Controlling block copolymer one-dimensional self-assembly in polymeric matrices.

The synthesis of one-dimensional (1D) nanostructures in polymeric matrices has become the focus of much research, as the presence of these highly anisotropic domains determines the transport behaviour and mechanical properties of the resulting nanostructured polymers. In this work, 1D PEO nanocrystals were synthesized from polystyrene--polyethylene oxide (PS--PEO) self-assembly in a polystyrene matrix. For this, three different block copolymers (BCP) were employed: L-BCP (PS = 32 000 Da and PEO = 11 000 Da), M-BCP, (PS = 59 000 Da and PEO = 31 000 Da), and H-BCP, (PS = 102 000 Da and PEO = 34 000 Da). The formation of 1D nanocrystals starts with the reaction-induced microphase separation of BCP during styrene photopolymerization at room temperature. Then, as matrix polymerizes, the primary crystalline micelles aggregate epitaxial crystallization by end-to-end coupling. The morphology of the resulting nanocrystals was highly dependent on the BCP employed. While L-BCP self-assembles into 1D ribbon-like nanocrystals, M-BCP macro-phase separates and, H-BCP self-assembles into short disk-like nanocrystals. This dissimilar behavior was mainly associated to the length of the stabilizing corona block. In the case of H-BCP, it was found that 1D self-assembly occurred when the conditions for core thickening were given, that is, when a non-reactive period was introduced in the cure cycle. During such a period, core thickening clears the lateral surface of the nanocrystals, allowing end-to-end coupling. The driving force for crystallization was also modified. An increase in undercooling resulted in an elevated nucleation rate and accelerated crystal growth. This led to a narrower size distribution of shorter 1D nanocrystals. This knowledge will enable the synthesis of customized 1D nanocrystals in a thermoplastic matrix, through the precise selection of the BCP formulation and curing conditions.