Single-Step Synthesis of Mesoporous Vinyl Polymers via Hierarchical Assembly of Stereocontrolled Chains and Their Unique Properties

Abstract

Mesoporous materials, vital in energy, environmental, and medical applications, require resource-intensive production. Mesoporous vinyl polymers, p-alkyl-N-phenyl-acrylamide (APAA) polymers is introduced, which offer unprecedented advantages in mass production. APAA monomers swiftly form syndiotactic chains through Monomer Aggregation-mediated Rapid, Radical Stereocontrolled (MARRS) polymerization, spontaneously creating mesoporous structures. Structural analyses (X-ray, NMR, DSC, FTIR, TEM, and Brunauer-Emmett-Teller measurements) and molecular mechanics simulations suggest the formation of Y-shaped clusters via intermolecular hydrogen bonding between the syndiotactic chains, which then form either a lamellar or hexagonal cylindrical structure containing mesopores. APAA polymers are highly processable, enabling the straightforward production of microfibers, films, and microparticles. They exhibit significant blue light emission (Quantum Yield: 7-18%) while maintaining exceptional transparency in the visible range. UV-crosslinked APAA polymer fibers, which have both superhydrophobicity and strong water adhesion (petal effect), along with crosslinked APAA polymer microparticles, are highly effective at absorbing liquid-phase volatile organic compounds (VOCs) such as chloroform, tetrahydrofuran, benzene, and toluene. They achieve both rapid absorption (<10 s) and high absorption capacity. Their remarkably simple and economical synthesis, together with their unique physicochemical properties, position APAA polymers as promising, commercially sustainable mesoporous materials with diverse applications such as UV absorbers, transparent blue-emitting films, anti-counterfeiting materials, and water remediation.