Todd M. Roper

The kinetics of vinyl acrylate photopolymerization

The photopolymerization of vinyl acrylate has been investigated using real-time FTIR. The acrylate and vinyl groups exhibit different polymerization kinetics with the acrylate functionality polymerizing at a much faster rate. Vinyl acrylate not only self-initiates its own free-radical polymerization, but also photoinitiates the polymerization of mono- and difunctional acrylates. Kinetic studies using a model monomer system indicate that it is essential for the acrylate and vinyl group to be part of the same molecule in order to function as an effective initiator for acrylate polymerization.

Design and Performance of a Thin-Film Calorimeter for Quantitative Characterization of Photopolymerizable Systems

A thin-film calorimeter (TFC) was designed for the quantitative characterization of photopolymerizable systems. A detailed description of its construction indicates the ease with which a TFC can be assembled and the flexibility inherent in its design. The mechanics of operation were optimized to yield a significantly faster instrument response time than other calorimetric methods such as photodifferential scanning calorimetry (photo-DSC). The TFC has enhanced sensitivity, more than an order of magnitude greater linear response range to changes in light intensity than that of the photo-DSC, resulting in the ability to measure both smaller and larger signals more accurately. The photopolymerization exotherm curves are reproducible and can be collected over a broad range of film thicknesses.