High‐Compatibility Crystallization Strategy Enabling Self‐Reinforced Elastomers for Green Tires

Structural reinforcement through crystallization is a widely adopted strategy for enhancing the properties of elastomers, wherein the compatibility between crystalline domains and the flexible amorphous phase plays a key role in determining the reinforcement efficiency. Inspired by strain‐induced crystallization in natural rubber, this work designed a chain‐entanglement network between a flexible matrix of high‐vinyl 1,2‐polybutadiene (HVPB) and crystalline 1,2‐polybutadiene (sPB). A novel crystallizable self‐reinforcing elastomer (sPB‐HVPB) was successfully prepared via in situ polymerization of butadiene in hexane. Owing to the favorable molecular compatibility among polybutadiene chains, HVPB established an effective interfacial bridge between crystalline and amorphous regions, ultimately forming a self‐supporting interpenetrating network structure characterized by “flexible chain–flocculated crystalline domain–flexible chain” within the elastomer. This structure significantly improved the mechanical properties of the material, with sPB‐HVPB exhibiting a 12% enhancement compared to conventional vinyl cis‐polybutadiene rubber (VCR). Furthermore, when sPB‐HVPB was blended with solution‐polymerized styrene–butadiene rubber and silica and applied in green tire tread compounds, it notably reduced rolling resistance (by 2.8%), improved wear resistance (by 3.15%), and enhanced wet‐skid resistance (by 36%), demonstrating promising potential as an ideal tread material. This study offers a new design strategy for high‐compatibility crystallite‐reinforced elastomers.