Exploiting the lower disorder-to-order temperature in polystyrene-<i>b</i>-poly(<i>n-</i>butyl acrylate)-<i>b</i>-polystyrene triblock copolymers to increase their flow resistance at high temperature

This work focuses on the temperature-dependent structural and rheological characterization of polystyrene-b-poly(n-butyl acrylate)-b-polystyrene triblock copolymers (PS-b-PnBA-b-PS) in the melt and, in particular, on their ability to show a lower disorder-to-order temperature (LDOT). To this aim, copolymers of varying block lengths, but keeping the PnBA block as a major component, were synthesized. Small-angle x-ray scattering revealed that the copolymers with short PS blocks (∼10 kg/mol) approach an LDOT but do not cross it. At room temperature, these copolymers exhibit higher moduli compared to a PnBA homopolymer due to the reinforcing effect of the PS but are flowing at temperatures above the glass transition of the PS. Increasing the PS and PnBA block length, to keep the same PS fraction, induces more profound changes in the structural and viscoelastic behaviors. Such a copolymer crosses the LDOT, leading to a microphase-separated and ordered state at high temperature. Contrary to the copolymers with short PS blocks, the flow regime was not reached, even at temperatures well above the glass transition of the PS. Instead, a low-frequency plateau was observed in rheology, showing the increased lifetime of the microphase-separated PS domains. ABA triblock copolymers exhibiting an LDOT behavior could, thus, be of interest for the design of thermoplastic elastomers or pressure-sensitive adhesives that can resist the flow at high temperatures