nature of this sample. Films were cast both from water and DMF on polyethylene substrate. In both cases, films were brittle. AFM characterization of the densely grafted brushes with poly(butyl acrylate)-b-poly(AMPSA) side chains was carried out for ((BPEM-g-(BA)₆o-b-(AMPSA-TBA)₇₅)284, and ((BPEM-g-(BA)₆o-b-(AMPSA)₇₅)284. The images were obtained on mica surfaces from aqueous solutions for both the tributylammonium salt and sulfonic acid form individual cylindrical brushes were observed. However, for the tributylammonium form, the contrast was much better. This may be due to the strong repulsion between charges along the brush side chain, and also to steric effects due to the tributyl ammonium group.

EXAMPLE 6 Example 6.1. Preparation of polypyrrole within triblock co-polymer micelles

Pyrrole was distilled under vacuum, in order to remove impurities. The P(AMPSA-b- BA-b-AMPSA) polymer micelles in water were prepared by adding 150 mg polymer to 5 mL of water and the mixture was added to a round bottom flask and cooled to O⁰C and vigorously stirred for 30 minutes, then pyrrole (14.2 microliters) was added, and the mixture was stirred for another 30 minutes, in order to allow pyrrole to 'migrate' to the AMPSA- containing portions of the solution. The oxidant ((NH₃)_ZSaO₈, 11.7 mg) was dissolved in 0.5 mL of water, and added dropwise to the mixture. The mixture was then stirred overnight, with ice maintaining the 0⁰C temperature for as long as possible. Next morning, the reaction was stopped by addition of 1 mL of NMP, and the water was removed by rotary evaporation. Another 1 mL of NMP was added, and a film was cast from the solution. A sample of the NMP/polypyrrole/polymer solution was subjected to AFM analysis.

The initial triblock copolymer (in DMF) had spherical morphology, or perhaps cylindrical perpendicular to the substrate. It seemed possible that addition of pyrrole (or any another conducting polymer or conducting polymer precursor) to the AMPSA phase would push the morphology to gyroidal or lamellar and indeed AFM images of the polymer solution (in NMP) after polymerization of the pyrrole show signs of a lamellar-type morphology. However the surface morphology was not uniformly well-defined and it looked as if the high surface concentration of poly(butyl acrylate) might obscure the extended organized bulk morphology of the AMPS A/pyrrole-containing parts of the sample: i.e. the surface layer of butyl acrylate is serving as an insulator and creates a lot of contact resistance in the film. It seems likely, given the AFM images (supported by the UV-Vis data, (see figure H)) that the pyrrole phase is continuous enough to give some conductivity. In the UV-Vis spectra, the large peak starting at approximately 800 nm and extending to 1500 nm is essentially the polaron peak, indicative of a high degree of charge derealization, both within the chain, and between different polypyrrole molecules. Such delocalization generally indicates a high degree of conductivity between chains. Combining this high degree of delocalization with the lack of conductivity measured from surface contact points on the film itself, and the AFM images from hard tapping that show a fairly continuous pyrrole/ AMPSA phase, it seems probable that the high mole fraction of butyl acrylate in the polymer might be posing the problem of good surface contact. This would not be a problem with embedded contacts in a film, fiber or article and from a materials aspect or with a more penetrating contact point. Further this "poor" surface contact phenomenon might be ameliorated by increasing the wt% of PAMPSA in the triblock matrix polymer — easily done by using a PBA macroinitiator with a lower molecular weight. Additionally, different conditions should change the characteristics of the micelles used as templates, which should allow one to increase the conductivities of the resulting blends.

Morphology of supramolecular (AMPSA)₂7(BA)46e(AMPSA)₂7 and polypyrrole

As disclosed above the block copolymer with 16wt% PAMPSA was mixed with pyrrole which was polymerized in order to form a supramolecular complex between polypyrrole and AMPSA. A solution of the complex in NMP with 100 mg/ml concentration was deposited on silicon wafer surface. The thick film exhibited an unusual worm-like structure (from hundred nanometers to several micrometers long) surrounding with an unclear amorphous matrix (Figure 12). One can observe multilayer individual worm-like structures.

