Acceleration of the cationic polymerization of an epoxy with hexanediol

Thin films of 3,4-epoxycyclohexyhnethyl 3',4'-epoxycyclohexane carboxylate were UV irradiated (1.1 J cm(-2)) under isothermal conditions ranging from 0 to 50degreesC. Under these conditions the polymerization advanced quickly but only to a conversion level of less than 10% before the reaction rate slowed by more than an order of magnitude. This drop off in rate was not caused by the glass transition temperature, T-g, reaching or exceeding the reaction temperature, T-rxn, since the epoxide's T-g remained at least 40degreesC below T-rxn. Raising the sample temperature above 60degreesC caused a sharp increase in the conversion level. At 100degreesC conversion exceeds 80% and the ultimate T-g approaches 190degreesC. The addition of 10 mass% 1,6-hexanediol, HD, to the epoxy caused the conversion at room temperature to quintuple over the level obtained without the alcohol present. The heat liberated from this alcohol epoxy blend during cure on a UV conveyor belt system caused the sample's temperature to increase by about 100degreesC above ambient whereas the epoxy alone under these conditions only experienced a modest temperature rise of about 26degreesC. If the amount of HD in the blend is increased above 10% the heat of reaction at 23degreesC decreases due to HD being trapped in a nonreactive crystalline phase. Boosting reaction temperatures above 50degreesC melts the HD crystals and yields significantly improved conversion ratios. As the level of alcohol blended with the epoxy is raised its ultimate T-g is lowered and when the concentration of alcohol in the blend nears 30 mass% T-g drops below room temperature.