Hyperbranched polyphenylquinoxalines from self-polymerizable AB2 and A2B monomers

A self-polymerizable AB2 monomer, 2,3-bis(4-hydroxyphenyl)-6-fluoroquinoxaline, and an A2B monomer, 2,3-bis(4-fluorophenyl)-6-(4-hydroxyphenoxy)quinoxaline, were prepared and polymerized to afford phenol-terminated and aryl fluoride terminated, hyperbranched polyphenylquinoxalines (HPPQs), respectively. MALDI−TOF analysis showed that intramolecular cyclization was a dominant process for the low molecular weight portion during the polymerizations. After isolation and complete dryness, the phenol-terminated HPPQ 1 was only soluble in strong organic acids, while the aryl fluoride terminated HPPQ 2 was soluble in most common organic solvents. HPPQ 1 was treated with allyl bromide to afford an allyl ether terminated HPPQ 3, which was also soluble in most organic solvents. Intrinsic viscosity measurements and SEC analysis indicated that HPPQ 2 had a much higher Mw and a much broader molecular weight distribution (PDI ∼ 60) than HPPQ 1 and HPPQ 3 (PDI ∼ 4). The results also suggested that HPPQ 1 formed aggregate...