After thermal treatment, a nextwork of rod-like structure was formed. These AFM images together with the thick film image tell us that the supramolecular complex formed micelles in NMP. While unlikely the PBA could form a core structure while the complex of AMPSA and polypyrrole form the shell of micelles. In order to test this assumption, a sub- monolayer film was prepared from a 0.2 mg/ml solution in DMF. Unfortunately, the supramolecular complex did not exhibit clear structures on the substrate but one could observe a clear sub-monolayer rod-like carbon film after thermal treatment. These results demonstrate that a micellar-like structure with a poly (butyl acrylate) shell was generated in this system.

Example 6.2. Preparation of polypyrrole/triblock complex with 3x the previous amount of pyrrole A suspension of the triblock copolymer in water (5 mL, 100 mg polymer) was added to a round bottom flask and stirred at O⁰C for 20 minutes. Pyrrole (42.6 microliters) was added, and the solution was stirred for 30 minutes to allow the pyrrole to complex with the tethered AMPSA. The oxidizing agent (ammonium persulfate, 35.1 mg) was dissolved in 0.5 mL of water, and added dropwise to the polymer/pyrrole solution. The solution turned a dark brown color within 15 minutes of the addition of the ammonium persulfate. The reaction was kept at 0⁰C for several hours, then allowed to slowly warm up to room temperature as the reaction was stirred overnight. The next day 2 mL of NMP was added, and the water was removed by rotary evaporation. The doping of the sample was measured by UV vis in NMP. This sample had a good amount of polaron derealization, indicating the possibility of good conductivity. The larger polaron band in the new sample (Figure 13, sample 2-23) may be due to a higher content of conductive polymer in me sample. A film was poured from the remaining reaction solution and dried over several days in the vacuum oven. It was not as flexible and reversibly extendable as the previous sample, which is to be expected from the higher pyrrole content. However, the film did not exhibit any greater conductivity than the previous film (with 1/3 the amount of pyrrole) did. This low conductivity may still be the result of the high molecular weight poly (butyl acrylate) mid-block forming an insulating layer reducing the efficiency of surface contact.

Example 6.3. Redissolving AMPSA27BA468AMPSA₂7 in water Given that water seems to be the most effective solvent for the polypyrrole preparation, it seemed important to know if it were possible to redissolve dried triblock copolymer in water. A portion of the polymer (1 g) was dissolved in 2 mL of DMF and stirred for 45 minutes. Water (2 mL) was then added dropwise with, stirring, followed by a faster addition of 5 mL of water. The solution turned a cloudy white in color. The DMF was removed via dialysis against water, but there was some precipitation after dialysis. This result indicates that the easiest way to get polymer micelles in water is to simply keep the polymer suspended in the water after dialysis and the ion exchange column.

Example 6.4. Preparation of lower MW poly (butyl acrylate) difunctional macroinitiator (150:1:0.5:0.5)

Degassed butyl acrylate (20 mL) was added to a reaction flask, followed by degassed anisiole (2 mL). The solution was then degassed for several minutes. The initiator (dibromo dimethyl heptanedioate, 101 microliters) was then added, followed by PMDETA (48.5 microliters) and CuBr (33.4 mg). The solution was degassed for several minutes after each addition was made. The reaction mixture was then lowered into a 70⁰C oil bath. The reaction was monitored by GC (with anisole as the internal standard). The conversion was fairly linear with time, and the reaction was stopped after 215 minutes (final conversion 50%). According to THF GPC results, the Mn was 19,800 g/mol, with a PDI of 1.14.

Example 6.5. Chain extension of PBA macroinitiator with AMPSA using ATRP (300:1:1:0.7)

