Stereocontrol during photo-initiated controlled/living radical polymerization of acrylamide in the presence of Lewis acids

Poly(acrylamide) (PAM) with controlled molecular weight and tacticity was prepared by UV-irradiation-initiated controlled/living radical polymerization in the presence of dibenzyl trithiocarbonate (DBTTC) and Y(OTf)₃. The rapid and facile photo-initiated controlled/living polymerization at ambient temperature led to controlled molecular weight and narrow polydispersity (M_w/M_n = 1.12-1.24) of PAM. The coordination of Y(OTf)₃ with the last two amide groups in the growing chain radical effectively enhanced isotacticity of PAM. The isotactic sequence of dyads (m), triads (mm) and pentads (mmmm) in PAM were 70.32%, 50.95%, and 29.97%, respectively, which were determined by the resonance of methine (CH) groups in PAM under ¹³C NMR experiment. Factors affecting stereocontrol during the polymerization were studied, including the type of Lewis acids, concentration of Y(OTf)₃, and monomer conversion. It is intriguing that the meso tacticity increased gradually with chain propagation and quite higher isotacticity (m = 93.01%, mm = 86.57%) was obtained in the later polymerization stage (conversion 65-85%).