Solution Self-Assembly of Blends of Crystalline-Coil Polyferrocenylsilane-block-polyisoprene with Crystallizable Polyferrocenylsilane Homopolymer

The self-assembly of block copolymers in solution leads to micellar structures with various morphologies. One way to modify the morphology of these micelles is to blend the block copolymer with a homopolymer corresponding to the core-forming block. Although the self-assembly of blends of amorphous homopolymers and block polymers has been extensively studied, there are few examples of solution self-assembly of blends of a core-crystalline block copolymer with a semicrystalline homopolymer. Here we describe a systematic study of the assembly in decane of blends of a polyferrocenylsilane- block -polyisoprene sample (PFS 48 - b -PI 264 ) with two different PFS homopolymer samples (PFS 50 and PFS 20 ). We examine the structures formed as a function of blend composition and compare them to the structures formed from the individual components. PFS 48 - b -PI 264 itself forms long cylindrical micelles, while the two homopolymer samples form stacks of lamellar crystals. Self-assembly of block copolymer mixtures leads to structures with an elongated planar core and fiber-like protrusions from the ends. The details of the structure vary in an interesting and systematic way as the ratio of homopolymer/block copolymer is increased, with important differences seen for the PFS50 and PFS20 homopolymer samples. This study demonstrates that cocrystallization plays a crucial role in determining the structures formed from these mixtures.