Xanthate-supported photo-iniferter (XPI)-RAFT polymerization: facile and rapid access to complex macromolecules.

Xanthate-supported photo-iniferter (XPI)-reversible addition-fragmentation chain-transfer (RAFT) polymerization is introduced as a fast and versatile photo-polymerization strategy. Small amounts of xanthate are added to conventional RAFT polymerizations to act as a photo-iniferter under light irradiation. Radical exchange is facilitated by the main CTA ensuring control over the molecular weight distribution, while xanthate enables an efficient photo-(re)activation. The photo-active moiety is thus introduced into the polymer as an end group, which makes chain extension of the produced polymers possible directly by irradiation. This is in sharp contrast to conventional photo-initiators, or photo electron transfer (PET)-RAFT polymerizations, where radical generation depends on the added small molecules. In contrast to regular photo-iniferter-RAFT polymerization, photo-activation is decoupled from polymerization control, rendering XPI-RAFT an elegant tool for the fabrication of defined and complex macromolecules. The method is oxygen tolerant and robust and was used to perform screenings in a well-plate format, and it was even possible to produce multiblock copolymers in a coffee mug under open-to-air conditions. XPI-RAFT does not rely on highly specialized equipment and qualifies as a universal tool for the straightforward synthesis of complex macromolecules. The method is user-friendly and broadens the scope of what can be achieved with photo-polymerization techniques.