Developing property and kinetic control strategies for radiation polymerization

Radiation polymerization is a rapid, sustainable process, requiring no environmentally damaging solvents and less energy than thermal polymerization methods. This process is used extensively each year to produce millions of tons of films, coatings, inks, and adhesives. In this work, kinetic- and property-control strategies were developed for three underdeveloped areas of radiation polymerization: free-radical electron beam (EB) polymerization, free-radical/cationic hybrid photopolymerization, and cationic shadow cure.

Raman spectroscopy, an analytical technique for studying photopolymerization kinetics, was established as a method of determining the conversion of EB-initiated polymer films. This technique, in conjunction with dynamic mechanical analysis (DMA), was used to investigate the impact of chemical structure on the magnitude of EB dose rate effects (DREs). A strong correlation was determined between the DRE magnitude and monomer size, which may be attributed to chain transfer opportunities. A preliminary predictive relationship was developed to estimate the magnitude of the DRE using the property shift caused by changes in dose, enabling scale-up of process variables for polymers prone to dose rate effects. In addition, a protocol was developed to produce films with equivalent energy deposition for both EB and photopolymerizations, allowing the effect of the initiating radiation to be studied. Distinct kinetic and physical property differences were shown in the resulting EB- and photo-initiated films, despite equivalent initiation energies and energy rates. Monomer chemistry was determined to be an important factor in the magnitude of these differences.

In order to control the phase separation that can occur in free-radical/cationic hybrid systems, the cationic AM mechanism was promoted through a hydroxyl group located on the (meth)acrylate, covalently bonding the (meth)acrylate and epoxide networks. The impact of the AM mechanism on the reaction kinetics and physical properties was studied using real-time Raman spectroscopy and DMA to compare a hydroxyl-containing acrylate and methacrylate to non-hydroxyl-containing controls. The promotion of the AM mechanism improved epoxide conversion and network homogeneity. The affect on the (meth)acrylate kinetics correlated to the propagation rate of the neat (meth)acrylate. It was also demonstrated that the glass transition temperature of the hybrid system could be controlled by varying the ratio of (meth)acrylate to epoxide.

Cationic shadow cure, which offers a means of circumventing the light penetration limitations in photopolymerization, was modeled using a central composite design. This model was shown to be predictive of both shadow cure length and gel fraction while varying effective irradiance, exposure time, exposure area, and sample depth. Moreover, the model helped ascertain the impact of each variable and its interactions: shadow cure length was most influenced by sample depth, but the gel fraction was reliant on the other three variables. Active center mobility was also qualitatively tracked, and it was established that the section of solid polymer formed during illumination was restricting the movement of the active centers, preventing complete cure. Through this discovery, a new method of shadow cure was developed, termed transferable shadow cure (TSC). This new method separates the initiation and propagation mechanisms, and, as the name suggests, allows for the active-center-containing monomer to be transferred to areas unreachable by light before solidifying. Conversion of the TSC, as determined via Raman spectroscopy, was also modeled using a central composite design. The model predicts TSC conversion is equally dependent on effective irradiance, sample depth, and exposure time, but independent of exposure area.

Through the development of control strategies in these three areas, this work provides a better fundamental understanding of radiation polymerization, as well as guidelines that aid in product design and technology expansion.