Sunlight Stimulated Photochemical Self‐Healing Polymers Capable of Re‐Bonding Damages up to a Centimeter Below the Surface Even Out of the Reach of the Illumination

• Published in: Advanced materials (Weinheim) 2023-04, Vol.35 (14), p.e2211009-n/a
• Main Authors: Li, Yan Mei, Zhang, Ze Ping, Rong, Min Zhi, Zhang, Ming Qiu
• Format: Article
• Language: English
• Subjects: Bonding; Chromophores; dithiocarbamate bonds; free radical transfer; Healing; Illumination; Luminous intensity; Mechanical properties; photo‐reversible; Polymers; sunlight‐induced self‐healing; Surface cracks; Surface layers; Tensile strength; Ultraviolet radiation; ultra‐deep healing capability
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202211009

The development of photochemical self‐healing polymers faces the the following bottlenecks: i) only the surface cracks can be restored and ii) materials’ mechanical properties are lower. To break these bottlenecks, cross‐linked poly(urethane‐dithiocarbamate)s carrying photo‐reversible dithiocarbamate bonds covalently linked to indole chromophores and benzyl groups are designed. The conjugated structure of the chromophore and benzyl enhances the addition reactivity of thiocarbonyl moiety and facilitates photo‐cleavage of CS bond, so that transfer of the created radicals among dithiocarbamate linkages is promoted. Accordingly, reshuffling of the reversibly cross‐linked networks via dynamic exchange between the activated dithiocarbamates is enabled in both surface layer and the interior upon exposure to the low‐intensity ultraviolet (UV) light from the sun. It is found that the damages up to a centimeter below the surface can be effectively recovered in the sunshine, which greatly exceeds the maximum penetration distance of UV light (hundreds of microns). Besides, tensile strength and failure strain of the poly(urethane‐dithiocarbamate) are superior to the reported photo‐reversible polymers, achieving the record‐high 33.8 MPa and 782.0% owing to the wide selectivity of soft/hard blocks, multiple interactions, and appropriate cross‐linking architecture. The present work provides a novel paradigm of photo self‐healing polymers capable of re‐bonding cracks even out of the reach of the illumination. Sunlight‐induced self‐healing polymers capable of remending cracks up to a centimeter deep based on long‐range free radicals transfer mechanism are developed by the incorporation of photo‐sensitive dithiocarbamate units. Furthermore, record‐high mechanical properties are acquired as compared with the reported photo‐reversible polymers.