We synthesized PPG-terminated tetra-carbamates as a new toughening additive for epoxy thermosets through facile addition reaction of hexamethylene diisocyanate (HDI) with poly(tetra-methylene glycols) (PTMG) and poly(propylene glycols) (PPG). The effects of prepared tetra-carbamates on the rheological behavior of neat epoxy resin were studied along with the various cured properties of their modified epoxy systems. Four carbamate groups (–NHCOO–) endow the prepared additives not only with good intramolecular interactions, but also with optimal intermolecular interactions with epoxy polymers. This results in the suitable miscibility of the additives with the epoxy matrix for the formation of the typical biphasic structure of microparticles dispersed in the epoxy matrix via polymerization-induced microphase separation. The impact strength and critical stress concentration factor (KIC) of cured modified epoxy systems with the additives are significantly higher than those of unmodified epoxy systems, without sacrificing the processability (Tg) and flexural strength. The toughening mechanism is understood as a synergism combination among the phase separation mechanism, the in situ homogeneous toughening mechanism, and the particle cavitation mechanism.Keywords:tetra-carbamates;epoxy polymer;toughening;microphase separation;particle
Deyi Zhan,Abdul Saeed,Zixuan Li,Chengming Wang,Zhiwu Yu,Junfeng Wang,Nanjing Zhao,Weihong Xu,Jinhuai Liu
Recently, exploring new luminescent metal–organic frameworks (LMOFs) to selectively detect nitro-aromatic compounds (NACs) has been a hot topic of research. Simultaneously, it is still a challenging issue to understand the sensing mechanism of luminescent MOFs interacting with NACs at the molecular level. In this work, highly fluorescent Sc-tetracarboxylate frameworks (Sc-EBTC) have been successfully synthesized through a solvothermal method. The as-prepared Sc-EBTC crystals have good thermal stability, chemical stability as well as strong fluorescence (λex = 320 nm and λem = 400 nm), and they can detect various NACs rapidly (as short as 30 s), selectively and efficiently by the “turn-off” fluorescence mechanism. The detection limits of Sc-EBTC toward 2,4-DNP and 4-NP are quantified to be 5.71 ppb and 6.26 ppb, respectively. Furthermore, to better understand the sensing mechanism, we attempt to use solid-state NMR and X-ray photoelectron spectroscopy to vividly characterize the charge transfer caused by the interaction between NAC molecules and the MOF at the molecular level. Additionally, test strips were made successfully for the practical detection of the NACs. This study demonstrates that the MOF constructed from the H4EBTC ligands might be a promising candidate for the detection of trace NACs.
危险品化学品经营许可证（带存储）