This review explores the different synthetic methods by which dispersity and MWD shape can be tuned and discusses the different properties and applications where this variation is beneficial.

Dispersity significantly affects the properties of polymers. However, current methods for controlling the polymer dispersity are limited to bimodal molecular weight distributions, adulterated polymer chains, or low end‐group fidelity and rely on feeding reagents, flow‐based, or multicomponent systems. To overcome these limitations, we report a simple batch system whereby photoinduced atom transfer radical polymerisation is exploited as a convenient and versatile technique to control dispersity of both homopolymers and block copolymers. By varying the concentration of the copper complex, a wide range of monomodal molecular weight distributions can be obtained (Đ=1.05–1.75). In all cases, high end‐group fidelity was confirmed by MALDI‐ToF‐MS and exemplified by efficient block copolymer formation (monomodal, Đ=1.1–1.5). Importantly, our approach utilises ppm levels of copper (as low as 4 ppm), can be tolerant to oxygen and exhibits perfect temporal control, representing a major step forward in tuning polymer dispersity for various applications.

Although dispersity (Đ) plays an important role in controlling polymer properties, there are very few chemical methods that can sufficiently tune it. Here we report a simple, batch, and environmentally benign photoinduced iron-catalyzed ATRP methodology that enables the efficient control of Đ for both homopolymers and block copolymers. We show that by judiciously varying the concentration of the FeBr3/TBABr catalyst, a range of dispersities can be obtained (1.18 < Đ < 1.80) while maintaining monomodal molecular weight distributions. High end-group fidelity was confirmed by MALDI-ToF-MS and was further supported by the efficient synthesis of in situ block copolymers where the dispersity of the second block could be controlled upon demand. Importantly, through the use of low ppm amounts of the catalyst, perfect temporal control could be attained during intermittent “on/off” cycles. This work considerably expands the chemical toolbox for tuning Đ of homo- and block copolymers.

Photo-ATRP has recently emerged as a powerful technique that allows for oxygen-tolerant polymerizations and the preparation of polymers with low dispersity and high end-group fidelity. However, the effect of various photo-ATRP components on oxygen consumption and polymerization remains elusive. Herein, we employ an in situ oxygen probe and UV−vis spectroscopy to elucidate the effects of ligand, initiator, monomer, and solvent on oxygen consumption. We found that the choice of photo-ATRP components significantly impacts the rate at which the oxygen is consumed and can subsequently affect both the polymerization time and the dispersity of the resulting polymer. Importantly, we discovered that using the inexpensive ligand TREN results in the fastest oxygen consumption and shortest polymerization time, even though no appreciable reduction of CuBr 2 is observed. This work provides insight into oxygen consumption in photo-ATRP and serves as a guideline to the judicious selection of photo-ATRP components for the preparation of well-defined polymers.

A facile, high-scale, and versatile technique to prepare biocompatible nanoparticles with tailorable properties from thermoresponsive macro-CTAs and macro-stabilizers.