Phase behavior and viscoelastic properties of entangled block copolymer gels

Triblock copolymers in midblock-selective solvents can form physical gels. However, at low triblock contents (near the percolation threshold), the bridging of chains between micelles can lead to macrophase separation. Adding a styrene-isoprene diblock to a styrene-isoprene-styrene triblock copolymer in squalene can eliminate macrophase separation, yielding a wide range of stable, single-phase gels with a disordered arrangement of micelles. The plateau modulus of these triblock gels scales with the 2.2 power of polymer content, indicating the importance of entanglements in dictating the modulus. Comparing gels made from the midblock-saturated derivative of the same polymer [styrene-(ethylene-alt-propylene)-styrene] in squalene reveals that the modulus differences in the gels are a direct consequence of the difference in the entanglement molecular weight of the midblock homopolymer in bulk. Finally, the broad relaxation spectrum of these triblocks is well-described by a recent theory for the dynamics of entangled star polymers, with the breadth of the relaxation spectrum dictated by the number of entanglements per midblock in the gel.