| Abstract: | Poly(vinyl alcohol)‐graft‐poly(1,4‐dioxan‐2‐one) (PVA‐g‐PPDO) with designed molecular structure was synthesized by a solid‐state polymerization. The solid‐state copolymerization was preceded by a graft copolymerization of PDO initiated with PVA as a multifunctional initiator, and Sn (Oct)2 as a coininitiator/catalyst in a homogeneous molten state. The polymerization temperature was then decreased and the copolymerization was carried out in a solid state. The products prepared by solid‐state polymerization were characterized by 1H NMR and DSC, and were compared with those synthesized in the homogeneous molten state. The degree of polymerization (Dp), degree of substitution (Ds), yield and the average molecular weight of the graft copolymer with different molecular structure were calculated from the 1H NMR spectra. The results show that the crystallization process during the solid‐state polymerization may suppress the undesirable inter‐ or intramolecular side reactions, then resulting in a controlled molecular structure of PVA‐g‐PPDO. The results of DSC measurement show that the molecular structures determine the thermal behavior of the PVA‐g‐PPDO. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3083–3091, 2006 |
