Glass transition temperatures of poly(methyl methacrylate) plasticized with low concentrations of monomer and diethyl phthalate



The effect of low plasticizer concentrations on the glass transition temperature of poly(methyl methacrylate) (PMMA) has been studied experimentally for diethyl phthalate (DEP) and methyl methacrylate (MMA) as plasticizers. Volume dilatometry, differential thermal analysis, and a torsional pendulum were used to determine glass transition temperatures. The monomer-plasticized PMMA samples were prepared by polymerizing MMA to a limiting conversion which was found to depend primarily on temperature. At temperatures slightly above the glass transition temperature of a MMA–PMMA system, a polymerization reaction occurred at a rate rapid enough to complicate the interpretation of the dilatometric and differential thermal analysis methods for determining the glass transition temperature. However, the torsional pendulum method could be used since it did not require measurements to be made at temperatures where polymerization could occur. The differential thermal analysis results showed that the temperature at which the polymerization reaction was first detectable was related to the glass transition temperature of the MMA–PMMA solution. The measured glass transition temperatures were compared with the predictions of the theories of Fox, Kelley, and Bueche, and Dimarioz and Gibbs on the effect of plasticizer concentration on the depression of the glass transition temperature.