Aqueous Assembly and Hydrogel Rheology of Sustainable Glyoxylate-Based Copolymers

The self-assembly of poly(ethyl glyoxylate)-poly(ethylene oxide)-poly(ethyl glyoxylate) (PEtG-PEO-PEtG) triblock copolymers in aqueous environments was systematically studied by using rheology and small-angle neutron scattering (SANS). These systems form associative micellar gels in water, with the PEtG end-blocks forming micelle cores and the PEO mid blocks forming loops in the micelle coronas and intermicellar bridges. As PEtG block length is increased, rheology shows slower relaxation behavior, consistent with a longer lifetime of intermicellar bridges and associations. The length of the self-immolative PEtG block can be used to tailor the mechanical properties, size of nanoscale hydrophobic domains, and larger-scale assembly behavior of the block copolymer gels. These results can guide the design of self-immolative block copolymers with desirable rheological properties and nanoscale structures for a variety of applications.