Vers de nouveaux systèmes amorceurs pour la photopolymérisation radicalaire et/ou cationique dans des conditions plus respectueuses de l’environnement

摘要

The photopolymerization reaction is used in an increasing number of industrial applications because of the remarkable performance of the process. The photopolymerization reactions require the presence of photosensitive compounds. These latter can absorb light and participate in the photoinitiation through the generation of reactive species. The main objective of this PHD was to develop efficient molecules as photoinitiators (PI) for the free radical photopolymerization (FRP), the cationic photopolymerization (CP) and the free radical promoted cationic photopolymerization (FRPCP). We were interested in new high performance photoinitiating systems (PISs) exhibiting excellent light absorption properties (especially in the visible wavelength range). The photopolymerization must be carried out under soft irradiation conditions (non harmful lamps, low energy consumption and low intensity sources: light-emitting diodes LED). Thus, a novel method involving concomitant radical/cationic photopolymerization in one step was examined. This approach involves the synthesis of interpenetrating polymer networks (IPNs) comprising the specific properties of each polymer. The efforts have been devoted to the development of new compounds with new chemical structures and excellent light absorption properties with high molar extinctions coefficients.Many PISs based on different photoinitiators structures have been developed in this work. The possibility to use dyes having a push-pull character, or dyes being characterized by a polyene or polyaromatic structures were considered. Also, originals xanthenes derivatives sensitive in the visible region have been proposed. In particular, this work has enabled the study of new PISs based on inorganic structures such as polyoxometalates and perovskites. Thus, the possibility to propose new iodonium salts based coumarin could be demonstrated. The best performance was achieved using two-components (PI/Ph2I+) or three-components (PI /Ph2I+/additive) photoinitiating systems under soft irradiation conditions. The kinetics of photopolymerization were evaluated using real time FTIR spectroscopy. The generated radicals were observed using the electron spin resonance (ESR) technique. The laser flash photolysis (LFP) was used as a complementary technique to study the efficiency and the reactivity of radicals generated.