Diversity-oriented synthesis of functional poly(trimethylene p-phenylene) through acetoacetate-di(bromomethyl)benzene polymerization

Diversity-oriented polymerization is a powerful synthetic approach for generating diversified polymers with novel structures and advanced functionalities. However, realizing diversity-oriented synthesis in two-component (bimolecular) polymerizations presents a significant challenge. Herein, the two-component polymerizations of alcohol-derived acetoacetates and di(bromomethyl)benzenes were reported to facilely fabricate 14 poly(trimethylene p-phenylene)s showcasing diverse, well-defined structures, high molecular weights (with M_w’s reaching 27.9 kDa), and impressive yields (up to 92 %). These polymers exhibit tailored thermal (T_d,5% exceeding 200 °C) stability and glass transition temperatures ranging from −18 to 50 °C, with the tetraphenylethene-containing variant displaying distinctive aggregation-induced emission (AIE) properties. Notably, the poly(trimethylene p-phenylene) bearing tert-butyl ester groups could be facilely post-modified through sequential hydrolysis and decarboxylation of acetoacetate groups. Thus, this work not only establishes a new diversity-oriented two-component polymerization but also yields a range of poly(trimethylene p-phenylene)s with customizable structures and properties.