A green
synthesis method for the preparation of polyglycidol in
buffer with a high degree of control is presented. Polymerizations
were conducted in phosphate buffered saline (PBS) of varying pH 3.8,
6.0, and 8.0 and deionized water at temperatures of 60, 80, and 100
°C. Taking advantage of the catalytic reactivity between water
and glycidol afforded a novel green polymerization technique for the
facile synthesis of polyglycidol systems with semibranched architectures
with a degree of branching (DB) of 0.24, which situates the polymers
between purely linear (DB = 0) and hyperbranched (DB = 0.56–0.63)
systems. This method sidesteps the strenuous polymerization conditions
required for most polyglycidol structures and provides well-controlled
and reproducible species with a high degree of linearity and narrow
polydispersities of 1.1–1.2 via the first green and nonexothermic
synthesis of polyglycidol.