Highly branched poly(arylene ether)s via oligomeric A2 + B 3 strategies

Qin Lin, Serkan Unal, Ann R. Fornof, Iskender Yilgor, Timothy E. Long

Research output: Contribution to journalArticlepeer-review

30 Scopus citations


Branched poly(arylene ether)s were prepared in an oligomeric A2 + B3 polymerization of phenol endcapped telecholic poly(arylene ether sulfone) oligomers as A2 and TFPPO as trifunctional monomer B 3. The molar mass of the A2 oligomer significantly influenced the onset of gelation and the DB. A high level of cyclization during polymerization of low molar mass A2 oligomers (U3 = 660 and U6= 1200 g · mol-1) led to a high conversion of functional groups in the absence of gelation, and the level of cyclization reactions in the polymerization decreased as the molar mass of the A2 oligomer was increased. The pronounced steric effect in the polymerization of higher molar mass A2 oligomers (U8 = 1800 and U 16 = 3400 g · mol-1) resulted in low reactivity of the third aryl fluoride in the B3 monomer. As a result, only slightly branched (U8=1800 g · mol-1) or nearly linear (U16 = 3400 g · mol-1) high molar mass products were obtained with higher molar mass A2 oligomers. The branched polymers exhibited lower Mark-Houwink exponents and [η] relative to linear analogs, and differences between the branched polymers and linear analogs were less significantas the molar mass of the A2 oligomers was increased due to a decrease in the overall DB.

Original languageEnglish (US)
Pages (from-to)576-586
Number of pages11
JournalMacromolecular Chemistry and Physics
Issue number6
StatePublished - Mar 24 2006
Externally publishedYes


  • A + B polymerization
  • Branched
  • Hyperbranched
  • Poly(arylene ether)
  • Polysulfone

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry


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