The effect of structural isomerism on block copolymer self-assembly*

The impact of structural isomerism on the self-assembly of block copolymers (BCPs) is generally demonstrated. However, to date, the precise control over structural isomerism of BCPs (SI-BCPs) and a systematic investigation on its effect on thermodynamics have not been fully realized. Here we demonstrate a high throughput platform for a library of well-defined SI-BCPs with identical dispersity and molecular weight. The isomerism is precisely controlled by manipulating the number and position of fluorine atoms of one block. A significant difference in domain periodicities of SI-BCPs was observed. The Flory-Huggins interaction parameter was estimated using self-consistent mean-field theory. The chain conformation of SI-BCPs was measured using scattering techniques. Finally, we believe this systematic investigation of SI-BCPs may lead to a better understanding of the structure-property relationship of polymeric materials and broaden the scope for new polymeric materials.