Adamantane (tricyclo[3.3.1.13,7]decane) is a unique compound that consists of fused cyclohexane rings with a fixed, highly symmetric, and thermodynamically stable structure same as the diamond lattice, leading to characteristics such as a high melting point, less intermolecular interaction, a low friction coefficient, and highly hydrophobicity. A large variety of adamantine-containing polymers have been synthesized for the uses as the thermoresistant polymers, rigid-chain polymers, high-performance membranes, photoresists, photoswichable supramolecular hydrogels, unimolecular polymer micelles, and host-guest materials. Poly(1-adamantyl acrylate) (PAdA) exhibits a high glass transition temperature (Tg), which is enough to be used as thermoplastic material with excellent thermal stability, while polyacrylates have been used as adhesives, paints, sealants, rubbers, and UV-curable resins. Thermally stable and transparent polymers are important for optical disk, fiber, lens, displays, digital signage, and lightingin the modern information and electronics technology fields.In this study, we prepared the sequence-controlled block copolymers consisting of PAdA and poly(n-butyl acrylate) block sequences as the hard and soft segments, respectively, including polar repeating units by the organotellurium-mediated living radical polymerization (TERP). The TERP technique is one of the most powerful method of the controlled radical polymerizations for the synthesis of high-molecular-weight polyacrylates including polar and functional side groups. We investigated the thermal, optical, and mechanical properties of the acrylate block copolymers including an adamantyl moiety as the new transparent acrylic polymers with a high Tg (Figure 1). The microphase-separated structures were confirmed by the DSC and AFM observations as well as dynamic mechanical measurements. The molecular motions of the hard and soft segments were observed and the transition temperatures and activation energies increased by the introduction of the polar hydroxy and carboxy moieties in the side groups of the soft segments due to the formation of intermolecular hydrogen bonding. The effects of the hydrogen bonding and the cross-linking of the polymers on their tensile elasticity, strength, and strain were also evaluated.

Synthesis of sequence-controlled poly(1-adamantyl acrylate)-<i>block</i>-poly(<i>n</i>-butyl acrylate)s containing polar side group by TERP and their thermal, optical, mechanical properties

248th National Meeting (2014)

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Synthesis of sequence-controlled poly(1-adamantyl acrylate)-block-poly(n-butyl acrylate)s containing polar side group by TERP and their thermal, optical, mechanical properties