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    Tuning the Properties and Self-Healing Behavior of Ionically Modified Poly(isobutylene-co-isoprene) Rubber
    (Washington, DC : Soc., 2017) Suckow, Marcus; Mordvinkin, Anton; Roy, Manta; Singha, Nikhil K.; Heinrich, Gert; Voit, Brigitte; Saalwächter, Kay; Böhme, Frank
    The focus of this work is on the nature of self-healing of ionically modified rubbers obtained by reaction of brominated poly(isobutylene-co-isoprene) rubber (BIIR) with various alkylimidazoles such as 1-methylimidazole, 1-butylimidazole, 1-hexylimidazole, 1-nonylimidazole, and 1-(6-chlorohexyl)-1H-imidazole. Based on stress-strain and temperature dependent DMA measurements, a structural influence of the introduced ionic imidazolium moieties on the formation of ionic clusters and, as a consequence, on the mechanical strength and self-healing behavior of the samples could be evidenced. These results are fully supported by a molecular-level assessment of the network structure (cross-link and constraint density) and the dynamics of the ionic clusters using an advanced proton low-field NMR technique. The results show distinct correlations between the macroscopic behavior and molecular chain dynamics of the modified rubbers. In particular, it is shown that the optimization of material properties with regard to mechanical and self-healing behavior is limited by opposing tendencies. Samples with reduced chain dynamics exhibit superior mechanical behavior but lack on self-healing behavior. In spite of these limitations, the overall performance of some of our samples including self-healing behavior exceeds distinctly that of other self-healing rubbers described in the literature so far.
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    Tailor-Made Functional Polymethacrylates with Dual Characteristics of Self-Healing and Shape-Memory Based on Dynamic Covalent Chemistry
    (New York, NY [u.a.] : Wiley InterScience, 2020) Mondal, Prantik; Behera, Prasanta K.; Voit, Brigitte; Böhme, Frank; Singha, Nikhil K.
    New shape memory polymers with self-healing behavior are obtained by thermoreversible Diels–Alder (DA) cross-linking of a furfuryl group-containing star-block copolymer with 1,1'-(methylenedi-4,1-phenylene)bismaleimide. The star-block copolymer consisting of a 3-arm polycaprolactone (PCL) core and a polyfurfuryl methacrylate shell is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. For this, a 3-arm macro-RAFT agent based on PCL is converted with an appropriate amount of furfuryl methacrylate in the presence of a radical initiator. Films of the DA network are partly insoluble at ambient temperatures. After annealing at 120 °C the films become completely soluble because of the progressing retro-DA reaction. Evaporation of the solvent and subsequent annealing at 60 °C restores the original insoluble state of the material. By means of a scratch test and tensile tests on cut and subsequently mended samples it is shown that the retro-DA reaction facilitates self-healing. Additionally, the films show pronounced shape memory effects with reasonable shape recovery and fixity ratios, which are attributed to the melting and crystallization of the PCL phase. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim