TY - JOUR
T1 - Oxygen-enhanced superoxido copper-catalyzed ATRP accelerated by light
AU - Casa, Sina Della
AU - Parkatzidis, Kostas
AU - Truong, Nghia P.
AU - Anastasaki, Athina
N1 - Funding Information:
Athina Anastasaki gratefully acknowledges ETH Zurich for financial support. Nghia P. Truong acknowledges the award of a DECRA Fellowship and DP from the ARC (DE180100076 and DP200100231). Kostas Parkatzidis thanks Onassis Foundation as this scientific paper was partially supported by the Onassis Foundation—Scholarship ID: FZQ051‐1/2020‐2021. Open access funding provided by Eidgenossische Technische Hochschule Zurich.
Publisher Copyright:
© 2023 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC.
PY - 2023/12/1
Y1 - 2023/12/1
N2 - Oxygen-enhanced atom transfer radical polymerization (ATRP) via the formation of a superoxido copper complex, has recently emerged as a powerful tool for the synthesis of well-defined polymers. However, relatively long reaction times (>8 h) were required to reach high monomer conversions. Herein, we explore the influence of light in this new polymerization procedure. Under UV irradiation, a significant enhancement over the polymerization rate was observed resulting in near-quantitative monomer consumption (>90%) within 2 h and narrow molar mass distributions (Đ = 1.07). The rate acceleration was attributed to the fast reduction of the superoxido copper complex to Cu(I)Br under UV irradiation, as confirmed via detailed UV–Vis kinetic experiments. In addition, the induction period was completely eliminated, which is in stark contrast to conventional photo-ATRP (utilizing Cu(II)Br), thus further highlighting the superiority of the presented system. The synergy of the superoxido complex and UV irradiation enabled the synthesis of low-dispersity homopolymers with molecular weights ranging from 6000 to 300,000. The high end-group fidelity of the system was further demonstrated via successful in-situ chain-extensions.
AB - Oxygen-enhanced atom transfer radical polymerization (ATRP) via the formation of a superoxido copper complex, has recently emerged as a powerful tool for the synthesis of well-defined polymers. However, relatively long reaction times (>8 h) were required to reach high monomer conversions. Herein, we explore the influence of light in this new polymerization procedure. Under UV irradiation, a significant enhancement over the polymerization rate was observed resulting in near-quantitative monomer consumption (>90%) within 2 h and narrow molar mass distributions (Đ = 1.07). The rate acceleration was attributed to the fast reduction of the superoxido copper complex to Cu(I)Br under UV irradiation, as confirmed via detailed UV–Vis kinetic experiments. In addition, the induction period was completely eliminated, which is in stark contrast to conventional photo-ATRP (utilizing Cu(II)Br), thus further highlighting the superiority of the presented system. The synergy of the superoxido complex and UV irradiation enabled the synthesis of low-dispersity homopolymers with molecular weights ranging from 6000 to 300,000. The high end-group fidelity of the system was further demonstrated via successful in-situ chain-extensions.
KW - oxygen-enhanced ATRP
KW - photo-ATRP
KW - ppm Cu ATRP
KW - superoxido copper complex
UR - http://www.scopus.com/inward/record.url?scp=85169936381&partnerID=8YFLogxK
U2 - 10.1002/pol.20230479
DO - 10.1002/pol.20230479
M3 - Article
AN - SCOPUS:85169936381
SN - 2642-4150
VL - 61
SP - 3087
EP - 3094
JO - Journal of Polymer Science
JF - Journal of Polymer Science
IS - 23
ER -