Single-Step Synthesis and Characterization of Non-Linear Tough and Strong Segmented Polyurethane Elastomer Consisting of Very Short Hard and Soft Segments and Hierarchical Side-Reacted Networks and Single-Step Synthesis of Hierarchical Hyper-Branched Polyurethane

Polyurethane elastomers are among the most versatile classes of industrial polymers—typically achieved through a two-step synthesis of segmented block copolymers, comprising very long and soft segments that provide elasticity and significantly long and hard segments that provide strength. The present research focused on the design of a single-step synthesis of a new segmented polyurethane consisting of very short soft and hard segments, crosslinked by preferentially side-reacted hierarchical tertiary oligo-uret network structures, thus exhibiting significant strength, elasticity, and toughness. Despite the theoretically linear structure, both FTIR and solid-state ¹³C NMR spectroscopy analyses indicated the quasi-equal presence of urethane groups and tertiary oligo-uret structures in the resulting polymer, indicating a preferential consecutive side reaction mechanism. Thermal analysis indicated the significant crystallization of soft segments consisting of only four ethylene oxide units, which was, hereby, demonstrated to occur via an extended chain mechanism. Tensile mechanical properties included significant strength, elasticity, and toughness. Increasing the soft segment length led to a decreased tertiary oligo-uret secondary crosslinking efficacy. The preferential hierarchical side reaction mechanism was, hereby, further confirmed through the synthesis of a completely new type of hyper-branched polymer via diisocyanate and a mono-hydroxy-terminated reagent. The structure–property relations and reaction mechanisms demonstrated in the present research can facilitate the design of new polyurethanes of enhanced performance and processing efficacy for a variety of novel applications.