Synthesis and characterization of poly(4-vinylpyridine)-block-poly(2,2,2-trifluoroethyl methacrylate) for manipulating periodic nanostructured architectures

Designing appropriate molecular structures is essential for employing the microphase-separated structures of block copolymers in a wide range of applications. This study selected poly(4-vinylpyridine)-block-poly(2,2,2-trifluoroethyl methacrylate) (P4VP-b-PTFEMA) owing to its strong repulsive interactions originating from the fluorine in PTFEMA and its compatibility with additives through P4VP. Thirty distinct P4VP-b-PTFEMA block copolymers with varying compositions were synthesized using reversible addition-fragmentation chain-transfer polymerization. d-spacings of 8.9–59.7 nm were obtained, highlighting the successful preparation of microphase-separated structures with various sizes. Additionally, the introduction of resol as a cross-linking agent, which selectively interacts with P4VP, significantly changed the microphase-separated structures. The findings of this study provide valuable insights into controlling and manipulating block copolymer structures, which has important implications for future applications.