Novel acrylic monomers functionalized with nucleobase-containing units (adenine and thymine) were prepared upon aza-Michael addition and successfully copolymerized with nbutyl acrylate. At a content of 7 mol %, adenine-containing units self-assembled into needle-like microstructures within amorphous polymer matrices as shown with atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD); thymine-containing units did not aggregate into distinct morphologies even to 30 mol %. Upon blending, thymine-and adenine-containing statistical copolymers associated into a thermodynamically stable complex, which was physically cross-linked through adenine−thymine base pairing. The molar fractions of the nucleobase monomer, nucleobase stacking interactions, and complementary hydrogen bonding principally influenced self-assembly. Additionally, the nucleobasefunctionalized polyacrylates exhibited tunable adhesive and cohesive strength.

Conventional free radical polymerization and anion metathesis of ammonium and phosphonium styrenics successfully generates high‐molecular‐weight polymerized ionic liquids (PILs). Phosphonium polyelectrolytes containing Cl‐ counterions display significantly higher thermal stabilities (>370 °C) compared with ammonium analogs (<220 °C). Anion exchange to BF4–, TfO–, and Tf2N– improves the thermal stability of all the PILs and depresses their Tg. Impedance‐spectroscopy‐probed ionic conductivities of PILs containing Tf2N–, and phosphonium PILs exhibit higher values than ammonium analogs. Phosphonium PILs displayed many advantages over ammonium PILs for emerging applications that demand higher thermal stabilities and ionic conductivities.

Phosphonium ion-containing acrylate triblock (ABA) copolymers were synthesized using nitroxide mediated radical polymerization. The polymerization of styrenic phosphonium-containing ionic liquid monomers using a difunctional alkoxyamine initiator, DEPN2, afforded an ABA triblock copolymer with an n-butyl acrylate soft center block (DP ∼ 400) and symmetric phosphonium-containing external reinforcing blocks (DP < 30). Two phosphonium monomers with different alkyl substituent lengths enabled an investigation of the effects of ionic aggregation of phosphonium cations on the physical properties of ABA block copolymer ionomers. Subsequently, the thermomechanical properties and morphologies of these materials were compared to a noncharged triblock copolymer analogue with neutral polystyrene external blocks. Shortening the alkyl substituents on the phosphonium cation enhanced the hydrophilicity of tributyl-4-vinylbenzyl phosphonium chloride (BPCl) relative to trioctyl-4-vinylbenzyl phosphonium chloride (OPCl). In both cases, phosphonium cations promoted microphase-separation and thermoplastic elastomer performance for the OPCl- and BPCl-containing triblock copolymers compared to a less well-defined, microphase segregated morphology for the styrene analogue. Dynamic mechanical analysis (DMA) of phosphonium-containing triblock copolymers exhibited well-defined rubbery plateau regions, whereas the plateau was shortened for the nonionic analogue. The solid state morphologies of the block copolymers were studied using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and both techniques revealed phase separation at the nanoscale. DMA studies indicated that phosphonium aggregation governed flow activation energies.