The PBA macroinitiator (3 g) was added to a 100 mL Schlenk flask, followed by AMPSA (18.63 g), and the flask was degassed for 30 minutes. Degassed TBA (5% molar excess vs AMPSA, 22.5 mL) was then added and allowed to stir for several minutes. Degassed DMF (54 mL) was then added, and the mixture was stirred until all the macroinitiator and AMPSA were dissolved. The solution was then degassed for 20 minutes. The catalyst was prepared in a separate flask. CuCl (89 mg) and bpy (98.4 mg) were added to a 10 mL Schlenk flask; air was removed by vacuum, followed by flushing with N₂. This cycle was repeated 4 times, in order to completely remove air from the flask. Degassed DMF (3 mL) was then added, and the mixture was stirred under nitrogen for 10 minutes in order to facilitate formation of the complex. A portion of this solution (1 mL, 29.7 mg CuBr, 32.8 mg bpy) was added to the reaction flask, and degassed for several minutes with stirring. The flask was then lowered into a 6O⁰C oil bath, and allowed to stir for two days. The reaction was stopped by addition of wet DMF, and the contents of the flask were poured into 150 mL of water, forming micelles with a green cast. The reaction mixture was purified by dialysis overnight, then a portion was passed through a Diowex ion exchange column to regenerate the acid form. This acid form was readily soluble in water, indicating a high weight percentage incorporation of AMPSA into the tri-block copolymer.

This polymer was used as a template for the polymerization of polypyrrole, in an effort to make the resulting film conductive by increasing the weight % of the conducting and acidic phases.

AMPSA was also polymerized by ATRP using TPMA as a ligand but control was no better than with bpy.

Additional examples include templated polymer systems with methacrylic acid as the donor segment and DMAEMA as the non-donor segment, providing a water soluble complex.

Also, the polypyrrole films already prepared will be doped with PFβ to see if the conductivity can be increased by post-processing doping. A RAFT preparation of PAMPSA with cumyl dithiobenzoate using a slow continuous addition of AMPSA as well as RAFT with purified/distilled methanol should result in improved polydispersity.

Some additional examples that were prepared using the procedures detailed above are:

PAMPSA-P((meth)acrylate) + PANi/AMPSA PAMPS A-P((meth) acrylic acid), (after hydrolysis of t-butyl((meth) aery late)

PAMPSA-P(methacrylate-co-PEO side chains) - targeted for ionic/electronic conductivity (batteries) PAMPSA-P((meth)acrylamide) P(StSulfAcid)-b-ofher (prepared by NMP) Post-functionalization of conjugated polymers with block copolymers comprising a functional insulating polymer block with pre-selected functionality is an efficient way to improve their solubility and enhance the mechanical and optical properties. The block copolymers can be used as templates for phase separation induced organization of the conductive polymer. Well defined conducting nano-structured materials were prepared using the self -organization of phase incompatible segmented copolymers.

Embodiments of the present invention are therefore directed at the preparation of conducting polymeric material comprising a phase separable segmented (co)polymer wherein at least one segment comprises a donor segment that forms a complex with an added conducting polymer or a conducting polymer precursor wherein the self assembly characteristics of the resulting phase separable segmented copolymer comprising the conducting polymer complex templates the nanostructure of the final conducting material. The phase separable segmented copolymers can comprise any structural topology including linear block copolymers, star copolymers, graft copolymers or brush copolymers such that one phase of the final nanostructure of the conducting material comprising a conducting polymer complex form a spherical, cylindrical, gyroidal or lamellar morphology. The final conductive polymer complex can additionally comprise additional donor molecules that can be added to the complex prior to or during preparation of the complex or in a post polymerization procedure. The conducting polymer or a conducting polymer precursor can be added to the first segmented copolymer comprising a donor segment as a monomer, oligomer or polymer in either a doped, partially doped or un-doped state. When the conducting polymer precursor is a monomer or oligomer and is added to the first segmented copolymer in a doped, partially doped or un-doped state it can be polymerized in the presence of the segmented copolymer to form the final complexed conductive phase. The resulting conducting polymeric material can have a final morphology that is either continuous or discontinuous and can be (reversibly) converted from one to another state by external stimuli: including solvent, vapors, T, pH, mechanical stresses. Additional doping agents can be used to adjust conductivity of the formed conductive polymeric complex or alloy and optionally the volume fraction of the conducting phase. The non-conductive second segment(s) in the segmented copolymer can provide further functionality to the conducting material. Indeed the final conducting polymeric material can also be a tri-phasic phase separated conducting material comprises a conducting polymer complexed with a donor segment and two additional phases one of which can be an ionic conductive phase or can be a functional segement. The final morphology of the non-donor phase in the bulk copolymer can be selected to provide desired phylicity to the complex and to provide a continuous or co- continuous matrix to enhance mechanical properties and processing of the polymer blends or can be selected to be the minor phase and thereby provide toughening of the conductive matrix. Therefore the conductive nanostructured materials can be formed into a foil, a fiber, a tube or a pipe, or a coating. Indeed the phase separation of the segmented polymer can occur during processing of the segmented copolymer and added conductive material or conductive material precursor as temperature or composition (e.g. by removal of solvent or other additive) is changed or by known mechanical means for orientation, or stretching of the first fabricated material. Each phase of the phase separable copolymer can comprise a homopolymer or a copolymer. The phase separable copolymer comprising a donor segment can be prepared by (co)polymerizing a donor monomer or one or more segments in a formed segmented copolymer can by functionalized to provide the donor functionality. The properties of the material is controlled by pre-selecting the final ratio of the two phases, the degree of phase separation between incompatible blocks, hence the aggregation of the conjugated polymer chain, the solubility /processability of the material resulting in control over mechanical properties, electrical properties, optical properties and inherent stability to environmental conditions. For example when the non-donor segment(s) of the segmented copolymer can comprise polymer segments with a Tg below use temperature thereby providing flexible and stretchable materials or can comprise polymer segments with a Tg above room temperature thereby providing a rigid material. Further the organization and topology or architecture of the copolymer and the nano-dimensions of each phase can be modified by the molecular weight of each segment or by the presence of selected solvents. We teach therefore a process for the preparation of a conductive polymer complex wherein a segmented copolymer comprising a donor segment is reacted with a conductive polymer, or conductive polymer precursor, optionally in the presence of a solvent and additional additives. The selected solvent can be a polar solvent preferentially selected to dissolve the polar segment of the copolymer and can optionally be water in which case the first segmented copolymer comprises a strongly phase separating water soluble segmented copolymer to complex with, confine, and organize, the conducting material within the formed phase comprising the conductive complex and the strongly acidic segment of the dopant segment of the copolymer.

