Free‐radical/cationic hybrid photopolymerizations of acrylates and epoxides were initiated using a three‐component initiator system comprised of camphorquinone as the photosensitizer, an amine as the electron donor, and a diaryliodonium salt. Thermodynamic considerations revealed that the oxidation potential of the electron donor must be less than 1.34 V relative to SCE for electron transfer with the photoexcited camphorquinone to take place. This electron transfer leads to the production of the active centers for the hybrid polymerization (two radicals and a cation). Further investigation revealed that only a subset of electron donors that meet the oxidation potential requirement resulted in polymerization of the epoxide monomer; therefore, a second requirement for the electron donor (pKb higher than 8) was established. Experiments performed using a combination of electron donors revealed that the onset of the hybrid system's cationic polymerization can be advanced or delayed by controlling the concentration and composition of the electron donor(s). These studies demonstrate that a single three‐component initiator system can be used to initiate and chemically control the sequential curing properties of a free‐radical/cationic hybrid photopolymerization and is a viable alternative to separate photoinitiators for each type of polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1747–1756, 2005

BACKGROUND: Four common free radical photoinitiators were evaluated for use in thick photopolymerizations illuminated with a medium‐pressure 200 W mercury–xenon arc lamp and a high‐intensity 400 nm light‐emitting diode (LED) lamp. For each photoinitiator/lamp combination, the spatial and temporal evolution of the photoinitiation rate profile was analyzed by solving the set of differential equations that govern the light intensity gradient and initiator concentration gradient for polychromatic illumination. RESULTS: The simulation results revealed that two of the four photoinitiators evaluated were ineffective for photoinitiating thick polymer systems. The photoinitiator bis(2,4,6‐trimethylbenzoyl)‐phenylphosphine oxide, in combination with the 400 nm LED lamp, was shown to be the most efficient photoinitiator/light source combination for photoinitiation of thick systems. CONCLUSION: The results show that some photoinitiators commonly used for photopolymerization of thin coatings are ineffective for curing thick systems. LED light sources provide advantages over traditional mercury lamps, and may have tremendous potential in the effective photoinitiation of thick polymer systems. Copyright © 2008 Society of Chemical Industry

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Thesis Supervisor: Professor Alec B. Scranton 1 Photopolymerizations offer many advantages (such as temporal and spatial control of initiation, cost efficiency, and solvent-free systems) over traditional thermopolymerization. While they are now well-established as the preferred option for a variety of films and coating applications, they are limited from many applications due to problems such as oxygen inhibition, light attenuation, additive interference, and the creation of shadow regions and oxygen pockets due to complex shapes. These problems can be solved by using an underutilized form of photopolymerization--cationic photopolymerization.Cationic photopolymerizations have unique active centers that are essentially nonterminating causing extremely long active center lifetimes. In this contribution, the unique characteristics of cationic active centers are explored for their use in many new applications where previous photopolymerization techniques failed. It was found that the long lifetimes of the active centers permitted them to be very mobile, allowing them to migrate into and polymerize regions that were never illuminated in a process termed shadow cure. The mobility of cationic active centers provides a very efficient means of photopolymerizing of thick and pigmented systems. The long lifetimes of the cationic active centers can be used in the creation of a sequential stage curable polymer system and in the development of novel methods to cure complex shapes, two applications previously unattainable by photopolymerization. The termination of the cationic active centers was found to be reversible and can be used as a technique for external temporal control of the photopolymerization after the illumination has ceased. These abilities have great potential and will allow cationic photopolymerization to be used in many new 2 applications where previous photopolymerization techniques failed, expanding their influence and benefits.Abstract Approved: ______________________________ Thesis Supervisor ______________________________