Frontal atom transfer radical polymerization of tri(ethylene glycol) dimethacrylate

Abstract

Abstract:The first frontal atom transfer radical polymerization (FATRP) has been successfully carried out using tri(ethylene glycol) dimethacrylate as a monomer. The effect of the catalyst/initiator ratio has been investigated and related to the front velocity and its maximum temperature. By comparing this new approach with classical radical polymerization routes and with conventional frontal polymerization, it was found that the so-obtained polymer is characterized by higher conversion, shorter reaction times, higher degradation temperature, and does not contain entrapped bubbles.

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

“…Free-radical polymerizations are the most common type of frontal systems, with over 80 published reports as of 2022 (refs , , , , − , , − , , − , , − , , , , , , − ). Three distinct mechanistic regimes exist for chain growth radical polymerizations (see the simplified Scheme ).…”

“…Four main ignition categories exist for frontal free-radical polymerizations: thermal (refs , , , , , , , , , − , , , , , − , , , − , − , , , , − , − , , , , , , ), photo (refs − , , , , , , − ), plasma (refs − ), and magnetocaloric (refs , ). Thermal triggering typically involves the use of a soldering iron or oil bath to heat a localized region.…”

“…While the vast majority of radical FP reactions employs organo-radical sources, early work from Bidali et al adapted atom transfer radical polymerization (ATRP) to frontal conditions. ATRP-type reactions involve the use of CuX salts and an organohalide co-initiator (e.g., CBr 4 ) as a means to generate carbon-centered radical species.…”

Frontal Polymerization

“…Frontal polyurethane polymerization [13][14][15], frontal atom transfer radical polymerization [16], and frontal ring-opening metathesis polymerization (ROMP) [17] all suffer from short pot lives: that is, bulk polymerization occurs in less than an hour. In some cases, the only way to avoid even faster bulk polymerization is to cool the reagents.…”

“…16 The front velocity for 1,6 hexanediol diacrylate polymerization as a function of the microcapsule (containing cumene hydroperoxide) size. Fronts of triacrylate polymerization propagating side by side in two dimensions.…”