Polyaniline sulfonated derivatives

Self-doping was eonfirmed by the similarity between absorption speetra of the sulfonated polyaniline and the emeraldine hydrochloride form (Figure 20.44). The effect of the sulfonate group on steric interactions between adjacent rings is evident from the blue shift in the absorption spectra of the sodium salt of the non-protonated sulfonated derivative compared to the emeraldine base (Figure 20.45). 

Polyaniline (PANI) can be formed by electrochemical oxidation of aniline in aqueous acid, or by polymerization of aniline using an aqueous solution of ammonium thiosulfate and hydrochloric acid. This polymer is finding increasing use as a "transparent electrode" in semiconducting devices. To improve processibiHty, a large number of substituted polyanilines have been prepared. The sulfonated form of PANI is water soluble, and can be prepared by treatment of PANI with fuming sulfuric acid (31). A variety of other soluble substituted AJ-alkylsulfonic acid self-doped derivatives have been synthesized that possess moderate conductivity and allow facile preparation of spincoated thin films (32). 

Polyaniline is less tolerant of preparation conditions than polypyrrole, and the list of anion dopants used in the preparation is more limited. However, subsequent replacement of the anion used in preparation by a dodecylben-zene sulfonate makes polyaniline become soluble in solvents such as Af-methyl pyrrolidone (NMP), or zn-cresol, and it can be spin-coated or otherwise solution-processed. In a similar way derivatives of aniline, such as... 

A number of water-soluble polyaniline derivatives have been developed in recent years. Incorporation of sulfonate groups onto the polymer backbone imparts water solubility to the polymer. In one process, this is accomplished by treating the polymer with fuming sulfuric acid which results in a sulfonic acid ring-substituted derivative that is alkali soluble but only upon conversion to the nonconducting sulfonate salt form. 

A second method of introducing sulfonate groups is accomplished by deprotonating polyaniline base and reacting with a sultone, i.e., 1,3-propanesultone [22]. This gives rise to an N-substituted polyaniline derivative that is water soluble. Another route involves the polymerization of sulfonated aniline monomer such as sodium salt of diphenylaminesulfonic acid [23]. 

Polyaniline and its substituted derivatives, such as poly(o-toluidine), poly(o-anisidine), poly(N-methylaniline), poly(N-ethylaniline), poly(2,3-dimethylaniline), poly(2,5-dimethylaniline) and poly (diphenylamine) have been reported [36] to show measurable responses (sensitivity 60%) for short chain alcohols (viz., methanol, ethanol and propanol) at concentrations up to 3000 ppm. The change (decrease) in resistance of the polymers on exposure to alcohol vapors has been explained based on the vapor-induced change in the crystallinity of the polymer. Polypyrrole (PPy) incorporated with dodecyl benzene sulfonic acid and ammonium persulfate has been reported to show a linear change in resistance when exposed to methanol vapor in the range 87-5000 ppm [37]. The response is rapid and reversible at room temperature. 

Using functional molecules as structural directors in the chemical polymerization bath can also produce polyaniline nanostructures. Such structural directors include surfactants [16-18], liquid crystals [19], polyelectrolytes (including DNA) [20,21], or complex bulky dopants [22-24]. It is believed that functional molecules can promote the formation of nanostructured soft condensed phase materials (e.g., micelles and emulsions) that can serve as soft templates for aniline polymerization (Figure 7.3). Polyelectrolytes such as polyacrylic acid, polystyrenesulfonic acid, and DNA can bind aniline monomer molecules, which can be polymerized in situ forming polyaniline nanowires along the polyelectrolyte molecules. Compared to templated syntheses, self-assembly routes are more scalable but they rely on the structural director molecules. It is also difficult to make nanostructures with small diameters (e.g., <50 nm). For example, in the dopant induced self-assembly route, very complex dopants with bulky side groups are needed to obtain nanotubes with diameters smaller than 100 nm, such as sulfonated naphthalene derivatives [23-25], fidlerenes [26], or dendrimers [27,28]. 

Different self-doped polyanilines have been prepared using aniline derivatives eontaining earboxylate or sulfonate groups, or the aeid funetionalities were ineor-porated during a post-modifieation step using the appropriate ehemieal or eleetro-ehemieal reaetions [158,197,254,303],... 

C. H. Yang, T. C. Wen, Polyaniline derivative with external and internal doping via electrochemical copolymerization of aniline and 2,5-diaminobenzene-sulfonic acid on Ir02-coated titanium electrode, of the Electrochemical Society 1994,141, 2624. 

Aside from considerations of the polymer form itself, polyaniline can be doped and derivatized in a variety of ways. First, polyaniline can be polymerized in the presence of a variety of acids, which critically influences the resulting electronic properties [1-15]. The particular acid used and polymerization process employed can affect the degree of crystallinity observed [10-15,17-29]. Multiple dopants and substitutions have been achieved in the hope of increasing both the conductivity and solubility of these materials. The derivatives are simple polyanilines functionalized with complex ions such as aryl-SOj, camphorsulfonates, and perfluoroalkyl (and aryl) sulfonates. Dopants vary from simple anions, to oxyanions, to the more typical iodide ions [10-15,17-29,38-44]. The functionalization and/or doping affects, the band population, and the polyaniline chain conformation in turn influence the resulting electronic and structural properties of the polymer. 

In addition to functionalization of polyanilines with sulfonic and carboxylic acids, the corresponding phosphonic acid derivatives have been prepared, o-Aminobenzylphosphonic acid was prepared as shown in Figure 20.54 [42,43]. Oxidative coupling of the above monomer in an acidic medium yielded poly(o-aminobenzylphosphonic acid) (Figure 20.55). Spectroscopic analysis was consistent with head-to-tail oxidative coupling through the /Jara-position. The as-prepared polymer was in its emeraldine oxidation state in which 43% of the N-atoms were protonated by the pendent acid. This polymer was insoluble in both non-aqueous solvents and aqueous acidic solutions. 

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