4.7 Article

Radical homopolymerization of tetrafluoroethylene initiated by perfluorodiacyl peroxide in supercritical carbon dioxide: Reaction mechanism and initiation kinetics

Journal

EUROPEAN POLYMER JOURNAL
Volume 48, Issue 8, Pages 1431-1438

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.eurpolymj.2012.05.012

Keywords

Perfluorodiacyl peroxide; Polytetrafluoroethylene (Ptfe); Supercritical carbon dioxide; Reaction mechanism

Funding

  1. 12th 5-year National Key Technologies R&D Program of China [2011BAE08B00]
  2. National Science Foundation of China [21104044]
  3. Shandong Provincial Natural Science Foundation of China [ZR2009FM057]
  4. Ph.D. Programs Foundation of Ministry of Education of China [20110073120040]
  5. Shanghai Leading Academic Discipline Project [B202]

Ask authors/readers for more resources

Radical homopolymerizations of tetrafluoroethylene (TFE) in supercritical carbon dioxide (sc-CO2) initiated by bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP) were conducted. Low molecular weight polytetrafluoroethylenes (PTFEs) which are widely used in diverse fields with stable end groups were successfully obtained. PTFEs were characterized by solid-state F-19 NMR and FT-IR spectroscopy. From rational assignment of the characteristic signals, an overall reaction mechanism explaining the homopolymerization processes is proposed. The carboxyl radicals resulted from thermal decomposition of BPPP were completely decarboxylated to n-C3F7OCF(CF3). before reacting with TFE. Additionally, a small amount of n-C3F2OCF(CF3) rearranged into n-C3F7. with decreased rearrangement fraction from 0.11 to 0.04 when the reaction temperature was lowered from 35 to 5 degrees C. Initiation rate constants (k(d)) were slightly increased with elevated pressure. The initiation activation energy derived from k(d) is 90.3 kJ mol(-1) which is much lower than those of the other systems where nonfluorinated diacyl peroxides are used. Such mechanism and kinetics insights into the homopolymerizations of TEE in sc-CO2 will be instructive for the syntheses of fluoropolymers with desired properties in future. (C) 2012 Elsevier Ltd. All rights reserved.

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