Claims

I . A conducting polymeric material comprising a phase separable segmented (co)polymer wherein at least one segment comprises a donor segment that forms a complex with an added conducting polymer or a conducting polymer precursor. 2. The conducting polymeric material of claim 1, wherein the self assembly characteristics of the resulting phase separable segmented copolymer comprising the conducting polymer complex templates the nanostructure of the final conducting material.

3. The conducting polymeric material of claim 1, wherein the first phase separable segmented polymer comprising a donor segment is one of a linear block copolymer, star copolymer, graft copolymer, bottlebrush copolymer or a brush copolymer tethered to a substrate.

4. The conducting polymeric material of claim 1, wherein the donor segment of the first segmented polymer and the conducting polymer or conducting polymer precursor form a complex that comprises one phase of the final nanostructure of the conducting material. 5. The conducting polymeric material of claim 4, wherein final nanostructure of the conducting segmented polymer comprising a conducting polymer complex form a spherical, cylindrical, gyroidal or lamellar morphology.

6. The conducting polymeric material of claim 4, wherein the segmented polymer comprising the conducting polymer phase comprise additional donor molecules. 7. The conducting polymeric material of claim 1, wherein the conducting polymer or a conducting polymer precursor is added to the first segmented copolymer comprising a donor segment as a monomer, oligomer or polymer in either a doped, partially doped or un-doped state.

8. The conducting polymeric material of claim 1, wherein a monomer or an oligomer is added to the first segmented copolymer in a doped, partially doped or un-doped state and is polymerized in the presence of the segmented copolymer to form the final complexed conductive phase.

9. The conducting polymeric material of claim 1, wherein the phase separated material has conductivity above IxIO^"3 S/cm. 10. The conducting polymeric material of claim 1, wherein the phase separated material has conductivity above 1 S/cm.

II. The conducting polymeric material of claim 1, wherein the stable conductive polymer films have as cast conductivities exceeding 10 S/cm under ambient conditions. 12. The conducting polymeric material of claim 1, wherein the phase separated conductive nanostructured materials can be formed into a film, a coating, a foil, a fiber, or a solid structural material or added to a another polymer to modify the electrical or antistatic properties. 13. The conducting polymeric material of claim 1, wherein the phase separated conducting materials are inherently cohesive materials that can be bent, rolled, dropped, pierced etc.

