Solid-state NMR characterization of unsaturated polyester thermoset blends containing PEO–PPO–PEO block copolymers

First, the NMR method proposed in our previous work was improved to provide more accurate measurement of interphase thickness in multiphase polymers. Then the improved method, in combination with other techniques, was applied to elucidate the phase behavior, miscibility, heterogeneous dynamics and microdomain structure in thermoset blends of unsaturated polyester resin (UPR) and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer. The experimental results were compared with those of epoxy resin (ER)/PEO–PPO–PEO blends to systematically elucidate the influence of binary polymer–polymer interaction on the phase behavior, domain size and especially the interphase thickness in thermoset blends of UPR and ER, respectively, with the same PEO–PPO–PEO triblock copolymer. It was found that UPR/PEO–PPO–PEO exhibits strong phase separation with considerably small interphase, and only a small fraction of PEO is mixed with UPR. Whereas ER/PEO–PPO–PEO exhibits weak phase separation with thick interphase, and a large amount of PEO is intimately mixed with ER. It was suggested that the thermodynamic interaction between the block copolymer and cross-linked thermoset resin is one of the key factors in controlling the phase behavior, domain size and interphase thickness in these blends. These NMR results are qualitatively in good agreement with the previous theoretical prediction of interphase properties between two immiscible polymers. Our NMR works on different thermoset blend systems with weak and strong microphase separations clearly demonstrate that the improved NMR method is a general and useful method for measuring the interphase thickness and elucidating the phase behavior and subtle microdomain structure in multiphase polymers with detectable heterogeneous dynamics.