Branched polyphosphazenes with controlled dimensions

Using living cationic polymerization, a series of polyphosphazenes is prepared with precisely controlled molecular weights and narrow polydispersities. As well as varying chain length through the use of a living polymerization, amine‐capped polyalkylene oxide (Jeffamine) side chains with varied lengths are grafted to the polymer backbone to give a series of polymers with varied dimensions. Dynamic light scattering and size exclusion chromatography are used to confirm the preparation of polymers with a variety of controlled dimensions and thus hydrodynamic volumes. Furthermore, it is demonstrated how the number of arms per repeat unit, and thus the density of branching, can also be further increased from two to four through using a one‐pot thiolactone conversion of the Jeffamines, followed by thiol‐yne addition to the polyphosphazene backbone. These densely branched, molecular brush‐type polymers on a biodegradable polyphosphazene backbone all show excellent aqueous solubility and have potential in drug‐delivery applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4467–4473