Controlled synthesis of ABCA' tetrablock terpolymers

•ABCA' tetrablock terpolymer syntheses with independently controlled Mn of each block.•Optimized processing conditions to avoid chain cross-linking or degradation.•TEM and AFM evidence of polymers with non-spherical domains.

Polystyrene-block-polyisoprene-block-polylactide-block-polystyrene tetrablock terpolymers were synthesized via sequential anionic, ring-opening, and reversible addition-fragmentation chain-transfer polymerizations. The optimized synthesis of these ABCA' tetrablock terpolymers yields polymers with low molar mass dispersity and allowed for straightforward and independent tuning of the Mn for each block. We determined that careful processing of these polymers was necessary to avoid deleterious side reactions during solvent casting or annealing. Preliminary microscopy data demonstrated the ability of these polymers to form non-spherical domains of the B and C blocks. The 26 tetrablock terpolymers synthesized will enable detailed studies of the ABCA' morphological map.

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