Controlling Molecular Weight Distributions through Photoinduced Flow Polymerization

Molecular weight distribution plays an important role by giving specific properties to polymeric materials. Despite the recent progress in controlled/“living” radical polymerization, polymer chemists do not have the ability to tune and manipulate the shape of molecular weight distributions (MWDs) (except for a few recent examples). In this article, new synthetic procedures have been developed for controlling MWDs using photoinduced electron/energy transfer–reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, in conjunction with flow processes. By adjusting the pump flow rates, the chemical concentrations and residence times of the reactant streams were tailored throughout the polymerization, leading to control over the MWD. Changes to the intensity and wavelength of the light source also induced changes in the polymerization, allowing alteration of the MWD. The protocols described here should be amenable to a range of polymerization techniques and reaction setups.