Hyperbranched polyfluorinated benzyl ether polymers: Mechanism, kinetics, and optimization

Matthew J. Quast, Anja Mueller

Research output: Contribution to journalArticlepeer-review

4 Scopus citations


Highly fluorinated, hyperbranched polymers were synthesized from the polycondensation of AB2 monomers, 3,5-bis[(pentafluorobenzyl)oxy] benzyl alcohol and 3,5-bis[(pentafluorobenzyl)-oxy]phenol with potassium carbonate base, and 18-crown-6 phase transfer agent in a variety of polar aprotic solvents. The regioselectivity of the polymerization was optimized and was found to be temperature dependent. The new polymerization technique produced higher molecular weight polymer using safer conditions than earlier methods. The resulting optimization was used to control substitution of oxygen-bearing nucleophiles along nonactivated fluoroaryl systems in high yield. Water was found to induce side reactions that generate a highly conjugated fluoroaryl phenol with lowered reactivity. The removal of a methylene spacer in the polymer backbone of the hyperbranched polymer produced a polymer with greater thermal stability. The reaction conditions for polymerization were found to be general for nucleophile-bearing perfluorinated systems.

Original languageEnglish
Pages (from-to)985-994
Number of pages10
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number7
StatePublished - Apr 1 2014


  • fluoropolymers
  • hyperbranched
  • kinetics (polym.)
  • polyethers
  • thermal properties


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