Study on aqueous polymerizations of vinyl monomers initiated by metal oxidant–chelating agent redox initiators

Wen‐Cheng ‐C Hsu, Jen‐Feng ‐F Kuo, Chuh-Yung Chen

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Abstract

In this study, a series of chelating type reductants containing redox pairs were tested as the initiator for aqueous polymerizations. The redox pairs consist of Ce(IV) or several first‐row transition metals coupled with chelating agents of amino acids, dibasic acids, or diamine. The initial rates and limiting conversions of acrylamide polymerization initiated by those redox pairs were determined. The reductive reactivity of the chelating agents with Ce(IV) and the oxidative half‐wave potential of Ce(III)‐chelating agent/Ce(IV)‐chelating agent were measured to evaluate the feasibility of these redox pairs as initiators. After the evaluation, the redox pairs other than Ce(IV)‐amino acid type chelating agent were precluded to be promising initiators for aqueous polymerizations. Those Ce(IV)‐amino acid type chelating agent redox pairs which could form at least two five‐ or six‐membered rings were found to be potential initiators. The Ce(IV)‐NTA pair was the most promising one. The mechanism of initiation of the redox pairs was proposed and further confirmed by the 13C‐ and 1H‐NMR spectra of NTA‐terminated polyacrylamide. The complex formation constants (K) and disproportionation constants (kd) of the Ce(IV)‐amino acid type chelating agent redox initiators for acrylamide polymerization were evaluated. The factors governing the parameters of chelated complexes and the performance of polymerizations were discussed. These redox pairs were also used as the initiators for aqueous polymerizations of acrylic acid and acrylonitrile. © 1993 John Wiley & Sons, Inc.

Original languageEnglish
Pages (from-to)3213-3222
Number of pages10
JournalJournal of Polymer Science Part A: Polymer Chemistry
Volume31
Issue number13
DOIs
Publication statusPublished - 1993 Jan 1

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All Science Journal Classification (ASJC) codes

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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