Cationic grafting from carbon black. VIII. Cationic ring‐opening polymerization and copolymerization of oxepane initiated by acylium perchlorate groups on carbon black

Abstract

Abstract The cationic ring‐opening polymerization of oxepane was found to be initiated by carbon black having acylium perchlorate (CO + CIO ) groups, which were introduced by the reaction of acyl chloride groups with silver perchlorate. It was confirmed that polyoxepane, i.e., poly(oxyhexamethylene), was propagated from CO + CIO groups on carbon black and effectively grafted on the surface. The rate of the polymerization and the percentage of grafting of poly(oxyhexamethylene) remarkably increased by the addition of epichlorohydrin (ECH) as a promoter: the percentage of grafting in the presence of ECH increased to about 100% with an increase in conversion. Furthermore, CO + CIO groups on carbon black have an ability to initiate the cationic ring‐opening copolymerization of oxepane with ECH to give poly(oxepane‐co‐ECH) with various composition. The ring‐opening copolymerization of oxepane with phthalic anhydride was also initiated by CO + CIO groups to give polyether ester, i.e., poly(hexamethylene phthalate) containing poly(oxyhexamethylene) sequence. In the copolymerization, polyether or polyether ester was effectively grafted from carbon black based on the propagation of these polymers from CO + CIO groups.