Attempts have been made to synthesize polyphosphazenes with pendent te
rtiary amino side units via macromolecular substitution. Incorporation
of -OCH2CH2N(CH3)(2), -OCH2CH2OCH2CH2N(CH3)(2), and -NHCH2CH2N(CH3)(2
) groups was studied. Polymers in which all the side groups consisted
of one type of aliphatic tertiary amino-containing unit and species th
at also contained 2,2,2-trifluoroethoxy or phenoxy groups as cosubstit
uents were examined. Related phosphazene cyclic trimers were also prep
ared as small molecule model systems to examine synthetic variables, c
haracterization techniques, and hydrolytic behavior. Those phosphazene
s in which the tertiary amino-containing side groups are linked to the
skeleton through an aliphatic oxygen-phosphorus bond are sensitive to
hydrolysis induced by the basicity of the terminal amino group. Howev
er, species in which the tertiary amino-containing units are linked to
the backbone through an alkyl nitrogen-phosphorus bond are stable to
water and are candidate materials for use in a range of membrane and s
urface applications. Small molecule model studies also identified reac
tions of P-Cl bonds in (NPCl2)(3) with N,N-dimethylbutylamine to form
dialkylamino-substituted phosphazenes and hydrolysis products.