Document Type


Date of Degree

Spring 2013

Degree Name

PhD (Doctor of Philosophy)

Degree In

Chemical and Biochemical Engineering

First Advisor

Julie L.P. Jessop


Photopolymerization, which uses light rather than heat to initiate polymerization, is a facile technique used to fabricate adhesives, protective coatings, thin films, photo-resists, dental restoratives, and other materials. Epoxide monomers, which are polymerized via cationic photoinitiation, have received less attention in fundamental research in comparison to free radical polymerized acrylate monomers. The characterization of propagation mechanisms, network structures, and physical properties is yet lacking.

This project focused on the reactivity and physical properties of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (EEC), and the kinetic and physical effects of chain transfer agents (CTAs) in EEC based formulations were characterized. This characterization was carried out using real-time Raman spectroscopy, real-time infrared spectroscopy, dynamic mechanical analysis, simple gel fraction measurements, and atomic force microscopy. The effects of water, organic alcohols, processing conditions (e.g., UV light intensity, humidity, post-illumination curing temperature), and photoinitiation systems were investigated.

In general, increasing the concentration of CTAs in a crosslinking epoxide resin increases the rate of polymerization and the overall epoxide conversion level. High CTA levels also correspond to lower glass transition temperatures (Tg) and lower crosslink densities. A post-illumination annealing was critical in obtaining stable physical properties for high Tg epoxide materials. In addition, humidity (water being the most universal contaminant type of CTA) was found to impact the surface properties of an epoxide polymer negatively by reducing the surface hardness.

Hybrid acrylate-epoxide systems are much more complex and unpredictable in curing behavior. The use of hydroxy acrylates in hybrid systems allows for grafting between the epoxide and the acrylate domains, via the AM mechanism. Another intricacy of hybrid systems is the initiation system. In order to maximize the conversion of both the epoxide and the acrylate moieties, the free-radical photoinitiator must not hinder the polymerization of the epoxide monomer. Some very efficient free-radical photoinitiators limit the epoxide polymerization by absorbing the majority of the deep-UV incident photons.

Finally, a renewable acrylate oligomer was synthesized to provide a green alternative to petroleum-based oligomers currently used. The oligomer was freely miscible and readily photopolymerized with a wide range of commercial monomers. The Tg relationship between the commercial monomers and the parent resin followed the Fox equation.

The results of this research provide strategies for controlling epoxide kinetics and physical properties in neat and hybrid systems. This information is useful for tailoring resin formulations to specific end-use applications, especially in films, coatings, and adhesives.

Hybrid epoxide-acrylate photopolymerization affords the unique opportunity to structure polymer networks in time and to engineer advanced material properties. These hybrid systems are based on formulations that contain both an epoxide moiety, which undergoes cationic ring-opening photopolymerization, and an acrylate moiety, which undergoes free-radical photopolymerization. Through the combination of these two independent reactive systems, hybrid polymers exhibit lower sensitivity to oxygen and moisture and offer advantages such as increased cure speed and improved film-forming properties. The ability to design the polymer network architecture and to tune mechanical properties can be realized through control of the cationic active center propagation reaction relative to the cationic chain transfer reaction. Specifically, grafted polymer networks can be developed through the covalent bonding of the epoxide chains to the acrylate chains via hydroxyl substituents. This work demonstrates the formation of these grafted polymer networks and overviews the physical properties obtained through control of hydroxyl content and hybrid formulation composition.


Acrylate, Coating, Epoxide, Glass Transition, Network, Physical Property


xv, 187 pages


Includes bibliographical references (pages 174-187).


Copyright 2013 Brian Frank Dillman