Photo-Cross-Linked Self-Assembled Poly(ethylene oxide)-Based Hydrogels Containing Hybrid Junctions with Dynamic and Permanent Cross-Links.

Homogeneous hydrogels were formed by self-assembly of triblock copolymers via association of small hydrophobic end blocks into micelles bridged by large poly(ethylene oxide) central blocks. A fraction of the end blocks were photo-cross-linkable and could be rapidly cross-linked covalently by in situ UV irradiation. In this manner networks were formed with well-defined chain lengths between homogeneously distributed hybrid micelles that contained both permanent and dynamically cross-linked end blocks. Linear rheology showed a single relaxation mode before in situ irradiation intermediate between those of the individual networks. The presence of transient cross-links decreased the percolation threshold of the network rendered permanent by irradiation and caused a strong increase of the elastic modulus at lower polymer concentrations. Large amplitude oscillation and tensile tests showed significant increase of the fracture strain caused by the dynamic cross-links.