Recyclable Shape-Memory Waterborne Polyurethane Films Based on Perylene Bisimide Modified Polycaprolactone Diol

Currently, much attention is given to the functionality and recyclability of waterborne polyurethane (WPU). Herein, ε-caprolactone was used as a chain extender for grafting onto perylene bisimide (PBI) and 1,4-butanediol (BDO) via ring-opening reactions to obtain PBI-PCL and BDO- PCL. Then, two kinds of WPU, namely PBI-WPU (PWPU) and BDO-WPU (BWPU), were fabricated using PBI-PCL/polytetrahydrofuran ether glycol (PTMG) and BDO-PCL/PTMG, respectively, as mixed soft segments. The properties and appearance of PWPU and BWPU emulsions were analyzed in terms of particle size, zeta potential and TEM images, and the results showed that PWPU emulsions had uniform particle size distribution and decent storage stability. AFM and DMA results revealed that PWPU films possessed a more significant degree of microphase separation and a higher glass transition temperature (T(g)) than BWPU films. The PWPU films displayed good shape-memory and mechanical properties, with tensile strength up to 58.25 MPa and elongation at break up to 1241.36%. TGA analysis indicated that PWPU films had better thermal stability than BWPU films. More importantly, the PWPU films could be dissolved in a mixed solvent of acetone/ethanol (v/v = 2:1) at room temperature. The dissolved PWPU could be dispersed in deionized water to prepare waterborne polyurethane again. After the recycling process was repeated three times, the recycled PWPU emulsion still exhibited good storage stability. The recycled PWPU films maintained their original thermal and mechanical properties. Comparing the properties of BWPU and PWPU showed that the soft segment structure had important influence on waterborne polyurethane performance. Therefore, PWPU may have great potential applications in making recycling and shape-memory coating or paint.