Degradation of Poly(methyl methacrylate) in Solution

The rate of degradation of poly(methyl methacrylate) (PMMA) to methyl methacrylate (MMA) was investigated in the liquid phase with toluene as the solvent. The degradation experiments were carried out in a tubular flow reactor at 1000 psig (6.8 MPa) and at four different temperatures (200, 225, 275, and 300 °C). The polymer concentration was varied from 1 to 4 g/L. A discrete model for the first-order rate of polymer degradation was derived and compared to the continuous kinetics approach. Both models lead to the same expression for monomer concentration increasing linearly with time. Rate constants were evaluated using the moments of the molecular weight distributions of the reacted and unreacted polymer. The rate was first order in polymer concentration, and the activation energy was 8.4 kcal/mol (34 kJ/mol). This activation energy suggests that the rate controlling step for the thermal degradation of PMMA is the depropagation process.