Polyphosphazenes with Glucosyl and Methylamino, Trifluoroethoxy, Phenoxy, or (Methoxyethoxy)ethoxy Side Groups

Four new types of polyphosphazenes have been synthesized that bear α-D-glucosyl side groups together with methylamino, trifluoroethoxy, phenoxy, or (methoxyethoxy)ethoxy cosubstituent groups. The formulas are [NP(Gl)_x(NHM_y),]n, [NP(Gl)_x(OCH₂CFs),]n [NP(Gl)_x(OPh)_y]_n, and [NP(G1)_x(0CH₂CH₂OCH₂-CH₂OCH₃)_y]_n, where Gl = α-D-glucosyl, χ + y = 2, and n ≈ 15 000. The syntheses were accomplished by the following sequence of reactions. First, the sodium salt of diacetone D-glucose or the cosubstituent nucleophile was allowed to react with poly(dichlorophosphazene) to generate an intermediate of formula [NP(di-A-Gl)_xCly]_n or [NPCl_xOR)_y,]_n, with the ratio of _χ to _y being determined by the ratio of the reactants. Second, the cosubstituent (NHR, OR, or di-A-Gl) was introduced by replacement of the remaining chlorine by reaction with methylamine or the appropriate alkoxide or aryloxide. Finally, the protecting groups on the glucosyl residues were removed by treatment with acid. A wide range of ratios of χ to y was explored, and the resultant polymers were studied with respect to solubility in water, hydrophilicity or hydrophobicity, cross-linking by γ-radiation or chemical reagents, and stability to hydrolysis. The new macromolecules offer a range of possibilities for utilization in membranes, hydrogels, biomaterials, and bioerodible polymers.