Microphase separation of highly amphiphilic, low polymers by photoinduced copper-mediated polymerization, achieving sub-2 nm domains at half-pitch

The lower limit of domain size resolution using microphase separation of short poly(acrylic acid) homopolymers equipped with a short fluorinated tail, posing as an antagonist 'A block' in pseudo AB block copolymers has been investigated. An alkyl halide initiator with a fluorocarbon chain was utilized as a first 'A block' in the synthesis of low molecular weight polymers (1400-4300 g mol −1 ) using photoinduced Cu( ii )-mediated polymerization allowing for very narrow dispersity. Poly( tert -butyl acrylate) was synthesized and subsequently deprotected to give very low degrees of polymerization ( N ), amphiphilic polymers with low dispersity ( = 1.06-1.13). By exploiting the high driving force for demixing and the well-defined 'block' sizes, we are able to control the nanostructure in terms of domain size (down to 3.4 nm full-pitch) and morphology. This work demonstrates the simple and highly controlled synthesis of polymers to push the boundaries of the smallest achievable domain sizes obtained from polymer self-assembly. Fluoro-polyacrylic acid block copolymers with vary narrow dispersity are shown to have sub-2 nm domain sizes on phase separation.