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Abstract Frontal polymerization (FP) of epoxy monomers is typically achieved with a radical‐induced cationic frontal polymerization (RICFP) process that combines a thermal radical initiator with an onium salt superacid generator. In this paper, we show that both thermal and UV‐initiated cationic frontal polymerizations are possible for common epoxy and vinyl ether monomers with only an iodonium superacid generator in the absence of a standalone thermal radical initiator. Increasing superacid generator concentration resulted in an increase in front velocity, as did the addition of vinyl ether to epoxies. The front velocity is reduced by the addition of 4‐methoxyphenol (MeHQ), indicating free‐radicals play a significant role.
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This content will become publicly available on September 15, 2025
Gas‐free initiation for free‐radical frontal polymerization through charge transfer complexes
Abstract Frontal polymerization is a process in which a localized reaction zone propagates through the coupling of thermal transport and the Arrhenius kinetics of exothermic polymerization. Most initiators that have been used produce volatile by‐products, which create bubbles and voids. Tetraalkyl ammonium persulfates have been used but these require synthesis and do not have long shelf lives. A charge transfer complex (CTC) composed of an iodonium salt, and a phosphine compound has been identified as a gas‐free initiator for free‐radical thermal frontal polymerization. This CTC has 4‐(dimethylamino)phenyldiphenly phophine (DMAPDP) as the donor and p‐(octyloxyphenyl)phenyliodonium hexafluoroantimonate as the acceptor (IOC‐8). The CTC was tested with several acrylates, and all were found to support bubble‐free fronts. We determined the CTC mole ratio for some monomers at which the front velocity reaches a plateau.
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- Award ID(s):
- 1946231
- PAR ID:
- 10583809
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Journal of Polymer Science
- Volume:
- 62
- Issue:
- 18
- ISSN:
- 2642-4150
- Page Range / eLocation ID:
- 4148 to 4154
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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