The synthesis of well-defined polystyrene-g-Nylon 6 copolymers is described. The materials were prepared for study of their rheological behaviour and to compare it with the recent findings for 2-phase block copolymer systems. The anionic polymerization of ϵ-caprolactam in the presence of polystyrene-ethyl acrylate copolymer was chosen as the preparative route. The reasons for the choice were (1) the fact that ester groups are known to be good initiators for the lactam polymerization and (2) that it has been previously established that uniform copolymers can be obtained from styrene and acrylate esters. The present paper describes initial results on preparation and characterization of graft copolymers. It was found that cross-linked materials resulted when the polystyrene copolymer contained more than 1 per cent by weight of ethyl acrylate. At lower ester concentrations, soluble and thermoplastic materials were obtained. The cross-linking reaction was tentatively identified as arising from the presence of the tertiary hydrogen alpha to the ester group. In agreement with this postulate, methacrylate copolymers produced soluble, thermoplastic grafts at concentrations as high as 5 weight per cent. The mechanical properties and the modulus-temperature behaviour of the 2-phase graft copolymer systems are also presented.
