Alzahrani Abeer A, Saed Mohand, Yakacki Christopher M, Song Han Byul, Sowan Nancy, Walston Joshua J, Shah Parag K, McBride Matthew K, Stansbury Jeffrey W, Bowman Christopher N
Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, CO.
Department of Mechanical Engineering, University of Colorado Denver, Denver, CO.
Polym Chem. 2018 Jan 7;9(1):121-130. doi: 10.1039/c7py01121k. Epub 2017 Nov 29.
This study is the first to employ the use of the copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization to form a tough and stiff, porous material from a well-defined network possessing a high glass transition temperature. The effect of the network linkages formed as a product of the CuAAC reaction, i.e., the triazoles, on the mechanical behavior at high strain was evaluated by comparing the CuAAC foam to an epoxy-amine-based foam, which consisted of monomers with similar backbone structures and mechanical properties (i.e., T of 115 °C and a rubbery modulus of 1.0 MPa for the CuAAC foam, T of 125 °C and a rubbery modulus of 1.2 MPa for the epoxy-amine foam). When each foam was compressed uniformly to 80% strain at ambient temperature, the epoxy-amine foam was severely damaged after only reaching 70% strain in the first compression cycle with a toughness of 300 MJ/m. In contrast, the CuAAC foam exhibited pronounced ductile behavior in the glassy state with three times higher toughness of 850 MJ/m after the first cycle of compression to 80% strain. Additionally, when the CuAAC foam was heated above T after each of five compression cycles to 80% strain at ambient temperature, the foam completely recovered its original shape while exhibiting a gradual decrease in mechanical performance over the multiple compression cycles. The foam demonstrated almost complete shape fixity and recovery ratios even through five successive cycles, indicative of "reversible plasticity", making it highly desirable as a glassy shape memory foams.
本研究首次采用铜催化的叠氮化物-炔烃环加成(CuAAC)聚合反应,从具有高玻璃化转变温度的明确网络结构中制备出一种坚韧且坚硬的多孔材料。通过将CuAAC泡沫与基于环氧-胺的泡沫进行比较,评估了作为CuAAC反应产物形成的网络连接(即三唑)对高应变下力学行为的影响,后者由具有相似主链结构和力学性能的单体组成(即CuAAC泡沫的玻璃化转变温度为115°C,橡胶态模量为1.0 MPa;环氧-胺泡沫的玻璃化转变温度为125°C,橡胶态模量为1.2 MPa)。在室温下将每种泡沫均匀压缩至80%应变时,环氧-胺泡沫在第一个压缩循环仅达到70%应变后就严重受损,韧性为300 MJ/m³。相比之下,CuAAC泡沫在玻璃态表现出明显的延性,在第一次压缩至80%应变循环后,韧性高出三倍,达到850 MJ/m³。此外,在室温下将CuAAC泡沫进行五次压缩至80%应变的循环后,每次压缩后将其加热至玻璃化转变温度以上,泡沫完全恢复其原始形状,同时在多次压缩循环中力学性能逐渐下降。即使经过五个连续循环,该泡沫仍表现出几乎完全的形状固定性和恢复率,表明具有“可逆可塑性”,使其成为一种非常理想的玻璃态形状记忆泡沫。