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Controlled Radical Polymerization: from Oxygen Inhibition and Tolerance to Oxygen Initiation

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Abstract

Molecular oxygen is a radical scavenger in both conventional and controlled radical polymerization (CRP), resulting in many time-consuming methods for physically removing oxygen before the polymerization. Different approaches have been developed to have oxygen tolerance by chemically consuming or converting molecular oxygen into non-initiating species to address this issue. Recently, we propose another approach called oxygen initiation that directly transforms molecular oxygen into the initiating carbon radical in CRP. This feature article summarizes our recent developments in this direction. Oxygen-initiated reversible addition-fragmentation transfer (RAFT) polymerization has been successfully conducted using oxygen and trialkylborane as co-initiators under the ambient conditions and atmosphere without any prior degassed procedures. This gas-triggered initiation provides the opportunity for spatiotemporal control of the polymerization by molecular oxygen or air. Rationally synthesized alkylborane compounds could derive the predesigned structure of the initiating alkyl radical to minimize the side reactions and free polymer chains, achieving the synthesis of ultra-high molecular weight polymers. The challenges and perspectives are also discussed in the end.

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Acknowledgments

We thank the financial support from State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University and the National Natural Science Foundation of China (Nos. 21871056, 21704017, and 91956122).

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Authors and Affiliations

  1. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China

    Ning Li & Xiang-Cheng Pan

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  1. Ning Li
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Correspondence to Xiang-Cheng Pan.

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Xiang-Cheng Pan is an associate professor and principal investigator in the State Key Laboratory of Molecular Engineering of Polymers and the Department of Macromolecular Science at Fudan University. In 2014, he obtained his Ph.D. in organic chemistry from the University of Pittsburgh under the guidance of Prof. Dennis P. Curran. He then spent three years of postdoctoral research at the group of Krzysztof Matyjaszewski at Carnegie Mellon University. In 2017, he returned to China and joined Fudan University. The research interest of his group focuses on the development of novel polymerization methods and sustainable polymers.

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Li, N., Pan, XC. Controlled Radical Polymerization: from Oxygen Inhibition and Tolerance to Oxygen Initiation. Chin J Polym Sci 39, 1084–1092 (2021). https://doi.org/10.1007/s10118-021-2597-9

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