Phase separation of organic networks derived from mixtures of reactive monomers and/or oligomers can take place through the formation of IPNs or precipitation of particles. The latter systems are widely used as a means of increasing the fracture toughness of thermosetting resins, and particularly for products obtained from mixtures of epoxy resins and functionalized aliphatic oligomers. In the present work several mixtures comprised of difunctional epoxy resins, silane functionalized perfluoroether oligomers, prehydrolyzed tetraethoxysilane, and an aromatic amine hardener were examined in a variety of compositions and preparative procedures. The aims were to control the kinetics of phase separation and the repartition of the different components in the two phases, so that the silica domains could be preferentially located within the precipitated soft particles. It was found that the silane functionalization of the perfluoroether oligomer provided an effective mechanism for the localization of the siloxane networks within the precipitated particles. However, phase separation by the precipitation of particles would only take place for systems in which the perfluoroether oligomer could be reacted with an excess of epoxy resin prior to adding the alkoxysilane solution and the hardener. Moreover, it was difficult to achieve the total localization of the siloxane component into the perfluoroether network. The siloxane species remaining dissolved in the resin gave rise to severe embrittlement of the products through reactions with the epoxy chains. Using mixtures of suitably functionalized perfluoroether oligomers it was possible to produce the conditions by which the localization of the silica domains into the precipitated particles could be maximized. This has resulted also in the formation of graded interphase regions and to a global improvement in mechanical properties, manifested as a concomitant increase in modulus, strength, and toughness.

ABSTRACT:Mixtures of an epoxy resin, hardener, and acid functionalized perfluoroether oligomers will readily undergo phase separation during curing. However, the conditions to bring about the growth of nuclei into microscopic particles have hitherto been found only for systems cured with anhydrides. In the present study perfluoroether oligomers were functionalized by established procedures to introduce both carboxylic acid groups and alkoxysilane groups in sites within the chain extended segments. The presence of alkoxysilane groups together with the prereaction step with an excess epoxy resin, prior to the addition of the aromatic amine hardener, induced phase separation by a nucleation-and-growth mechanism. The dual functionality in the perfluoroether oligomer was even more beneficial when the alkoxysilane groups were hydrolyzed prior to the addition of the amine hardener. Under such circumstances the precipitation of the perfluoroether oligomer occurred quantitatively, as indicated by the complete absence of any plasticization effects in the epoxy matrix. From electron microscopy examinations, thermal analysis, and measurements of mechanical properties it was possible to deduce a plausible mechanism for the formation of the typical coreshell aggregates within the precipitated particles for these systems, which could also be applied to other systems, such as those using carboxylic-acid-terminated butadiene acrylonitrile oligomers.