The synthesis and characterization of poly­(phenylene polysulfide) networks (PSNs) with controlled average sulfur ranks, from elemental sulfur (ES) and p-diiodobenzene (DIB), are investigated. The PSN films, prepared via simple hot pressing, are found to possess large extensibility up to around 300% and complete recovery of shape and mechanical properties after deformation, which are attributed to the loosely cross-linked network structures mainly consisting of linear poly­(phenylene polysulfide) chains. The covalent polysulfide linkages in the PSNs also exhibit dynamic behaviors under ultraviolet (UV) or thermal treatment, thus, enabling self-healing and reprocessing of the films when scratched and broken, respectively. Combined with the unique mechanical properties of the PSNs, their high refractive index and excellent infrared (IR) transparency contribute to the preparation of stretchable, healable, and reprocessable IR transmitting materials for potential deformable and stretchable optical applications.

Thermadapt shape memory polymers (SMPs), utilizing a variety of dynamic covalent bond exchange mechanisms, have been extensively studied in recent years but it is still challenging to address several constraints in terms of limited accuracy and complexity for constructing 3D shape memory structures. Here, an effective and facile preparation of thermadapt SMPs based on elemental sulfur‐derived poly(phenylene polysulfide) networks (PSNs) is presented. These SMPs possess intrinsic near‐infrared (NIR)‐induced photothermal conversion properties for spatiotemporal control of their plasticity and elasticity. The NIR‐controllable plasticity and elasticity of the PSNs enable versatile shape manipulation of 3D multi‐shape memory structures, including building block assembly, reconfiguration, shape fixing/recovery, and repair.

Front Cover: In article 2000013, Dong‐Gyun Kim, Ho Gyu Yoon, Yong Seok Kim, and co‐workers report an effective and facile preparation of thermadapt shape‐memory polymers based on elemental‐sulfur‐derived poly(phenylene polysulfide) networks (PSNs), which possess intrinsic near infrared (NIR)‐induced photothermal conversion properties for enabling spatiotemporal control of their plasticity and elasticity. The NIR‐controllable plasticity and elasticity of the PSNs eventually lead to the realization of versatile shape manipulation of 3D multi‐shape memory structures, including building‐block assembly, reconfiguration, shape fixing/recovery, and repair.

No abstract