Temperature-Responsive Behavior of Double Hydrophilic Carboxy-Sulfobetaine Block Copolymers and Their Self-Assemblies in Water

The block copolymer poly(2-((2-(methacryloyloxy)ethyl)dimethylammonio)acetate)-b-poly(3-(N-(2-metharyloylethyl)-N,N-dimethylammonio)-propanesulfonate) (PGLBT-b-PSPE) was synthesized by reversible addition-fragmentation chain transfer (RAFT) technique under precise control. The PGLBT-b-PSPE block copolymers showed upper critical solution temperature (UCST) behavior originating from PSPE moieties. Unlike PSPE homopolymers, the transmittance change with temperature was gradual, and unexpected retardation or slight changes in a reverse direction were found at the intermediate stage. Light scattering and H-1 NMR studies proved that the block copolymers formed spherical micelles that were composed of a PSPE core and PGLBT shell around room temperature and lower temperatures, and slowly disassociated with temperature increase. During the transition, fast (small particle) and slow (large particle) diffusive modes were detected by dynamic light scattering (DLS), which implied that the unimers were escaping from the self-assembled structure and swollen micelles, respectively. At sufficiently high temperatures where the solutions became almost transparent, the slow mode eventually disappeared, and only the fast mode remained. In addition, once the polymeric particles are formed, the size did not vary much with additional cooling. The transition point and the pattern of transmittance alteration were dependent on the degree of polymerization and the [PGLBT]:[PSPE] ratios; more PGLBT made the block copolymer less responsive to temperature and led the cloud point to lower degrees. However, random copolymers PGLBT-r-PSPE did not show any temperature-responsivity, and even small amount of GLBTs (10%) distributed in a PSPE chain significantly suppressed the transition.