Despite
the variety of energetic polyoxetane binders, the oxirane-based
glycidyl azide polymer (GAP) has largely succeeded in the market due
to its advantageous properties. Nevertheless, it suffers from various
drawbacks such as non-uniform chain termination, possible chlorine
content (flame retardant), and toxic epichlorohydrin required for
its synthesis. These problems can be bypassed using the structurally
related poly(3-azidooxetane). Unfortunately, it is only accessible
in moderate yield by polymerization of 3-azidooxetane. Herein, we
describe its synthesis by polymer-analogous transformation using the
new polymers poly(3-tosyloxyoxetane) and poly(3-mesyloxyoxetane) as
precursors. This results in a significantly increased yield and improved
safety as handling of the very sensitive 3-azidooxetane is avoided.
The aforementioned prepolymers were prepared using boron trifluoride
etherate as well as triisobutylaluminum as catalysts. The latter provides
polymers of particularly high molecular weight, and the corresponding
poly(3-azidooxetane) species was obtained and studied for the first
time. In order to shed light on the applicability of poly(3-azidooxetane)
as a GAP substitute, it was thoroughly studied with regard to thermal
behavior, energetic performance (EXPLO5), plasticizer compatibility,
and curing. Moreover, the aquatic toxicity of all involved monomers
was analyzed and compared to epichlorohydrin. Here, poly(3-azidooxetane)
turned out as a fully adequate, if not more environmentally benign,
substitute.