Enhanced Heat Resistance and Adhesive Strength of Styrene–Acrylic Triblock Copolymer Elastomers by Incorporating Acrylic Acid

[Image: see text] Herein, we present an industrially applicable strategy to enhance the heat resistance and adhesive properties of ABA triblock copolymer-based elastomers composed of styrene (St) and n-butyl acrylate (nBA) by incorporating acrylic acid (AA) at different segments. Three types of triblock copolymers, namely, poly(St-r-AA)-b-poly(nBA)-b-poly(St-r-AA), poly(St)-b-poly(nBA-r-AA)-b-poly(St), and poly(St)-b-poly(nBA)-b-poly(St), were synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Large-scale RAFT polymerization afforded industrially applicable AA-containing triblock copolymers with moderate molecular weights and predetermined comonomer compositions (St/nBA/AA = 15/83/2–24/73/3, number-average molecular weight (M(n)) = 30,000–110,000, and resulting product > 200 g). The heat resistance and pressure-sensitive adhesive properties of the triblock copolymers were evaluated. Among them, poly(St-r-AA)-b-poly(nBA)-b-poly(St-r-AA), having poly(nBA) as the middle soft segment and poly(St-r-AA) as hard segments at both ends, exhibited excellent heat creep resistance and increased adhesiveness to stainless steel. The feasibility to manipulate the heat resistance and adhesive properties by incorporating AA units into hard and soft segments, in addition to the ease of operation, high block efficiency, and metal-free nature owing to the RAFT process, is highly beneficial for practical applications of these copolymers.