Synthesis and polymerization of 2‐alkylanilines

Abstract 2‐Alkylanilines with alkyl groups in the range of 4–15 carbon atoms were synthesized via a known method as well as via a more general path which should allow the introduction of a larger variety of substituted alkyl groups into the ortho position of aniline, e.g., alkenyl or OH, NH2, COOH, and phenyl functionality. Polymerization was found to be achievable according to a method previously described for unsubstituted aniline, i.e., chemically with Cu(ClO4)2 · 6H2O in acetonitrile. Intrinsic viscosities of the obtained poly(2‐alkylaniline)s lay between 0.10 and 0.26 dL/g (97% H2SO4 at 30°C). The dc conductivity of the HCl salts decreased with increasing length of the alkyl side chains from 1 S/cm (polyaniline) over 3 X 10−4 S/cm [poly(2‐butylaniline)] to 1 X 10−6 S/cm poly(tridecylaniline). Further characterization of the polymers were performed by means of UV/VIS/NIR‐and‐IR spectroscopy, in dilute solutions or as KBr pellets, respectively, and by solubility tests.