14. The conducting polymeric material of claim 1, wherein one phase of a bi- or tri-phasic phase separated conducting material comprises a conducting polymer complexed with a donor segment.

15. The conducting polymeric material of claim 14, wherein the final morphology of the non-donor phase in the bulk copolymer can be continuous or discontinuous.

16. The conducting polymeric material of claim 14, wherein the final morphology can be continuous or discontinuous and can be (reversibly) converted from one to another state by the mole fraction of added conductive material or by external stimuli: including solvent, vapors, T, pH, mechanical stresses.

17. The conducting polymeric material of claim 14, wherein conducting polymer phase comprises one of an oligo-polymeric material, substituted and unsubstituted, poly(para- phenylene)s, poly(para-phenylenevinylene)s, polypheny leneethynylene such as poly(p- phenylenepentadienylene), poly anilines, polyazines, polythiophenes, polythienylenevinylene, poly(para-phenylene sulfide)s, polyfurans, polypyrroles, polyfluorene, polyselenophene, polyacetylenes, polynaphthalenes and polyethylene dioxythiophene.

18. The conducting polymeric material of claim 14, comprising a strongly phase separating segmented copolymer to confine, and organize, the conducting material within the formed phase comprising a strongly acidic segment of the copolymer.

19. The conducting polymeric material of claim 14, comprising a strongly phase separating amphiphilic segmented copolymer to complex with, confine, and organize, the conducting material within the formed phase comprising the conductive complex and the strongly acidic segment of the dopant amphiphilic copolymer. 20. The conducting polymeric material of claim 19, wherein incorporation of the conducting polymer within the dopant phase can change the volume fraction of the dopant phase thereby forming a continuous conductive phase.

21. The conducting material of claim 14, wherein the added conductive polymer can initially be a precursor of a conductive polymer comprising a monomer, oligomer or a (co)polymer and can be added to the initial segmented copolymer as the sole additive or as one component of a mixture of additives.

22. The conducting material of claim 21, wherein additional doping agents can be used to adjust conductivity of the formed conductive polymeric complex or alloy and optionally the volume fraction of the conducting phase.

23. The conducting material of claim 21, wherein additional doping agents can be used to adjust the solubility of the added conductive polymer phase precursor and thereby, optionally, the volume fraction of the final conducting phase in the conducting material.

24. The conducting polymeric material of claim 14, wherein a second segment of the segmented copolymer can be selected to provide a continuous or co-continuous matrix to enhance mechanical properties and processing of the polymer blends or can be selected to be the minor phase and thereby provide toughening of the conductive matrix.

25. The conducting polymeric material of claim 24, wherein a second segment in the segmented copolymer provides further functionality to the conducting material. 26. The conducting polymeric material of claim 24, wherein the second segment provides ionic conductivity.

27. The conducting polymeric material of claim 25, wherein the second segment that provides further functionality to the conducting material is itself a segmented copolymer thereby forming a tri-phasic material. 28. The conductive polymeric material of claim 1, wherein the conductive material is a processable polymeric material.

29. The conductive polymeric material of claim 28, where the conductivity of the material can be controlled.

30. The conductive polymeric material of claim 28, wherein the conductive nanostructured materials can be formed into a foil, a fiber, a tube or a pipe, or a coating.

31. The conductive polymeric material of claim 28, wherein the phase separable segmented copolymer is one of a block copolymers, star copolymers or graft copolymers, core shell copolymers or bottlebrush copolymers having a portion or segment capable of donating a proton to a conductive polymer, or conductive polymer precursor, and a segment or portion that acts to organize the phase separable segmented copolymer.

32. The conductive polymeric material of claim 31 , wherein the phase separable segmented copolymer comprising a portion or segment capable of donating a proton to a conductive polymer or conductive polymer precursor comprise donor monomer units including acids (including salts or anhydrides of acids), unsubstituted amides, N-hydrocarbyl- substituted amides, including N-vinyl amides, sulfoalkyl esters, or sulfoalkyl amides.

33. The conductive polymeric material of claim 32, wherein the donor acid monomer units comprise acidic functionality including carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acidic half esters of maleic and fumaric acids where the alcohol-derived moiety contains 1 to 8 carbon atoms, and maleamic acids. •

34. The monomer units comprising acidic functionality of claim 33, where the preferred acids contain 3 to 10 carbon atoms 35. The monomer units comprising acidic functionality of claim 33, where the preferred acids contain preferably 3 to 5 carbon atoms.

