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Spontaneously Healable Thermoplastic Elastomers Achieved through One-Pot Living Ring-Opening Metathesis Copolymerization of Well-Designed Bulky Monomers

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posted on 02.05.2016, 00:00 by Ji-Xing Yang, Ying-Yun Long, Li Pan, Yong-Feng Men, Yue-Sheng Li
We report here a series of novel spontaneously healable thermoplastic elastomers (TPEs) with a combination of improved mechanical and good autonomic self-healing performances. Hard–soft diblock and hard–soft–hard triblock copolymers with poly­[exo-1,4,4a,9,9a,10-hexahydro-9,10­(1′,2′)-benzeno-l,4-methanoanthracene] (PHBM) as the hard block and secondary amide group containing norbornene derivative polymer as the soft block were synthesized via living ring-opening metathesis copolymerization by use of Grubbs third-generation catalyst through sequential monomer addition. The microstructure, mechanical, self-healing, and surface morphologies of the block copolymers were thoroughly studied. Both excellent mechanical performance and self-healing capability were achieved for the block copolymers because of the interplayed physical cross-link of hard block and dynamic interaction formed by soft block in the self-assembled network. Under an optimized hard block (PHBM) weight ratio of 5%, a significant recovery of tensile strength (up to 100%) and strain at break (ca. 85%) was achieved at ambient temperature without any treatment even after complete rupture. Moreover, the simple reaction operations and well-designed monomers offer versatility in tuning the architectures and properties of the resulting block copolymers.