Poly(3-azidemethyl-3-methyl oxetane) (PAMMO) is an azide-containing
polymer that has been widely studied, but some problems, such as its
complex synthetic route, high preparation costs, and low elongation,
restrict its practical applications. Therefore, it is of great significance
to design and synthesize an azide polyether that is low in cost, highly
flexible, and has a comparable energy level to that of PAMMO. In this
paper, we synthesized an azide polyether, poly(2-azidemethyl-1,3-dioxolane)
(PADOL), through a simple two-step reaction. The first step was a
cationic ring-opening polymerization using 2-chloromethyl-1,3-dioxane
(CDOL) as a monomer, and the second step was an azidation reaction.
The synthesized PADOL had a controlled molar mass and low dispersity,
and the degree of functionality of the terminal hydroxyl group was
close to the theoretical value. In addition, 3,3-bisazidemethyl oxetane-2-azidemethyl-1,3-dioxolane
random copolymers (PBAMO-ADOLs) were also synthesized using CDOL and
3,3-bischloromethyl oxetane (BCMO) as monomers in the same two-step
reaction scheme discussed above. The copolymerization kinetics showed
that the reactivity ratios of CDOL and BCMO were similar, and the
copolymerization process was close to an ideal copolymerization. When
the ADOL content in the PBAMO-ADOL copolymer was up to 27%, the crystallinity
of the BAMO chain segment was effectively reduced, and an amorphous
azide-containing polymer was obtained. Thanks to the higher oxygen
content and short side chain length, PADOL exhibited a lower glass
transition temperature and viscosity than PAMMO, and the prepared
energetic thermoplastic elastomer (ETPE) had a higher fracture elongation.
Moreover, the higher oxygen content in PADOL promoted the decomposition
of the polymer backbone, resulting in a higher absolute value of the
heat of combustion and lower residual carbon content.