36. The conductive polymeric material of claim 32, wherein the donor acid monomer units comprising acidic functionality include salts or anhydrides of such acids and wherein the salts include ammonium salts, amine salts, and metal salts such as, in particular, alkali metal salts and alkaline earth metal salts.

37. The salts of claim 36, wherein the specific preferred metals include lithium, sodium, and potassium salts.

38. The conductive polymeric material of claim 32, wherein the donor acid monomer units comprise a sulfonic acid or a salt thereof. 39. The conductive polymeric material of claim 38, wherein the donor monomer units comprise sulfonic acids or salts thereof include acrylamidoalkane sulfonic acids such as 2- acrylamido-2-methylpropanesulfonic acid, as well as such monomers as 2-sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, and methallylsulfonic acid or a sulfoalkyl ester such as 2-sulfoethylmethacrylate, 3-sulfopropyl acrylate, or 3-sulfopropylmethacrylate.

40. The conductive polymeric material of claim 32, wherein the donor acid monomer units comprise a phosphonic acid or a salt or anhydride thereof.

41. The donor monomer units of claim 40, comprising phosphonic acids or salts or anhydride thereof including monomer units such as phosphonomethylacrylate, phosphonomethyl methacrylate, vinyl phosphonic acid, and allyl phosphonic acid.

42. The conductive polymeric material of claim 32, wherein the donor monomer units comprise an amide including unsubstituted amides such as acrylamide, or methacrylamide, or a N-substituted derivative thereof such as an N-hydrocarbyl-substituted amide derivative. 43. The donor monomer units of claim 42, comprising amides further include amides such as N-methylacrylamide, N,N-dimethyl acrylamide, N-methylmethacrylamide, N,N- dimethylmethacrylamide, as well as such materials as t-butylacrylamide, substituted amides include those having N-substituents with polar functional groups such as hydroxy or carbonyl groups, such as CH.sub.2 .dbd.CHC(O)NH-CH.sub.2 CH (OH) CH. sub.3 or CH.sub.2 .dbd.CHC(O)NH-C(CH.sub.3).sub.2 CH.sub.2 C(O)CH.sub.3 or CH.sub.2 .dbd.CHC(O)NH-CH.sub.2 CO.sub.2 H.

44. The donor monomer units of claim 42, comprising N-substituted derivatives wherein each such hydrocarbyl group will preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Preferably, also, each nitrogen atom of the amide will contain only one such substituent.

45. The conductive polymeric material of claim 32, wherein the donor monomer units comprise sulfoalkyl amides including sulfomethyl acrylamide and related materials.

46. The conductive polymeric material of claim 32, wherein donor polymer segment comprises a copolymer.

47. The conductive polymeric material of claim 32, wherein donor polymer segment initially comprises a donor monomer precursor which, after incorporation into the polymer, can be converted into a donor monomer.

48. The donor monomer precursor of claim 47, comprising a monomer unit that can be subjected to hydrolysis to convert the donor precursor monomer units into a donor monomer unit comprising alcohol, acid or amide units.

49. The donor monomer precursor of claim 47, comprising a monomer unit that can be functionalized by a substitution reaction to form a donor substituent on the first monomer unit. 50. The conducting polymeric material of claim 1, wherein the phase separation of the segmented polymer can occur during processing of the segmented copolymer and added conductive material or conductive material precursor as temperature or composition (e.g. by removal of solvent or other additive) is changed or by known mechanical means for orientation, or stretching of the first fabricated material. 51. The conducting polymeric material of claim 1, comprising a conducting poly aniline or oligo aniline-based material that forms a complex with, and is templated by, the self-assembly of a block copolymer comprising acrylamido-2-methyl-N-propanesulfonic acid monomer units and alkyl((meth) acrylate) monomer units. 52. The conducting polymeric material of claim 51, wherein the polyaniline was incorporated into the block copolymer as the emeraldine base.

53. The conducting polymeric material of claim 1, comprising a conducting polythiophene, substituted thiophene or oligothiophene-based material that forms a complex with and is templated by the self-assembly of a block copolymer comprising a donor segment.

