Ring-opening polymerization of various oxirane derivatives using organotin phosphate condensate; Selective synthesis of the polyether containing oxirane ring in the side chain

Abstract

Ring-opening polymerization (ROP) of various oxirane derivatives of the type, 2,2-R¹,R²-CCH₂O [R¹ = H (1), CH₃ (2); R² = CH₃ (a), CH₂Cl (b), CH₂OCH₃ (c)], using organotin phosphate (Bu₂SnO-Bu₃PO₄) condensate has been explored. The ROP of monosubstituted oxiranes (1a-c) afforded ring-opened polymers in high yields (1a, 1c = 99% and 1b = 69%); the resultant polymers from monomers 1a and 1b possessed high molecular weights (M_n = 9.49 × 10⁴, 10.60 × 10⁴, respectively). In contrast, both polymer yields and molecular weights for resultant polymers in the polymerization of disubstituted oxiranes (2a-c) were considerably lower than those in the polymerization of monosubstituted monomers (1a-c). ROP of glycidyl 2-methylglycidyl ether (3) possessing two oxirane groups with different reactivity was thus conducted by organotin catalyst; the high molecular weight polyether (M_n = 9.17 × 10⁴) containing oxirane ring in the side chain has successfully been obtained in moderate yield.