Polymerization of 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane. Kinetics and polymer microstructure

The polymerization of 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane (1), initiated with aluminium triisopropanolate in CH2Cl2 as solvent, was studied. Under the chosen conditions one molecule of initiator produces one polymeric chain. At low conversion exclusively linear chains of poly[oxy(methoxyphosphoryl)oxyethylene] [poly(1)] are formed. Later, chain transfer to polymer leads to extensive branching. Kinetic studies strongly indicate propagation on covalent active species. Rate constants of initiation and propagation, found from non‐stationary kinetics at 25°C, are equal to 6,5 · 10−3 mol−1 · 1 · s−1 and 4,5 · 10−1 mol−1 · 1 · s−1, respectively.