Novel nanostructures from self-assembly of chiral block copolymers.

A diblock copolymer system constituting both achiral and chiral blocks, polystyrene-block-poly(L-lactide) (PS-PLLA), was designed for the examination of chiral effects on the self-assembly of block copolymers (BCPs). A unique phase with three-dimensional hexagonally packed PLLA helices in PS matrix, a helical phase (H*), can be obtained from the self-assembly of PS-rich PS-PLLA with volume fraction of PLLA f PLLAv = 0.34, whereas no such phase was found in racemic polystyrene-block-poly(D.L-lactide) (PS-PLA) BCPs. Moreover, various interesting crystalline PS-PLLA nanostructures can be obtained by controlling the crystallization temperature of PLLA (T(c,PLLA) ), leading to the formation of crystalline helices (PLLA crystallization directed by helical confined microdomain) and crystalline cylinders (phase transformation of helical nanostructure dictated by crystallization) when T(c,PLLA)  < T(g,PS) (the glass transition temperature of PS) and T(c,PLLA)  ≧ T(g,PS) , respectively. As a result, a spring-like behavior of the helical nanostructure can be driven by crystallization so as to dictate the transformation (i.e., stretching) of helices and to result in crystalline cylinders. For PS-PLLA with PLLA-rich fraction (f PLLAv = 0.65), another unique phase, a hexagonally packed core-shell cylinder phase with helical sense (CS*), in which the PS microdomains appear as shells and PLLA microdomains appear as matrix and cores, can be found in the self-assembly of PLLA-rich PS-PLLA BCPs. The formation of those novel phases: helix and core-shell cylinder is attributed to the chiral effect on the self-assembly of BCPs, so we named this PS-PLLA BCP as chiral BCP (BCP*). For potential applications of those materials, the spring-like behavior with thermal reversibility might provide a method for the design of switchable nanodevices, such as nanoscale actuators. In addition, the PLLA blocks can be hydrolyzed. After hydrolysis, helical nanoporous PS bulk and PS tubular texture can be obtained and used as templates for the formation of nanocomposites.