화학공학소재연구정보센터
Macromolecules, Vol.54, No.3, 1452-1464, 2021
Arresting Elevated-Temperature Creep and Achieving Full Cross-Link Density Recovery in Reprocessable Polymer Networks and Network Composites via Nitroxide-Mediated Dynamic Chemistry
Thermosets and thermoset composites constitute an extraordinary challenge for recycling and participation in a circular economy because their permanent covalent cross-links prevent spent thermosets from being melt processed into new products. With annual world-wide production in the tens of billions of kilograms, the inability to recycle thermosets into high-value products represents major economic and sustainability losses. While recent research into polymer networks with dynamic covalent cross-links has indicated promise for reprocessability at common melt-state processing temperatures, a crucial shortcoming has been identified: such reprocessable networks and network composites commonly exhibit creep at use conditions due to their dynamic nature, which may prevent their use in applications that require long-term dimensional stability. Here, we use a strategy based on nitroxide-mediated polymerization to synthesize reprocessable networks and network composites containing alkoxyamine dynamic bonds. The resulting networks, including those synthesized from lab-grade polybutadiene and industrial-grade natural rubber/carbon black composites, exhibit full cross-link density recovery and essentially no creep at 80 degrees C, where alkoxyamine cross-links are nearly static, after multiple molding cycles at 140/160 degrees C, where alkoxyamine cross-links are dynamic. This capability to "turn on" and "arrest" dynamic chemistry over a relatively narrow temperature window is attributed to the high activation energy (similar to 120 kJ/mol) and thus strong temperature dependence of the alkoxyamine dissociation reaction. With this key element of high activation energy for the dissociation reaction in systems undergoing dynamic reversion or the dynamic exchange reaction in vitrimers, it is possible to design covalent network materials with acute temperature response allowing for reprocessability with outstanding elevatedtemperature creep resistance.