A Transformable and Bulky Methacrylate Monomer That Enables the Synthesis of an MMA‐nBA Alternating Copolymer: Sequence‐Dependent Self‐Healing Properties

Abstract In this study, we designed a methacrylate molecule with an alkyl‐substituted trichloro salicylic acid pendant as a transformable bulky monomer to enable the synthesis of an alternating copolymer of methyl methacrylate (MMA) and n ‐butyl acrylate ( n BA). The adamantyl‐substituted methacrylate monomer ( 1‐Ad ) showed very low homopolymerization propensity in radical polymerizations, but afforded the alternating copolymer with n BA via copolymerization. The 1‐Ad units in the resultant copolymer were quantitatively and selectively transformed into MMA via transesterification with methanol to yield the alternating copolymer of MMA and n BA. Its alternating sequence was clearly demonstrated by a structural analysis via 13 C NMR spectroscopy as well as the low reactivity ratios for the 1‐Ad and n BA pair. Finally, we verified the superior self‐healing ability of the alternating copolymer compared to that of the corresponding 1 : 1 statistical copolymer.