The low toxicity, biocompatibility and structural similarity to naturally occurring biomacromolecules make phosphorus-containing polymers desired materials for biological and pharmaceutical applications. Poly(oxyethylene phosphonate)s with different macromolecular architecture were synthesized via polycondensation of commercially available dimethyl-H-phosphonates taken in excess to linear and branched poly(ethylene glycol)s. The number average molecular weight of the polymers was established by vapor pressure osmometry, size-exclusion chromatography (SEC) and NMR. The hydrolysis of poly(oxyethylene phosphonate)s at different conditions was studied independently by SEC and 31P NMR. The results showed that at neutral pH the initial concentration of the polymer strongly affects the degree of ensuing hydrolysis (60% higher at 50 mg/mL than at 10 mg/mL). It might be assumed that the observed differences are caused by the concentration-driven changes in the solution behavior and aggregation mechanism of the poly(oxyethylene phosphonate)s. The influence of the poly(oxyethylene) segment length and architecture on the properties of the resulting polymers was studied, as well.
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