Modulation of flexo-rigid balance in photoresponsive thymine grafted copolymers towards designing smart healable coating. Issue 62 (10th December 2021)

• Record Type: Journal Article
• Authors: Miglani, Chirag; Joseph, Jojo P.; Gupta, Deepika; Singh, Ashmeet; Pal, Asish
• Is Part Of: RSC advances. Volume 11:Issue 62(2021)
• Page Start: 39376
• Page End: 39386
• Publication Date: 2021-12-10
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1ra07425c
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Photo-crosslinking using [2 + 2] cycloaddition in thymine grafted low viscosity polymer generates flexorigid domain to result self-healing polymer with increased hydrophobicity for potential use as smart coating material. Abstract : Efficacy and durability of the photovoltaic device mandates its protection against hot, humid weather condition, high energy of UV light and unwanted scratches. Such challenges can be mitigated by smart polymeric coating with inherent properties e.g. hydrophobicity to prevent moisture, optimal viscocity for better processibility and crack-healing. The hydrophobic polymers TP1–TP4 containing pendant photo-crosslinkable thymine moieties are designed that undergo [2 + 2] photocycloaddition upon UVB irradiation and can be dynamically reverted back upon irradiation with UVC light. A judicious control of solvent environment, chain length, functionality% and concentration of the polymers regulate the aspects of photodimerization thereby, rendering intra or inter-chain collapse to form diverse nanostructures. Photodimerization of the thymine moieties renders coil to globule transformation in dilute condition whereas irradiation performed at high macromolecular concentration regime exhibits higher order nanostructures. The photoresponsive chain collapse leads to the formation of rigid crosslinked domains within flexible polymer chains akin to the hard–soft phases of thermoplastic elastomers. Such rigidification of the crosslinked segments endows a tool to photomodulate the glass transition temperature ( T g ) that can dynamically revert back upon decrosslinking. Further, the structural modulation of the polymers is explored towards autonomic and nonautonomic self-healing behaviour at ambient conditions. Moreover, the self-healing efficacy can be tuned with the film thickness and it remains unaltered upon using solar simulator or direct sunlight. Overall, such hydrophobic low T g polymers display photo-regulated self-healing mechanism consisting of both autonomic and non-autonomic self-healing and may find applications in designing smart protective coatings for photovoltaic devices.