Macromolecules, Vol.52, No.7, 2642-2650, 2019
Effects of Randomly End-Linked Copolymer Network Parameters on the Formation of Disordered Cocontinuous Phases
Randomly end-linked copolymer networks (RECNs) provide a robust route to cocontinuous nanoscale structures, yielding opportunities to integrate desirable and distinct properties of the constituent materials. In this report, we rely on gravimetric and mechanical analysis of polystyrene (PS)/poly(DL-lactide) (PLA) RECNs to characterize the continuity of both phases as a function of four key network parameters. (1) For symmetric (M-n,M-PS approximate to M-n,M-PLA) RECNs, variations in strand length reveal a critical segregation strength of chi(N-PS + N-PLA) approximate to 11 required for microphase separation, above which the disordered cocontinuous phase spans roughly 30 wt % in composition, with dispersed domains of the minority phase residing on either side. Increasing the strand length above this threshold increases the characteristic d spacing but has little effect on the boundaries of the cocontinuous phase. (2) For asymmetric strand lengths, M-n,M-PS not equal M-n,M-PLA, the d spacing is shifted to adopt the preferred size set by the minority domains, but the breadth and location of the cocontinuous window are not altered. (3) An increase in the dispersity D of PLA strands widens the cocontinuous window and shifts it toward the PLA-rich end of the phase diagram. (4) Finally, an increase in the dispersity in junction functionality f expands the cocontinuous window toward both sides of the phase diagram, yielding an overall width of roughly 45 wt %. The understanding provided on how network parameters influence self-assembly of RECNs offers guidelines for the robust design of cocontinuous nanostructures.