New functional polyphosphoesters bearing 1,3-dioxolan-2-one and P-H or P-OCH3 groups, or urethane and hydroxyl groups have been synthesized and characterized. Poly(oxyethylene H-phosphonate) was used as precursor polymer. It was reacted with 4-ethenyl-1,3-dioxolan-2-one through the addition of the polymer P-H groups to the double C = C bond of the cyclic carbonate derivative. The non-reacted P-H groups in the product were further transformed into phosphate P-OCH3 groups under Atherton-Todd reaction conditions. The 1,3-dioxolan-2-one functions were also modified via aminolysis affording new polyphosphoester bearing hydroxyuretane fragments in the side chains. It was found that the addition of the P-H group to the carbon double bond of 4-ethenyl-1,3-dioxolan-2-one proceeded in the presence of peroxides while KF and CdI2 did not promote the addition reaction. Structure of the newly synthesized polymers was elucidated by means of NMR and IR spectroscopy studies. (C) 2008 Elsevier Ltd. All rights reserved.