The development of visible light
3D printing technology and the
preparation of high-tech composites under mild conditions remain a
huge challenge. This article is devoted to the development of dual
thermal/photochemical initiators both for visible light 3D printing
and composite preparation under mild conditions. Dual thermal and
photochemical polymerization initiators are presented, a dual ability
scarcely encountered in the literature. In detail, here, a series
of charge transfer complexes (CTCs) that are demonstrated to be formed
between phosphines (electron donors) and iodonium salt as electron
acceptor are investigated as dual thermal and photochemical free radical
polymerization (FRP) initiators. The CTCs exhibit excellent photo
and/or thermal initiating properties for the benchmarked methacrylate
resin and can be efficiently used for the curing of glass fibers or
carbon fiber composites. To the best of our knowledge, this is the
first access to high-tech carbon fiber composites using dual photo/thermal
initiators. The formations of the CTCs were confirmed by several techniques,
such as 31P NMR, UV–vis, and molecular orbital (MO)
calculations. Laser write experiments at 405 nm show excellent spatial
resolution performances. These systems are commercially available,
stable, and environmentally friendly. Additionally, safer storage
of the thermal initiators is expected (as formed in situ) compared
to traditional thermal initiators (e.g., this is highly worthwhile
for the replacement of peroxides). Dual approaches (photo/thermal
curing) can also be used, as the same initiating system can initiate
both polymerization processes, e.g., fast curing by light of the surface
associated with a dark thermal curing in depth.