Unique Interphase and Cross-Linked Network Controlled by Different Miscible Blocks in Nanostructured Epoxy/Block Copolymer Blends Characterized by Solid-State NMR

• Published in: Journal of physical chemistry. C Vol. 118; no. 24; pp. 13285 - 13299
• Main Authors: He, Xin, Liu, Yuan, Zhang, Rongchun, Wu, Qiang, Chen, Tiehong, Sun, Pingchuan, Wang, Xiaoliang, Xue, Gi
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19.06.2014
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp5036772

A variety of multiscale solid-state NMR techniques were used to characterize the heterogeneous structure and dynamics of the interphase and cross-linked network in nanostructured epoxy resin/block copolymer (ER/BCP) blends, focusing on the role of ER-miscible blocks containing poly(ε-caprolactone) (PCL) or poly(ethylene oxide) (PEO) blocks having different intermolecular interactions with ER. 1H spin-diffusion experiments indicate that the interphase thickness of PEO-containing blends is obviously smaller than that of PCL-containing blends. High-resolution 1H fast magic-angle spinning (MAS) spin-exchange experiments reveal detailed interfacial mixing between ER and BCPs for the first time, and two different types of interphase structure are found. 1H fast MAS double-quantum filter experiments provide a fast and convenient detection of interphase composition, including immobilized BCPs and partially cured or local damaged ER network. The driving force for the interphase formation and miscibility in PCL-containing blends was successfully determined by high-resolution 13C CPMAS experiments, demonstrating the formation of hydrogen bonds between PCL and ER; competing hydrogen bonding interactions were also found when ER was blended with PEO-b-PCL (EOCL). A new calculation method is proposed to quantitatively determine the distribution of different blocks in the interphase and dispersed phase for PCL-containing blends in combination with 13C CPMAS and 1H spin-diffusion experiments. A 13C T 1 spin–lattice relaxation experiment provides a quantitative determination of the amount of local destroyed network in the interphase. Furthermore, it is found that incorporation of BCPs induces unexpected enhanced rigidity of the cross-linked network. On the basis of NMR results, we propose a model to describe the unique structure and dynamics of the interphase and cross-linked network as well as their underlying formation mechanism in ER/BCP blends.