Thin-film nanostructure and polymer architecture in semicrystalline syndiotactic poly(p-methylstyrene)-(cis-1,4-polybutadiene) multiblock copolymers

The thin-film morphology of stereoregular syndiotactic poly(p-methylstyrene)-(cis-1,4-polybutadiene) (sP(pMS-B)) multiblock copolymers has been investigated using tapping mode atomic force microscopy with variation of the polymer composition and monomer block lengths. The morphology of the thin films ranges from isolated circular domains of sP(pMS) embedded into a matrix of polybutadiene (PB) to isolated domains of PB embedded into a matrix of sP(pMS), passing through bicontinuous (jagged) lamellae when the pMS concentration is in the range 20-67 mol%. Multiple folding of the polymer segments, i.e. where reciprocal inclusions of polymer segments to each other phase are able to generate greater domain, has been postulated and validated by considerations on the polymer architecture and the thermal and crystalline behaviour. (c) 2019 Society of Chemical Industry