Thermally-induced hyperbranching of bromine-containing polyesters by insertion of in situ generated chain-end carbenes.

Hyperbranched, biodegradable PCL-based polymers are obtained through a random but invasive migration of an in situ generated carbene end group which is unmasked via the thermolysis of its precursor diazirine moiety. These hyperbranched cores are used as macroinitiators for 'grafting-from' polymerisation using controlled radical polymerisation to achieve amphiphilic copolymers which can subsequently be self-assembled into spherical core-shell micelles.