54. The conducting polymeric material of claim 53, wherein the precursors of the polythiophene, or substituted thiophene comprises ethylenedioxythiophene unit which is added to the first segmented donor containing segmented copolymer as a monomer, oligomer or polymer.

55. The conducting polymeric material of claim 1, comprising a conducting polypyrrole, substituted polypyrrole or oligopyrrole-based material forms a complex with and is templated by the self-assembly of a block copolymer comprising a donor segment.

56. The conducting polymeric material of claim 53, wherein the precursors of the polypyrrole, or substituted polypyrrole comprises pyrrole units which are added to the first segmented donor containing segmented copolymer as a monomer and are therein polymerized.

57. The conducting polymeric material of claim 1, wherein the properties of the material is controlled by pre-selecting the final ratio of the two phases, the degree of phase separation between incompatible blocks and hence the aggregation of the conjugated polymer chain, the solubility /processability of the material resulting in control over mechanical properties, electrical properties, optical properties and inherent stability to environmental conditions.

58. The conducting polymeric material of claim 1, wherein the non-donor segments of the segmented copolymer comprise polymer segments with a Tg below use temperature thereby providing flexible and stretchable materials.

59. The flexible polymer segments of claim 58, wherein the non-donor segments of the segmented copolymer comprise monomer units wherein said monomer(s) are of the formula:

R¹ R³

\ / C=C

/ \ R² R⁴

wherein R¹ and R² are independently selected from the group consisting of H, halogen, CN, CF₃, straight or branched alkyl of from 1 to 20 carbon atoms, α,β-unsaturated straight or

branched alkenyl or alkynyl of 2 to IO carbon atoms, α,β-unsaturated straight or branched alkenyl of 2 to 6 carbon atoms substituted with a halogen, C₃-Cg cycloalkyl, heterocyclyl, C(=Y)R⁵, C(= Y)NR⁶R⁷ and YC(=Y)R⁸; where Y may be NR⁸ or O; R⁵ is alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms, aryloxy or heterocyclyloxy; R⁶ and R⁷ are independently H or alkyl of from 1 to 20 carbon atoms, or R⁶ and R⁷ may be joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6- membered ring; and R⁸ is H, straight or branched Ci-C_2O alkyl or aryl; and

R³ and R⁴ are independently selected from the group consisting of H, halogen, Ci-C₆ alkyl and COOR⁹, where R⁹ is H, an alkali metal, or a Ci-C₆ alkyl group; or R¹ and R³ may be joined to form a group of the formula (CHa)_n ¹ or a group of the formula C(=O)-Y-C(=O), where n' is from 2 to 6, the group (CHz)_n' may be substituted with from 1 to 2n' halogen atoms or C₁-C4 alkyl groups, and Y is as defined above; and at least two of R¹, R², R³ and R⁴ are H or halogen.

60. The conducting polymeric material of claim 1, wherein the non-donor segments of the segmented copolymer comprise polymer segments with a Tg above room temperature thereby providing a rigid material.

61. The conducting polymeric material of claim 1, wherein the material is suitable for use in flexible photovoltaic diodes, flexible electroluminescent diodes, plastic field transistors as semiconductors and in the conducting state antistatic protection, electromagnetic shielding, modified electrodes or sensors.

62. The conducting polymer of claim 26, wherein the morphology of the second ionic conducting phase is modified by addition of a solvent.

63. The conducting polymer of claim 62, wherein the morphology of the final membrane is gyroidal. 64. The conducting polymeric material of claim 1, wherein the organization and topology or architecture of the copolymer and the nano-dimensions of each phase can be modified by the molecular weight of each segment or by the presence of selected solvents.

65. A process for the preparation of a conductive polymer complex wherein a segmented copolymer comprising a donor segment is reacted with a conductive polymer, or conductive polymer precursor in the presence of a solvent.

66. The process of claim 65, wherein the solvent is a polar solvent.

67. The process of claim 66, wherein the polar solvent is water.

68. The conducting polymeric material of claim 65, wherein the first segmented copolymer comprises a strongly phase separating water soluble segmented copolymer to complex with, confine, and organize, the conducting material within the formed phase comprising the conductive complex and the strongly acidic segment of the copolymer.