Achievement of quasi-nanostructured polymer blends by solid-state shear pulverization and compatibilization by gradient copolymer addition

Nanoblends, in which dispersed-phase domains exhibit length scales of order 100 nm or less, are made using a continuous, industrially scalable, mechanical process called solid-state shear pulverization (SSSP). An 80/20 wt% polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend processed by SSSP and consolidated by platen pressing, without melt processing, exhibits a quasi-nanostructured morphology with many irregular, minor-phase domain sizes of ∼100 nm or less. After short-residence-time single-screw extrusion, the pulverized blend exhibits spherical dispersed-phase domains with a number-average diameter of 155 nm. Thus, SSSP followed by certain melt-processing operations can yield nanoblends. However, the pulverized blend exhibits significant coarsening of the dispersed-phase domains during long-term, high-temperature static annealing, indicating that SSSP followed by other melt processes may yield microstructured blends. In order to suppress coarsening, a styrene (S)/methyl methacrylate (MMA) gradient copolymer is synthesized by controlled radical polymerization. When 5 wt% S/MMA gradient copolymer is added to the PS/PMMA blend during SSSP, the resulting blend exhibits a nanostructure nearly identical to that of the blend without gradient copolymer, and coarsening is nearly totally suppressed during long-term, high-temperature static annealing. Thus, SSSP with gradient copolymer addition can yield compatibilized nanoblends. Morphologies obtained in the pulverized PS/PMMA nanoblend are compared with those in blends of PS/poly(n-butyl methacrylate) and PS/high-density polyethylene made using identical SSSP conditions, providing for commentary on the ability of SSSP to produce nanostructured blends as a function of blend components.