Influence of reaction conditions on degree of branching in hyperbranched aliphatic polyethers from 3-ethyl-3-(hydroxymethyl)oxetane

The cationic ring-opening polymerization of 3-ethyl-3-(hydroxymethyl)oxetane to form hyperbranched polyethers has been studied. The polymerizations have been performed in bulk using sulfonium salt initiators. To produce polymers of different degrees of branching, the reaction conditions (reaction temperature and initiator) have been varied. Polymerizations have also been performed in the presence of a trifunctional core molecule, trimethylolpropane. The conversion of monomer turned out to be the main factor determining the degree of branching in the resulting polymer. Polymers with degrees of branching ranging from 0.15 to 0.41 were synthesized. When 3-ethyl-3-(hydroxymethyl)oxetane was polymerized by slow addition of monomer to a core molecule, a lower degree of branching was obtained compared to the one-step synthesis with full conversion of monomer. The polydispersity was generally slightly lower when a core molecule was used than in the one-step homopolymerization of 3-ethyl-3(hydroxymethyl)oxetane.