UV polymerizations in the presence of a photobleachable initiator are studied. The photoinitiator concentration vs time and the UV radiation intensity evolution within the sample are calculated according to rate equations. Polymerization and temperature profiles inside the sample are calculated assuming steady-state conditions. Thermal boundary conditions are chosen for orthopedic applications. The polymerization is then investigated under a range of photoinitiation conditions to access the ability to form thick materials. Theoretical results indicate that both cure depth and temperature rise can be controlled through the use of a photobleachable initiator and variation of the initiating UV radiation intensity during the polymerization.

Aldoketenes are well known to undergo fast dimerization and trimerization even at low temperatures but have never been polymerized so far. For the first time, ethylketene, synthesized following the Staudinger procedure modified by McCarney, was polymerized anionically in THF with various initiators, at different temperatures (–40 and –78 °C), and with several monomer/initiator ratios. The resulting polymer was composed exclusively of polyester units, and the initiator did not affect the stereoregularity. Molecular weights up to 24 000 g · mol−1 were obtained with lithium‐based initiators. Transfer reactions and the failure to make block copolymers highlighted a non‐living polymerization. Tg values around –18 °C and thermal stability up to 160 °C were measured. magnified image