Poly(methylenepyridinium)s by Poly(N-alkylation) of Substituted Pyridines: Structural and Kinetic Study

摘要

The solution polymerization of 4-bromomethylpyridine (M1) and 3-bromomethyl pyridine hydrobromides (M2) was studied by NMR spectroscopy. A mechanism involving a series of bimolecular reactions of the monomer, dimer, and higher oligomers closely fits with the experimental variations of bromomethyl end group concentrations with time. M1 presents a higher reactivity than M2 and an unusual behavior, since the oligomers are more reactive than the monomer. An explanation based on a mesomeric phenomenon is proposed. The influence of the anion on the solubility and thermal stability of the poly(methylenepyridinium)s were studied after various anion exchanges. Bis(trifluoromethylsulfonyl)imide anion (Tf2N) yielded the more stable and the more organosoluble polymers.