Poly(styrene‐butadiene‐methylmethacrylate) (SBM) and poly(methylmethacrylate‐butyle‐acrylate‐methylmethacrylate) (MAM) triblock copolymers have been dissolved in liquid DGEBA epoxy resin which is subsequently polymerized by meta‐xylene diamine (MXDA) or Jeffamine EDR‐148. A chemorheology study of these formulations by plate‐plate rheology and by thermal analysis has allowed to conclude that the addition of these copolymer blocks improve the reactive rotational moulding processability without affecting the processing time. Indeed, it prevents the pooling of the formulation at the bottom of the mould and a too rapid build up of resin viscosity of these thermosetting systems. The morphology of the cured blends examined by scanning electron microscopy (SEM) shows an increase of fracture surface area and thereby a potential increase of the toughness with the modification of epoxy system. Dynamic mechanical spectroscopy (DMA) and opalescence of final material show that the block PMMA, initially miscible, is likely to induce phase separation from the epoxy‐amine matrix. Thereby, the poor compatibilisation between the toughener and the matrix has a detrimental effect on the tensile mechanical properties. The compatibilisation has to be increased to improve in synergy the processability and the final properties of these block copolymer modified formulations. First attempts could be by adapting the length and ratio of each block.

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