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The mechanical properties of multiblock copolymer thermoplastic elastomers (TPEs) are governed by the interplay of different reversible dynamics [e.g., hard block (HB) association and chain entanglements]. Understanding how these physical processes influence the high-temperature deformation behavior is relevant as many TPEs lose toughness with increasing temperature. Increasing molecular weight (Mw) improves their temperature resistance that is attributed to an increase in network connectivity. Indeed, longer chains are characterized by more HBs per chain and by a longer lifetime of the entanglements in the amorphous phase. Both the associating HB and disentanglement dynamics are temperature and rate dependent. To further understand the interconnected role of Mw, temperature and rate dependencies on the mechanical properties, we perform Temperature Scanning Stress Relaxation (TSSR) tests. The method consists of measuring the stress relaxation of the materials as the temperature monotonically increases, allowing us to probe the stress response as the HBs progressively disassociate due to the increase in temperature. The results show that increasing Mw improves the high-temperature relaxation behavior, allowing the material to retain more stress than its low Mw counterpart as the temperature increases. This distinction does not show itself when performing standard small strain dynamic mechanical thermal analyses. Depending on the deformation experienced before the TSSR is performed, different relaxation behaviors are observed illustrating the importance of the current microstructure in determining the mechanical properties. The TSSR approach is well-suited to benchmark the high-temperature stress-bearing properties of network-based polymers whose morphology and, hence, properties are strongly deformation dependent.

We discuss the connection between high-temperature mechanics, block structure, and composition of a model series of industrially relevant, soft, thermoplastic elastomers (TPEs) containing polydisperse hard blocks (HBs). The high-strain deformation behavior of these materials results from the combination of multiple dynamics in the system, i.e., the HB associations and the mobile and entangled amorphous phase. Many soft-TPEs show a reduction in toughness with increasing temperature. Molecular weight (Mw) has been shown to improve the temperature-dependent mechanics by increasing network connectivity. In this work, we investigate the possibility to increase the network connectivity by tuning block length at constant Mw and composition. The average number of HBs per chain can be used to quantify network connectivity; however, by using block statistics, we show how increasing this value is not enough to increase the high-temperature mechanics, especially in the case of polydisperse HBs. Since temperature affects the HB ability to associate with each other, only the number of associated HBs per chain determines network connectivity. The experimental results are consistent with modeling predictions, revealing how decreasing the average block length influences the crystal stability, which ultimately controls network connectivity, and how this relationship is affected by temperature.