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Conventional and controlled radical polymerization redox-initiated by Cerium(IV) and Acrylamide as an intrinsically reducing inimer: a facile strategy to branched polyacrylamide

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Abstract

Since cerium(IV) ammonium nitrate (CAN) could oxidize amidyl N–H moieties into nitrogen-centered radicals under proper conditions to initiate radical polymerization, CAN-acrylamide (AAm) redox-initiated radical homo/co-polymerization in a conventional or controlled manner was exploited with AAm as an intrinsically reducing inimer. CAN oxidized AAm to initiate conventional radical homopolymerization at 50–60 °C, and viscosity-average molecular weight (MW) of polyacrylamide (PAAm) steadily increased with conversion because of the oxidation of amidyl N–H moieties of in-chain -AAm- units, but MW was in a range from 104 to 105. CAN-AAm redox-initiated radical co-polymerization of N,N-dimethylacrylamide (DMAAm) proceeded readily under optimized conditions and formed PAAm-co-PDMAAm with MW in a range from 105 to 106, and increasing simultaneously with conversion. CAN-AAm redox-initiated controlled radical homopolymerization was performed with FeCl3 complexes as the deactivator, and the polymerization proceeded in a mechanism of reverse atom transfer radical polymerization (ATRP) and MW of PAAm increased in proportion to conversion. The PAAm chains contained a C–Cl terminal, which was confirmed by block co-polymerization with DMAAm via standard ATRP with PAAm as the macro-initiator.

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Acknowledgement

This work was supported by the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

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Authors and Affiliations

  1. Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials, School of Materials Science and Engineering, Changzhou University, Changzhou, 213164, China

    Yiwen Sun & Guangqun Zhai

  2. Jiangsu Collaborative Innovation Centre of Photovoltaic Science and Engineering, Changzhou University, Changzhou, 213164, Jiangsu, China

    Yiwen Sun

  3. National Experimental Demonstration Center for Materials Science and Engineering, Changzhou University, Changzhou, 213164, P.R. China

    Guangqun Zhai

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  1. Yiwen Sun
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Correspondence to Guangqun Zhai.

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Sun, Y., Zhai, G. Conventional and controlled radical polymerization redox-initiated by Cerium(IV) and Acrylamide as an intrinsically reducing inimer: a facile strategy to branched polyacrylamide. Polym. Bull. 79, 1751–1765 (2022). https://doi.org/10.1007/s00289-021-03587-z

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  • DOI: https://doi.org/10.1007/s00289-021-03587-z

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