Rheological study of structural transitions in triblock copolymers in a liquid crystal solvent

Rheological properties of triblock copolymers dissolved in a nematic liquid crystal (LC) solvent demonstrate that their microphase separated structure is heavily influenced by changes in LC order. Nematic gels were created by swelling a well-defined, high molecular weight ABA block copolymer with the small-molecule nematic LC solvent 4-pentyl-4'-cyanobiphenyl (5CB). The "B" midblock is a side-group liquid crystal polymer (SGLCP) designed to be soluble in 5CB and the "A" endblocks are polystyrene, which is LC-phobic and microphase separates to produce a physically cross-linked, thermoreversible, macroscopic polymer network. At sufficiently low polymer concentration a plateau modulus in the nematic phase, characteristic of a gel, abruptly transitions to terminal behavior when the gel is heated into its isotropic phase. In more concentrated gels, endblock aggregates persist into the isotopic phase. Dramatic changes in network structure are observed over small temperature windows (as little as 1 °C) due to tccche rapidly changing LC order near the isotropization point. The discontinuous change in solvent quality produces an abrupt change in viscoelastic properties for three polymers having different pendant mesogenic groups and matched block lengths.