Cationic two-photon induced polymerization with high dynamic range

Cationic-induced two-photon photo-polymerization is demonstrated at 710 nm, using an isopropylthioxanthone / diarylidonium salt initiating system for the cationic polymerization of an epoxide. In-situ monitoring of the polymer conversion using interferometry allows for determination of the polymerization threshold J2th, polymerization rate R and its dependence of initiator's concentration z. Best J2th achieved is 1 GW/cm 2 , with a dynamic range of > 100, i.e. the material can be fully polymerized at intensities > 100 times the threshold level without damage. The R is found to be proportional to the m=1.7 power of the intensity, or R =[C(J-J2th)]m =[C(J-J2th)]1.7 , which implies a significantly stronger localization of the photochemical response than that of free radical photoinitiators. Both R and J2th significantly improve when the concentration z of the initiator (onium salt) increases, reduction of J2th exhibiting z -m trend.