Catalytic Synthesis and Characterization of Biodegradable ...
Catalytic Synthesis and Characterization of Biodegradable ...
Catalytic Synthesis and Characterization of Biodegradable ...
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Chapter 1<br />
1.5.1.2 Polypyrrole (PPy)<br />
Among conducting polymers, polypyrrole is especially promising for commercial<br />
applications because <strong>of</strong> its good environmental stability, facile synthesis, <strong>and</strong> higher<br />
conductivity than many other conducting polymers (Figure 1.5.1B). PPy can be easily<br />
prepared by either a chemical or electrochemical polymerization <strong>of</strong> pyrrole. However, the<br />
synthetically conductive PPy is insoluble <strong>and</strong> infusible. To improve the processibility, many<br />
approaches have been developed. For example, several kinds <strong>of</strong> soluble PPy have been<br />
synthesized, such as poly (3-alkylpyrrole) with an alkyl group equal to or greater than a butyl<br />
group. 102 Poly (3-alkylpyrrole) is easily soluble in common solvents or soluble in water when<br />
the substituents bear hydrophilic groups, such as –SOH3. However, poly (N-substituted<br />
pyrroles) has much lower conductivity due to greatly suppressed conjugation along the<br />
103, 104<br />
polymer chains by the substituents on nitrogen.<br />
1.5.1.3 Poly(thiophene) (PT)<br />
Like polypyrrole, poly(thiophene) is also an important poly(heterocyc1es) (Figure 1.5.1C).<br />
From a theoretical viewpoint, PT has been <strong>of</strong>ten considered as a model for the study <strong>of</strong><br />
charge transport in conductive polymers with a nondegenerate ground state, while on the<br />
other h<strong>and</strong>, the high environmental stability <strong>of</strong> both its doped <strong>and</strong> undoped states has led to<br />
its wide applications. 105 PT is essentially prepared by means <strong>of</strong> two main routes: the chemical<br />
<strong>and</strong> the electrochemical syntheses. Although it is likely that chemical syntheses are the most<br />
adequate methods to prepare oligomers with defined structure, until now, the most<br />
extensively conjugated <strong>and</strong> most conductive PT have been prepared by electrochemical<br />
polymerization. Unsubstituted PT is conductive after doping, but is intractable <strong>and</strong> soluble<br />
only in solutions like mixtures <strong>of</strong> arsenic trifluoride <strong>and</strong> arsenic pentafluoride. 106 However,<br />
examples <strong>of</strong> organic-soluble PT were reported when it was substituted. Nickel-catalyzed<br />
Grignard cross-coupling was used to synthesize two soluble PTs, poly(3-butylthiophene) <strong>and</strong><br />
poly(3-methylthiophene-co-3'-octylthiophene), which could be cast into films <strong>and</strong> doped with<br />
iodine to reach conductivities <strong>of</strong> 4 to 6 S/cm. 107 Hotta et al. synthesized<br />
poly(3-butylthiophene) <strong>and</strong> poly(3-hexylthiophene) electrochemically 108 , <strong>and</strong> characterized<br />
the polymers in solution <strong>and</strong> cast into films. 109 The soluble PATs demonstrated both<br />
thermochromism <strong>and</strong> solvatochromism in chlor<strong>of</strong>orm <strong>and</strong> 2,5-dimethyltetrahydr<strong>of</strong>uran. 110<br />
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