Synthesis of PS-P2VP modified by the POSS group and its self-assembly behavior

To address the challenge of controllable and precise regulation of the phase behavior of block copolymers, this study proposes a novel strategy to regulate the self-organization behavior of PS-P2VP block copolymers through supramolecular self-assembly. PS-P2VP was synthesized via the RAFT method, and three POSS molecules with different non-covalent interactions were synthesized and used to form complexes with the PS-P2VP copolymers. Characterization techniques such as NMR, GPC, FT-IR, TGA, DSC, SAXS, and SEM, along with theoretical methods, were employed to analyze the impact of POSS on the phase behavior of PS-P2VP. The results demonstrate that POSS is particularly effective in modulating the self-assembled phase behavior in the lamellar phase of block copolymers, with BPOSS-Cl showing the most significant modulation, enabling the complexes to achieve third-order peaks in SAXS measurements. This conclusion is further supported by theoretical calculations. The study not only reveals the mechanism by which POSS regulates the self-assembly behavior of PS-P2VP but also provides a promising direction for advancing autonomous phase selection in block copolymers.