Modulation of the Aerobic Oxidative Polymerization in Phenylazomethine Dendrimers Assembling Copper Complexes

The aerobic oxidative polymerization of phenol derivatives can provide poly(phenylene oxide)s, which are known as engineering plastics. This oxidation can be carried out with atmospheric oxygen molecules as the oxidizing reagent in the presence of copper complexes as the catalyst; however, stoichiometric or excess amounts of bases are also generally required. By using a phenylazomethine dendrimer complexed with several equivalent amounts of copper chloride, the additive (base)‐free polymerization of 2,6‐difluorophenol was successful with a very small amount of the catalyst (0.7 mol % of copper for the monomer) because the dendrimer was composed of many Schiff base units, affording a base and catalyst (copper complex) condensed reaction field. The resulting polymer was nearly linear and the molecular weight was very high. When the equimolar amount of the copper complex in one dendrimer molecule was increased, the polymer obtained under this reaction condition was rather branched, resulting in a higher glass transition temperature.