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In this work, we investigated the nanostructures and mechanical properties of epoxy thermosets containing a macromolecular miktobrush composed of poly(ε-caprolactone) (PCL) and polydimethylsiloxane (PDMS) side chains. The novel macromolecular miktobrush was synthesized via the combination of reversible addition–fragmentation chain transfer and ring-opening polymerizations. In the brush-like copolymer the molar ratio of PCL to PDMS was controlled to be 1:1 and the length of PCL chains was controlled to be close to that of PDMS chains (i.e., LPDMS = 1000). The densely grafted miktobrush copolymer was incorporated into epoxy and the nanostructured thermosets were obtained as evidenced by means of transmission electron microscopy and dynamic mechanical thermal analysis. The results of small-angle X-ray scattering showed that the formation of nanostructures in the thermosets followed a self-assembly mechanism. The measurement of critical stress intensity factor ( K1C) showed that the nanostructured thermosets displayed the improved fracture toughness owing to the formation of nanostructures. [ABSTRACT FROM AUTHOR]

Abstract: Benzoxazine-terminated poly(ethylene oxide) telechelics (Ba-terminated PEO) was synthesized and incorporated into polybenzoxazine to obtain the nanostructured thermosets. The morphology of the thermosets was investigated by means of atomic force microscopy (AFM), small angle X-ray scattering (SAXS) and dynamic mechanical analysis (DMA). The formation of the nanophase structures in the thermosetting composites was addressed on the basis of the mechanism of reaction-induced microphase separation (RIMPS), which was in marked contrast to the case of the binary thermosetting blends of polybenzoxazine with hydroxyl-terminated poly(ethylene oxide). The occurrence of RIMPS resulted from the copolymerization reaction of the end groups of Ba-terminated PEO telechelics with the precursor of thermosetting matrix (i.e., benzoxazine), which suppressed the occurrence of the macroscopic phase separation. It was found that the formation of the nanostructures has a significant effect on the melting behavior of PEO in the thermosets, thermal transition properties of the PBZ thermosets. [Copyright &y& Elsevier]

Amino-terminated poly(propylene oxide) (ATPPO) was incorporated into epoxy resin to toughen thermosets. It was found that nanostructured thermosets were obtained; the nanostructures were characterized by means of atomic force microscopy and small-angle X-ray scattering. The formation of the nanostructures is interpreted on the basis of the occurrence of the reaction of terminal groups of ATPPO with diglycidyl ether of bisphenol A; this reaction is suggested to result in the formation of star-shaped block copolymers composed of poly(propylene oxide) (PPO) and epoxy blocks. Due to the presence of the star-shaped block copolymer produced in situ, the phase separation of PPO induced by the reaction was confined to the nanometer scale. The glass-transition behavior and fracture toughness of the nanostructured thermosets were investigated by means of differential scanning calorimetry, dynamic mechanical thermal analysis, and the measurement of critical stress intensity factors. The epoxy thermosets were significantly toughened by the inclusion of a small amount of ATPPO. The thermal and mechanical properties of the nanostructured thermosets are compared to the binary blends of epoxy resin containing hydroxyl-terminated poly(propylene oxide) (HTPPO) with identical molecular weight. With the identical composition, the nanostructured thermosets displayed higher fracture toughness than that of their binary blends. The difference in morphology and properties is interpreted in terms of the formation of the nanostructures. [ABSTRACT FROM AUTHOR]