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Regulating Radical Flux in Frontal Polymerization.

Darya A Ivannikava1, Audrey N McMullin1, Kevin A Stewart1

  • 1Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States of America.

ACS Macro Letters
|April 29, 2026
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Summary
This summary is machine-generated.

Tuning initiator temperature in frontal radical polymerization (FRaP) enables linear polymer formation. This breakthrough allows for solution characterization and deeper understanding of polymerization kinetics and thermal profiles.

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Area of Science:

  • Polymer Chemistry
  • Chemical Engineering
  • Materials Science

Background:

  • Frontal radical polymerization (FRaP) typically yields branched polymers due to rapid flow outcompeting polymerization kinetics.
  • Achieving linear polymer architectures via FRaP under ambient conditions has been a significant challenge.

Purpose of the Study:

  • To investigate the temperature dependence of radical flux in FRaP for linear polymer synthesis.
  • To explore methods for controlling FRaP to enable solution-state characterization and fundamental kinetic studies.

Main Methods:

  • Systematic variation of initiator activation temperature to control radical flux.
  • Development of a multi-initiator system for sequential radical generation.
  • Analysis of thermal profiles and front stability during polymerization.

Main Results:

  • Tuning initiator temperature successfully promoted linear polymer formation, overcoming previous limitations.
  • A multi-initiator approach provided control over radical flux, termination, and thermal profiles.
  • Solution-state characterization of polymers produced via FRaP became feasible.

Conclusions:

  • Initiator selection is a critical parameter for controlling radical flux, front stability, and thermal characteristics in FRaP.
  • This work provides a pathway to synthesize linear polymers using FRaP, enabling advanced characterization.
  • The findings offer deeper insights into the thermo-kinetic principles governing frontal polymerization.