Self-doped polymers polyaniline

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... 

The various ring-substituted PANI systems include one that embodies the concept of self-doping sulphonated polyaniline (SPAN). In SPAN, about half the number of phenyl rings of emeraldine salt arc monosubstituted with an — SOj" group (Yue et al. [327]). This polymer is x-ray amorphous, as is its de-protonated, non-conductive salt form obtained upon dissolution of... 

As the degradation of polyaniline occurs via an imine intermediate [281,284], Kim et al. [285] prepared self-doped polymer by alkylsulphonate substitution in the polymer backbone, Besides self-doping for a facile redox process, the perceived advantage of this bulky substituent includes the protection of nitrogen centres from nucleophiles responsible for irreversible degradation of polyaniline. Poly(aniline N-butylsulphonate) retained its reversible electrochromic response up to 150 000 cycles when scanned between its oxidized and reduced states (between 0.2 and 0.5 V) then started diminishing slowly. The excellent redox cyclability of poly(aniline N-butylsulphonate) over unsubstituted polyaniline was also confirmed by chronoabsorptom-etry by Kim et al. [285],... 

Soluble conducting polymers can be solvent cast to form coatings. The addition of appropriate substituents to the polymer backbone or to the dopant ion can impart the necessary solubility to the polymer. For example, alkyl or alkoxy groups appended to the polymer backbone yield polypyrroles [117,118], polythiophenes [118], polyanilines [119,120], and poly(p-phenylenevinylenes) [97] that are soluble in common organic solvents. Alternatively, the attachment of ionizable functionalities (such as alkyl sulfonates or carboxylates) to the polymer backbone can impart water solubility to the polymer, and this approach has been used to form water-soluble polypyrroles [121], polythiophenes [122], and polyanilines [123]. These latter polymers are often referred to as self-doped polymers as the anionic dopant is covalently attached to the polymer backbone [9]. For use as a corrosion control coating, these water-soluble polymers must be cross-linked [124] or otherwise rendered insoluble. 

Han et al. [79] reported preparation of highly conductive and thermally stable, self doping propylthiosulfonated polyanilines. The polymer was illustrated as follows ... 

Structural modifications of polyaniline have mainly been exploited to achieve improved processability and environmental stability. In general, the substituted polyanilines can be obtained via oxidative polymerization of the corresponding monomer. However, inductive and steric effects can make such monomers difficult to polymerize [42]. Several substituted polyanilines have been prepared by varying the nature (alkyl, alkoxy, halogen, etc.) and the position (2- vs 3-, 5-positions) of the substituent [24, 27-32, 34, 37, 43, 44]. These studies have shown that regardless of the nature and position of the substituent group, there is an adverse effect on polymerization and the properties of the polymer such as conductivity and electroactivity. To overcome these limitations, various synthetic methods have been developed to prepare self-doped sulfonated polyanilines. These methods involve controlled postpolymerization modifications by synthetic reactions on the whole polymer and copolymerization of less reactive monomers with aniline as described below. 

The discovery of self-doped polyanilines was a major breakthrough in the field of conducting polymers due to their desirable properties such as water solubility, pH and temperature independent conductivity, redox activity over a wider pH range and thermal and environmental stability. These polymers can be prepared chemically and electrochemically by various methods discussed in the above sections 2.2-2A. The distinctive properties of self-doped sulfonated polyanilines are discussed in this section. 

Similarly, self-doped PABA can be prepared using excess of saccharide and one equivalent of fluoride to monomer. Complexation between saccharides and aromatic boronic acids is highly pH dependent, presumably due to the tetrahedral intermediate involved in complexation [25]. Because the pKa of 3-aminophenylboronic acid is 8.75, complexation requires pH values above 8.6. This pH range is not compatible with the electrochemical synthesis of polyaniline, which is typically carried out near a pH value of 0. However, Smith et al. have shown that the addition of fluoride can stabilize the complexation of molecules containing vicinal diols with aromatic boronic acids [23]. Based on this work, it was postulated that the electrochemical polymerization of a saccharide complex with 3-aminophenylboronic acid in the presence of one molar equivalent of fluoride at pH values lower than 8 is possible if a self-doped polymer is produced in the process. 

Figure 3.24 shows the redox behavior of PABA thin films observed at neutral pH in the presence of NADH and NAD" ". The PABA film was redox inactive at neutral pH (Figure 3.24,a) due to deprotonation and loss of dopant as with polyaniline [150,151). However, in the presence of NADH (Figure 3.24, b) and NAD" " (Figure 3.24, c), PABA films became redox active due to complexation of boronic acid with cis-2,3-ribose diols and subsequent formation of self-doped polymer. In the presence of NADH, the cyclic voltammogram of PABA thin film exhibited a single redox couple at pa 0.05 and pc —0.10 V. In contrast, a second redox couple was observed in the presence of NAD+ at pa 0.34 and pc... 

Malinauskas et al. have used an in situ Raman spectroelectrochemical technique to study the degradation kinetics of self-doped sulfonated polyaniline. When a positive potential (-1-0.9 V vj. Ag/AgCl) was applied to the polymer in a solution (pH ranging from 0.5 to 9), the intensity of Raman bands decreases with time due to electrochemical degradation of polymer, and the rate of which increased with decreasing pH. 

Sulfonation of emeraldine base produces ring-substituted polyaniline. The ring-substituted polyaniline is self-doped and offers solubility in basic aqueous solutions [17,18]. The key feature of this self-doped polymer is its ability to maintain its conductivity up to pH 7, while the unsubstituted polyaniline is converted to an insulator at pH greater than about 4. 

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