Morphological Stabilization of Block Copolymer Worms Using Asymmetric Cross-Linkers during Polymerization-Induced Self-Assembly

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Block copolymer worm stabilization via cross-linking during polymerization-induced self-assembly (PISA) is challenging. This is because block copolymer worms typically occupy a narrow regime in the phase diagram, and in situ cross-linking may hinder a morphological transition from sphere to worm. In this work, in situ cross-linking of block copolymer worms during PISA was studied using three different asymmetric cross-linkers, each bearing a pair of double bonds with different reactivities. Specifically, ethanolic PISA syntheses targeting poly(2-(dimethylamino)ethyl methacrylate)- b -poly(benzyl methacrylate) diblock copolymer worms were investigated in the presence of vinyl methacrylate, allyl methacrylate, or 4-allyloxybenzyl methacrylate. The copolymerizations of benzyl methacrylate with the asymmetric cross-linkers underwent progressive branching to finally cross-linking of the block copolymer worms. While all the three asymmetric cross-linkers were able to cross-link worms, 4-allyloxybenzyl methacrylate with a structure mimicking benzyl methacrylate showed the best results with minimal perturbation to the worm morphology.