Polyaniline solubility

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). 

In a complementary study of the interaction between polyanilinc and ITO, oligomeric polyaniline model compounds, namely phenyl-capped amino (PC2) and imino (PC20X) dimers [113, 114] have been used. The chemical structures of the polyaniline oligomers are displayed in Figure 5-20. Both substances are soluble in... 

Ideal electrochemical polymerization was considered to give ideal linear and conjugated polymeric chains. The real situation is that films electrogenerated from the basic monomers are insoluble and infusible. Only polyaniline films are partially soluble in some solvents. 

Jung JW, Lee JU, Jo WH (2009) High-efficiency polymer solar cells with water-soluble and self-doped conducting polyaniline graft copolymer as hole transport layer. J Phys Chem C 114 633... 

Alva KS, Marx KA, Kumar J, Tripathy SK (1996) Biochemical synthesis of water soluble polyanilines poly(p-aminobenzoic acid). Macromol Rapid Commun 17(12) 859-863... 

Electrically conducting polymer particles such as polypyrrole and polyaniline could also be prepared by dispersion polymerization in aqueous ethanol (31). The oxidation polymerization of pyrrole and aniline has been carried out at the electrode surfaces so far and formed a thin film of conducting polymer. On the other hand, polypyrrole precipitates as particles when an oxidizing reagent is added to a pyrrole dissolved ethanol solution, which contains a water-soluble stabilizer. In this way electrically conducting polymer particles are obtained and, in order to add more function to them, incorporation of functional groups, such as aldehyde to the surface, and silicone treatment were invented (32). 

Generally speaking, if achiral dopant acid is a strong acid, that is, pKa < 3, and soluble in water, ZV-mcthyl-2-pyrrolidinone, dimethyl sulfoxide, or N,N -dimethylformamide can be used to generate helical polyaniline. 

Soluble polyaniline has been reported as being prepared in the presence of aromatic sulphonic acids 272). 

Sample Preparation. Chemically polymerized 2-ethyl polyaniline, with reported molecular weight of 5000, was prepared by the method outlined by Leclerc et al. (15). Treatment of the insoluble product with ammonium hydroxide solution resulted in transforming the salt into the soluble EB form, which exhibited slight solubility in methanol. The soluble EB form of PANi is known to be readily protonated under acidic conditions, producing the highly insoluble ammonium salt form (16.17). In order to maintain the free amine base form in solution, it was necessary to synthesize the silica gel in the presence of a minimal amount of acid catalyst. 

During the last decade, immobilization of oxidase type enzymes by physical entrapment in conducting or ionic polymers has gained in interest, particularly in the biosensor field. This was related to the possibility for direct electron tranfer between the redox enzyme and the electroconducting polymers such as polypyrrole (1,2), poly-N-methyl pyrrole (3), polyindole (4) and polyaniline (5) or by the possibility to incorporate by ion-exchange in polymer such as Nafion (6) soluble redox mediators that can act as electron shuttle between the enzyme and the electrode. 

Practical applications have been reported for PVP/cellulosics (108,119,120) and PVP/polysulfones (121,122) in membrane separation technology, eg, in the manufacture of dialysis membranes. Electrically conductive polymers of polyaniline are rendered more soluble and hence easier to process by complexation with PVP (123). Addition of small amounts of PVP to nylon 66 and 610 causes significant morphological changes, resulting in fewer but more regular spherulites (124). 

More recently, Buchwald has reported the polymerization of the monomer in Eq. (38) [220]. This monomer was polymerized at 80 °C for 24 h in the presence of a catalyst comprised of Pd2(dba)3 and ligand 14. The polymers generated from this monomer bearing a Boc group are soluble in THF and chloroform with the aid of sonication. After isolation, the Boc group could be removed by thermolysis at 185 °C or by protonolysis in air. Emeraldine or the emeraldine salt forms of polyaniline result. 

In an attempt to overcome the low infusible character and low solubility of aniline, dispersion polymerization of aniline was conducted in water-dispersible colloidal particles that can be cast as films or blended with other materials to prepare composites. HRP mediated polymerization of aniline in a mixture of phosphate buffer and organic solvent resulted in polyaniline composed of ortho-directed units and para-directed units. Increasing the pH or adopting an organic solvent with a high dielectric constant, enhanced the production of ortho-directed units [54]. These ortho-directed polyanilines were more thermally flexible and electrically conductive. 

Samuelson LA, Anagnostopoulos A, Alva KS et al (1998) Biologically derived conducting and water soluble polyaniline. Macromolecules 31 4376 1378... 

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