Effect of end-groups on sulfobetaine homopolymers with the tunable upper critical solution temperature (UCST)

One-step syntheses of well-defined Poly(3-((2-(Methacryloyloxy) ethyl) (dimethyl) ammonio)-1-propanesulfonate) (PDMAPS) with a carboxylic acid end-functional reversible addition-fragmentation chain transfer (RAFT) agent and further end-group modification were described. The upper critical solution temperature (UCST) of homo-zwitterions can be precisely adjusted by the surrounding pH due to the presence of a carboxyl end-group. Meanwhile, after esterification of the carboxylic acid group by methyl, ethyl, hexyl, phenethyl alcohol, UCST of all resulted PDMAPS with ester terminated groups showed more significant increases. Dynamic light scattering (DLS), Zeta-potential and small-angle X-ray scattering (SAXS) results demonstrated that the ionization/protonation from the carboxylic end-group and hydrophobicity of ester groups contribute significantly to the tunability. This end-group modification technique provides an easy and economical way of synthesizing temperature-responsive homo-polyzwitterions with precise and controllable temperature range owing to the designability of RAFT polymerization, where the products are suitable for biomedical and environmental engineering applications.