Fabrication of High χ-Low N Block Copolymers with Thermally Stable Sub-5 nm Microdomains Using Polyzwitterion as a Constituent Block

In this work, we used zwitterionic poly(4-vinylpyridine) propane-1-sulfonate (PVPS) as a constituent block to construct high chi-low N block copolymers (BCPs) with different neutral polymers as the other block, including polystyrene (PS), poly(ethylene oxide) (PEO), and poly(L-lactide) (PLLA). Lamellar structures with sub-5 nm microdomains were observed in all three types of BCPs. Due to the tendency of self-aggregation induced by electrostatic interaction in polyzwitterion, the Flory-Huggins parameters (chi) between PVPS and most neutral polymers are relatively high, which provides a facile and efficient way to fabricate high chi-low N BCPs. In addition, the dimension of the sub-5 nm structures formed in PVPS-containing BCPs showed high thermal stability with a small fluctuation (+/- 0.1 nm) of domain spacings upon heating.