Conducting functional polymer films

Functionalized conducting monomers can be deposited on electrode surfaces aiming for covalent attachment or entrapment of sensor components. Electrically conductive polymers (qv), eg, polypyrrole, polyaniline [25233-30-17, and polythiophene/23 2JJ-J4-j5y, can be formed at the anode by electrochemical polymerization. For integration of bioselective compounds or redox polymers into conductive polymers, functionalization of conductive polymer films, whether before or after polymerization, is essential. In Figure 7, a schematic representation of an amperomethc biosensor where the enzyme is covalendy bound to a functionalized conductive polymer, eg, P-amino (polypyrrole) or poly[A/-(4-aminophenyl)-2,2 -dithienyl]pyrrole, is shown. Entrapment of ferrocene-modified GOD within polypyrrole is shown in Figure 7. 

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

Figure 13. Schematic diagram of the measurement of the ionic conductivity of a conducting polymer membrane as a function of oxidation state (potential), (a) Pt electrodes (b) potentiostat (c) gold minigrid (d) polymer film (e) electrolyte solution (0 dc or ac resistance measurement.133 (Reprinted with permission from J. Am Chem Soc. 104, 6139-6140, 1982. Copyright 1982, American Chemical Society.)...

Tetra(o-aminophenyl)porphyrin, H-Co-Nl TPP, can for the purpose of electrochemical polymerization be simplistically viewed as four aniline molecules with a common porphyrin substituent, and one expects that their oxidation should form a "poly(aniline)" matrix with embedded porphyrin sites. The pattern of cyclic voltammetric oxidative ECP (1) of this functionalized metal complex is shown in Fig. 2A. The growing current-potential envelope represents accumulation of a polymer film that is electroactive and conducts electrons at the potentials needed to continuously oxidize fresh monomer that diffuses in from the bulk solution. If the film were not fully electroactive at this potential, since the film is a dense membrane barrier that prevents monomer from reaching the electrode, film growth would soon cease and the electrode would become passified. This was the case for the phenolically substituted porphyrin in Fig. 1. 

A very common and useful approach to studying the plasma polymerization process is the careful characterization of the polymer films produced. A specific property of the films is then measured as a function of one or more of the plasma parameters and mechanistic explanations are then derived from such a study. Some of the properties of plasma-polymerized thin films which have been measured include electrical conductivity, tunneling phenomena and photoconductivity, capacitance, optical constants, structure (IR absorption and ESCA), surface tension, free radical density (ESR), surface topography and reverse osmosis characteristics. So far relatively few of these measurements were made with the objective of determining mechanisms of plasma polymerization. The motivation in most instances was a specific application of the thin films. Considerable emphasis on correlations between mass spectroscopy in polymerizing plasmas and ESCA on polymer films with plasma polymerization mechanisms will be given later in this chapter based on recent work done in this laboratory. 

Large numbers of functionalized LB films have been prepared. Highly ordered LB films have been formed by the inclusion of surface-active cobaltous phthalocyanine [168] amphiphilic TCNQ was assembled to function as conducting LB films [169] liquid-crystalline LB films, potentially capable of undergoing thermotropic or lyotropic phase transitions [170, 171], have also been generated. Spacer groups introduced into polymeric surfactants (23) helped to stabilize the LB films which they formed by decoupling the motion of pendant polymers (see Fig. 13) [172]. 

Functionalized polymers are of interest in a variety of applications including but not limited to fire retardants, selective sorption resins, chromatography media, controlled release devices and phase transfer catalysts. This research has been conducted in an effort to functionalize a polymer with a variety of different reactive sites for use in membrane applications. These membranes are to be used for the specific separation and removal of metal ions of interest. A porous support was used to obtain membranes of a specified thickness with the desired mechanical stability. The monomer employed in this study was vinylbenzyl chloride, and it was lightly crosslinked with divinylbenzene in a photopolymerization. Specific ligands incorporated into the membrane film include dimethyl phosphonate esters, isopropyl phosphonate esters, phosphonic acid, and triethyl ammonium chloride groups. Most of the functionalization reactions were conducted with the solid membrane and liquid reactants, however, the vinylbenzyl chloride monomer was transformed to vinylbenzyl triethyl ammonium chloride prior to polymerization in some cases. The reaction conditions and analysis tools for uniformly derivatizing the crosslinked vinylbenzyl chloride / divinyl benzene films are presented in detail. 

Conducting polymer films are commonly characterized using cyclic voltammetric techniques, while their morphology and the presence of specific functional groups are achieved using SEM, NMR and FTIR spectroscopy. 

Fig. 4.27 Typical design for AFM hotstage (left), and effect of tip/cantilever on true sample surface temperature in air (right). Here the differential of sample surface temperature (i.e., temperature overestimate) normalized to the temperature differential between cantilever and true surface temperature is plotted as function of film thickness for typical polymers according to the experimental data and heat transfer modeling described in [52] (right). The thermal conductivities of PS, PEO, and HDPE are 0.14 W/(K m), 0.205 W/(K m), and 0.39 W/(K m), respectively. Reproduced with permission from [52]. Copyright 2002. American Chemical Society...

Cao and coworkers reported that problems in processing of doped PANi could be solved by the use of functionalized protonic acids. Indeed, solutions of camphor-sulfonic acid doped with PANi in m-cresol show liquid crystallinity and high electrical conductivity, according to Smith and his coworkers. This prompted additional work with this and other polymers. Unfortunately, the conductivity of cast films of solutions of polypyrrole (PPy) doped with dodecyl benzene sulfonic acid in m-cresol is low (ca. 10 S/cm). 

In view of the above, conductivity measurements were conducted in asymmetric systems Au-polymer-Si for polystyrene and polysilazane, and Au-polymer-In for polysiloxane. The difference in barrier height between Au-polymer and Si-polymer estimated on the basis of measurements of the Au-Si barrier is ca. 0.5 eV (M) which, in the case of the conductivity limited by the electrodes, should produce a difference in the intensity of the currents of opposite polarizations equal to about 8 orders of magnitude. The difference in work function of Au and In, on the other hand, is ca. 1 eV so, on the assumption of the Schottky mechanism of conductivity, the difference in the intensity of opposite polarizations should amount to 17 orders of magnitude ( ). As can be seen in Fig. 4 in the case of an asymmetric polysilazane sample there is a difference in the intensity of the currents although this difference does take the expected course, it is several times smaller than expected, and is thus virtually negligible. A similar result was obtained for the polystyrene sample, while in the case of the asymmetric system based on polysiloxane there was no difference in the intensity of the opposite-biassed fields over the entire range of fields used - up to 3 x 10 V/m. It can thus be assumed that the conductivity in the films under study is dominated by the Poole-Frenkel volume generation independent of the contact effects. Such were also the conclusions of the workers who studied the conductivity in polystyrene (29) and polysiloxane (21). 

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