Hydrophobically Modified Polycarboxybetaine: From Living Radical Polymerization to Self-Assembly

Polybetaines have received widespread attention due to their smart response properties and structures which resemble biological polymers like peptides and DNA. However, few studies have focused on the controlled synthesis and self-assembly of hydrophobically modified polybetaines due to the difficulty of synthesizing these materials. We report the first molecular weight-controlled synthesis of hydrophobically modified polycarboxybetaines (HMPCB). Poly(dodecyl grafted aminocrotonate -methacrylic acid) (P(DACRO-MAA)) was synthesized via the reversible addition-fragmentation chain-transfer (RAFT) polymerization approach. The two different tautomers of the monomer were also successfully identified and separated via thin layer chromatography (TLC) and column chromatography, making it possible to obtain pure polycarboxybetaine via RAFT synthesis. Both the successfully separated enamine form of the monomer and the resulting polycarboxybetaine were confirmed via FTIR and NMR. The polycarboxybetaine was found to have a low polydispersity (PDI) of 1.214, and its molecular weight was determined as 70590 g/mol via gel permeation chromatography (GPC) measurements. Spherical, rodlike, and fractal assembled structures for the P(DACRO-MAA) were observed with pH change using TEM, zeta sizer, and dynamic light scattering (DLS). The unique self-assembled structures of HMPCB synthesized via RAFT provide an opportunity to understand fundamental polymer science and can be engineered for broad applications.