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

Richard Whitfield, Kostas Parkatzidis, Manon Rolland, Nghia P. Truong, Athina Anastasaki

Research output: Contribution to journalArticleResearchpeer-review

70 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)13323-13328
Number of pages6
JournalAngewandte Chemie - International Edition
Issue number38
Publication statusPublished - 16 Sep 2019
Externally publishedYes


  • ATRP
  • block copolymers
  • photochemistry
  • polymerization

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