Tuning Dispersity by Photoinduced Atom Transfer Radical Polymerisation: Monomodal Distributions with ppm Copper Concentration

• Published in: Angewandte Chemie International Edition 2019-09, Vol.58 (38), p.13323-13328
• Main Authors: Whitfield, Richard, Parkatzidis, Kostas, Rolland, Manon, Truong, Nghia P., Anastasaki, Athina
• Format: Article
• Language: English
• Subjects: Accuracy; ATRP; Block copolymers; Control methods; Coordination compounds; Copper; Copper compounds; Dispersion; Molecular weight; photochemistry; Polymerization; Polymers; Reagents; Tuning
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201906471

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. Tuning molecular weight distributions can substantially affect the properties of synthesised polymeric materials. Photoinduced atom transfer radical polymerisation (photo‐ATRP) was used to control the dispersity of homopolymers and block copolymers by varying the concentration of copper complex. A wide range of monomodal molecular weight distributions are obtained where Mn and Mw can be tuned upon demand.