Poly(methyl methacrylate)‐modified epoxy/amine system for reactive rotational moulding: crosslinking kinetics and rheological properties

BACKGROUND: The rotational moulding of thermosetting resins is hampered by their low viscosity and the abrupt increase in their viscosity as they polymerize. This study investigates the use of poly(methylmethacrylate) (PMMA) as a rheological processing aid in reactive blends of an aromatic diepoxy resin (diglycidyl ether of bisphenol‐A, DGEBA) and an aromatic diamine (diethyltoluenediamine, DETDA) by studying the miscibility, curing, rheology, dynamic properties and morphology of the uncured solutions and of the resulting highly crosslinked polymer blends. RESULTS: The PMMA was miscible in the uncured resins as expected from consideration of their solubility parameters, and the effect of PMMA concentration on the glass transition temperature, measured via differential scanning calorimetry (DSC), was fitted to several models. Addition of PMMA significantly increased the viscosity of the uncured blend which obeyed the log‐additivity rule. The curing behaviour was monitored using DSC, infrared spectroscopy and dynamic rheology and it was found that addition of PMMA caused a small reduction in rate due to a dilution effect. The dynamic and steady shear rheologies were used to determine the gel point and gel relaxation index. Dynamic mechanical thermal analysis provided evidence for phase separation of the components into PMMA‐rich domains and an epoxy‐rich matrix and this was confirmed with electron microscopy studies. CONCLUSION: These results indicate that addition of small amounts of PMMA to DGEBA/DETDA enlarges the processing window with regards to the rotational moulding of thermosets. In addition, the blending of small amounts (ca 10 wt%) of PMMA with the DGEBA/DETDA resin appears to cause only a modest sacrifice in thermal resistance. Copyright © 2009 Society of Chemical Industry