Polyolefins based crystalline block copolymers: Ordered nanostructures from control of crystallization

In this paper the morphologies and crystallization properties of crystalline block copolymers are reviewed. The equilibrium morphologies expected in crystalline-amorphous diblock copolymers and the different modes of crystallization, such as, breakout, templated crystallization, confined crystallization and pass through crystallization are described. The effects of confinement on crystallization mode and crystallization kinetics are also analyzed in detail. The paper is focused on the morphologies and nanostructures produced in crystalline block copolymers based on polyolefins. Early studies performed on block copolymers containing highly defective polyethylene block, synthesized by hydrogenation of block copolymers containing 1,4-polybutadiene blocks prepared by classic anionic living polymerization, are described in the first part of the paper. Then, the paper features recent advances in the synthesis and characterization of crystalline block copolymers containing stereoregular polyolefins, such as stereoregular polypropylene and linear polyethylene prepared using novel organometallic catalysts able to promote the living and stereoselective polymerization of α-olefins. Strategies for creating nanoscale patters exploiting the ability to induce desired orientations of the crystalline phase through epitaxial crystallization of the crystallizable blocks on crystalline substrates are described. According to this strategy, the desired orientations of the crystalline phase may be suitably designed and act as templates to create the desired final ordered nanostructure.