Well-defined benzoxazine/triphenylamine-based hyperbranched polymers with controlled degree of branching

Well-defined thermally polymerizable hyperbranched polymers (TPA–BZs) containing various numbers of triphenylamine (TPA) and benzoxazine (BZ) units have been prepared using a “click-like” reaction concept, through one-pot Mannich condensations of 4-(bis(4-aminophenyl)amino)phenol (TPA–2NH(2)–OH, as the AB(2) branching groups), aniline (as the focal groups), CH(2)O, and phenol in 1,4-dioxane, with a unique feeding approach. Two design strategies for the chemical construction were applied: (i) simple hyperbranched TPA–BZs, such as those containing one or three TPA units, developed from the focal or the terminal group direction to form the resultant monomers; (ii) three dendritic TPA–BZs containing four TPA units possessing different degrees of branching (DBs) for the conformation study. The exothermic temperature for the dendritic TPA–BZs decreased upon increasing the DB. The bathochromic shifts of the dendritic TPA–BZs increased upon increasing the number of TPA units, in UV-Vis absorption and PL emission spectra, presumably because of an increase in the effective conjugation length. In addition, the polymerized dendritic TPA–BZ DG1 possessed thermal properties superior to those of the hyperbranched TPA–BZ polybenzoxazines, possibly because the segmental mobility in the polymer network was restricted by the dendrimer core group and because of its symmetrical construction. The hyperbranched TPA–BZ possessed unique photophysical properties, suggesting potential applications in optoelectronic devices.