Toward Green Atom Transfer Radical Polymerization: Current Status and Future Challenges

Abstract

Dedicated to Professor Klaus Muellen on the occasion of his 75th birthdayReversible-deactivation radical polymerizations (RDRPs) have revolutionized synthetic polymer chemistry. Nowadays, RDRPs facilitate design and preparation of materials with controlled architecture, composition, and functionality. Atom transfer radical polymerization (ATRP) has evolved beyond traditional polymer field, enabling synthesis of organic-inorganic hybrids, bioconjugates, advanced polymers for electronics, energy, and environmentally relevant polymeric materials for broad applications in various fields. This review focuses on the relation between ATRP technology and the 12 principles of green chemistry, which are paramount guidelines in sustainable research and implementation. The green features of ATRP are presented, discussing the environmental and/or health issues and the challenges that remain to be overcome. Key discoveries and recent developments in green ATRP are highlighted, while providing a perspective for future opportunities in this area.

Atom Transfer Radical Polymerization: A Mechanistic Perspective

“…ATRP can be crucial in the mandatory ecological transition toward a circular plastic economy. , Besides the development of greener polymerization systems, more efforts must be directed toward the preparation of degradable and recyclable polymers via ATRP. Therefore, it is critical to study the reactivity and eventual side reactions of various bioderived monomers and of degradable functionalities or dynamic bonds.…”

“…The relatively low cost and biocompatibility of several robust Fe complexes (e.g., Fe porphyrins or simple Fe halides) 105 makes Fe-catalyzed ATRP a greener alternative to traditional ATRP with Cu catalysts. 106 In Fe-catalyzed ATRP, Fe II species activate alkyl halide initiators or dormant chains, whereas halogenated Fe III species deactivate propagating radicals. Fe-catalyzed ATRP has seen much narrower adoption and mechanistic scrutiny than Cucatalyzed ATRP.…”

Porphyrinbasiertes organisches Netzwerk bestehend aus nachhaltigen Kohlenstoffpunkten für die Photopolymerisation

“…Die Photochemie zeigt ein großes Potential bei der Etablierung neuer Zielsetzungen auf unterschiedlichen Gebieten der Materialsynthese, der Biologie, der Umweltwissenschaften und der fortschrittlichen Fertigung [1–10] . Unter allen Photoreaktionstypen haben jene, welche mit einem Sensibilisator arbeiten, der einen anschließenden photoinduzierten Elektronentransfer ( PET ) eingeht, die größte Bedeutung erlangt [2, 3] .…”

Controllable synthesis and structural design of novel all-organic polymers toward high energy storage dielectrics

“…Polymers with various topologies, such as block, graft, gradient, star, brush, dendrimer and hyperbranched polymers could be synthesized by CRP technology. In addition, CRP is also a commonly used method to modify materials in order to adjust their chemical and physical properties ( Figure 2 ) ( Bagheri et al, 2021 ; Corrigan et al, 2021 ; Gong et al, 2021 ; Zhou et al, 2021 ; Antonopoulou et al, 2022 ; Zhang et al, 2022b ; Li et al, 2022b ; Zhou et al, 2022c ; Corbin and Miyake, 2022 ; Dworakowska et al, 2022 ). ROMP is a relatively new research field in the preparation of polymer materials, which has all the characteristics of olefin metathesis reactions.…”