Nucleobase-functionalized acrylic ABA triblock copolymers and supramolecular blends

Reversible addition-fragmentation chain transfer (RAFT) polymerization afforded the unprecedented synthesis of well-defined acrylic ABA triblock copolymers with nucleobase-functionalized external blocks and a central poly(n-butyl acrylate) (PnBA) block. Size exclusion chromatography (SEC) confirmed the molecular weight and molecular weight distribution of the central block. ¹H NMR spectroscopy revealed the successful chain extension of the PnBA macro-chain transfer agent (CTA) using adenine or thymine-functionalized acrylic monomers. The acrylic monomer with a flexible spacer to the pendant nucleobases promoted intermolecular recognition of nucleobases and long range segmental motion of polymer main chains. The external block glass transition temperatures (T_g's) of thymine (T) and adenine (A) functionalized blocks were 52°C and 76°C, respectively. Thermomechanical and morphological analysis revealed the effect of processing conditions on self-assembly and microphase-separated morphology of nucleobase-functionalized ABA copolymers. Thymine and adenine-functionalized ABA triblocks formed a thermodynamically stable, hydrogen-bonded complex upon blending. The supramolecular blend exhibited a cylindrical microphase-separated morphology with an extended plateau window compared to the individual block copolymers. The complementary hydrogen bonding between adenine and thymine formed a thermally labile, physically crosslinked, network that exhibited enhanced mechanical performance with melt processability. Thus, these ABA nucleobase-functionalized block copolymers demonstrate potential as thermoplastic elastomers for hot melt adhesives and coatings.