Role of Branching Architecture on the Glass Transition of Hyperbranched Polyethers

The influence of branching architecture on the glass transition of hyperbranched polyethers has been investigated. For amorphous samples, the glass transition temperature (T-g) first increases with the degree of branching (DB), passes through a maximum, and then decreases sharply. An attempt is made to explain this by the competition between the junction density and the free volume of terminal units. For the crystalline samples, the crystallization of polymer chains makes the relationship of DB and T-g more complicated. By the introduction of branching architecture, the crystallization ability of the branched polymer is weakened gradually. When the samples are isothermally crystallized for a long time, the T-g of polyethers decreases monotonically with DB.