In situ intercalative polycondensation is applied for the preparation of polyamide (PA) n,6-clay nanocomposites, namely poly(ethylene adipamide) (PA 2,6), poly(hexamethylene adipamide) (PA 6,6), and poly (dodecamethylene adipamide) (PA 12,6). For this purpose, two different polymerization routes are considered; a low-temperature melt polymerization technique and the conventional solution-melt one. Under the specific experimental conditions, lack of clay exfoliation is detected through XRD measurements, which is proved irreversible even when twin-screw extrusion is attempted as an additional step. The resulting PA n,6-clay structures are found dependent on the diamine moiety length; more specifically, an intrinsic interaction between the polyamide monomer and the organoclay surfactant is indicated. An ion exchange occurs between the two competitive species, that is, diamine and surfactant cations, leading to flocculated clay structures. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3291-3302, 2010