Semi-crystalline polymethylene-b-poly(acrylic acid) diblock copolymers: aggregation behavior, confined crystallization and controlled growth of semicrystalline micelles from dilute DMF solution.

In this paper, we have systematically investigated the aggregation behavior, confined crystallization and controlled growth of a novel polyolefin analogue-containing block copolymers (BCPs), i.e., polymethylene-b-poly(acrylic acid) diblock copolymers (PM-b-PAA). On cooling from a homogenous DMF solution at 80 °C, PM-b-PAA was found to crystallize and aggregate with well-defined disk-like micelles. The aggregate behavior and in-plane morphology of PM-b-PAA could be easily controlled by modifying the block ratio, solution pH and solvent composition (DMF-water), by manipulating the crystallization of PM block and the stretching degree of solvated PAA corona. Further investigation of the crystalline feature of PM-b-PAA indicated that the crystallization of PM was retarded by tethered amorphous PAA segments. The crystalline micelle could construct a nano-confined environment with PM folding as the core into a thickness of the mono-layered polyethylene. Finally, when cultured in dilute DMF solution at 50 °C, the initial crystalline micelles, being as self-seeds, could follow a living growth mechanism and develop into single crystals, with well-defined lozenge-shaped morphology.