Chemoselective Polymerization of Asymmetric Diacrylate Enabled by B(C6F5)3-Induced s-cis or s-trans Monomer Conformation: Facile Preparation and Application of Polymeric Multisite-Cross-Linkers

Chemoselective polymerization of divinyl monomers enables the synthesis of polymers bearing reactive side chains, which are versatile precursors for functionalized polymers and non-linear architectures. However, retaining the highly polymerizable functional groups, such as α,β-unsaturated carbonyls, during polymerization is challenging. In this study, the polymerization of 2-(methacryloyloxy)ethyl acrylate (1) using Lewis pair (LP) catalysts composed of B(C6F5)3 with PPh3 or PCy3 proceeded exclusively at the acryloyl moiety without cross-linking, thus retaining the methacryloyl group in the polymer side chain. Nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) computations revealed that the complete chemoselectivity of this reaction, preferentially occurring at the acryloyl moiety rather than the methacryloyl moiety, could be attributed to the conformational preference of the 1–B(C6F5)3 complexes. Specifically, a highly electrophilic s-trans conformer formed upon coordination of the acryloyl group, whereas a much less reactive s-cis conformer formed upon coordination of the methacryloyl group. Additionally, acrylic copolymers of 1 bearing multiple methacryloyl groups were synthesized and employed as polymeric cross-linkers for the radical photopolymerization of ethyl acrylate (EA). The resulting poly(EA) elastomers exhibited increased stress at high strains and greater mechanical robustness than elastomers synthesized from a divinyl cross-linker.