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Solvent-Free UV Polymerization of n-Octadecyl Acrylate in Butyl Rubber: A Simple Way to Produce Tough and Smart Polymeric Materials at Ambient Temperature

2021    Su, Esra; Bilici, Cigdem; Bayazit, Gozde; Ide, Semra; Okay, Oguz

One of the most fascinating challenges in recent years has been to produce mechanically robust and tough polymers with smart functions such as self-healing and shape-memory behavior. Here, we report a simple and versatile strategy for the preparation of a highly tough and highly stretchable interconnected interpenetrating polymer network (c-IPN) based on butyl rubber (IIR) and poly(n-octadecyl acrylate) (PC18A) with thermally induced healing and shape-memory functions. Solvent-free UV polymerization of n-octadecyl acrylate (C18A) at 30 +/- 2 degrees C in the presence of IIR leads to IIR/PC18A c-IPNs with sea-island or co-continuous morphologies depending on their IIR contents. The lamellar crystals with a melting temperature T-m of 51-52 degrees C formed by side-by-side packed octadecyl (C18) side chains are responsible for more than 99% of effective cross-links in c-IPNs, the rest being hydrophobic associations and chemical cross-links. The c-IPNs exhibit varying stiffness (9-34 MPa), stretchability (72-740%), and a significantly higher toughness (1.912 MJ.m(-3)) than their components, which can be tuned by changing the IIR/PC18A weight ratio. The properties of c-IPNs could also be tuned by incorporating a second, noncrystallizable hydrophobic monomer, namely, lauryl methacrylate (C12M), in the melt mixture. We show that the lamellar clusters acting as sacrificial bonds break at the yield point by dissipation of energy, while the ductile amorphous continuous phase keeps the structure together, leading to the toughness improvement of c-IPNs. They exhibit a two-step healing process with >90% healing efficiency with respect to the modulus and a complete shape-recovery ratio induced by heating above Tm of alkyl crystals. The temperature-induced healing occurs via a quick step where C18 bridges form between the damaged surfaces followed by a slow step controlled by the interdiffusion of C18A segments in the bulk. We also show that the strategy developed here is suitable for a variety of rubbers and n-alkyl (meth)acrylates of various side-chain lengths.