Kinetics, Characterization, and Applications in the Development of Next-Generation Cure-on-Demand Polymeric Materials through Frontal Polymerization

Frontal polymerization (FP) is a process in which a front propagates in a localized reaction zone converting monomer into polymer. This work explored the kinetics and applications of FP for the development of cure-on-demand materials. The kinetic effects of fillers on frontal polymerization have not been thoroughly explored. In Chapter 2, various fillers were used, and their effects on front velocity and front temperature were determined. Clay minerals are primarily used, but the thermal conductive effects of milled carbon fiber were also explored. It was found that some fillers inhibit frontal polymerization through radical scavenging, while others increased the front velocity through thermal effects. Non-skid coatings are applied to the decks of marine vessels to provide both an anti-slip surface and corrosion protection. In Chapter 3, a base formulation for a one-component cure-on-demand coatings based on frontal polymerization was developed and studied. The coating is based on free-radical polymerization of acrylates and cures within minutes with the use of an infrared heater. In Chapter 4, the base formulation was applied as a non-skid coating engineered for a cure-to-service within minutes after cure initiation. The extended pot life and ability to selectively cure the coating will reduce waste, prevent error due to short working times, and improve operational availability by reducing the downtime from long cure-to-service times. The performance of the coating showed high value and potential application to marine vessels. Potential ways to improve the current non-skid coating are also discussed. Charge Transfer Complexes (CTCs) based on electron donor and acceptor interactions have been shown to act as dual thermal and photoinitiators. The first study done using charge transfer complexes as thermal initiators in frontal polymerization is presented in Chapter 5. Various iodonium salts and amines were explored as electron acceptors and donors, respectively. The mole ratio of the iodonium salt to the amine, steric effects, and electronic effects were explored. It was found that the front velocity reached a maximum at a certain mole ratio of amine to iodonium salt. The relationship between the type of iodonium salt and front velocity was also explored. Chapter 6 concludes the work