Synergistic effect of silicate clay and phosphazene-oxyalkyleneamines on thermal stability of cured epoxies

Abstract

Amine substitution of hexachlorocyclophosphazene (HCP) with poly(oxypropylene)diamines (POP) afforded HCP–POP adducts which were subsequently intercalated into a layered silicate clay. The relative thermal stabilities of the epoxies cured with the phosphazene-amines and the intercalated clays were studied. The organoclays, with the confined HCP–POP from 400 and 2000 g/mol M w amines, are nongelled products when using 1/6 M ratio of HCP/POP starting materials in tetrahydrofuran solvent. The intercalation of HCP–POP polyamine salts into sodium montmorillonite afforded the HCP–POP-embedded organoclays with an expanded interlayer silicate spacing (2.4–5.1 nm) from the original 1.2 nm spacing (X-ray diffraction). The effect of silicate clays was evaluated by blending the HCP-POP/clay hybrids into a two-component epoxy system (diglycidyl ether of 4,4′-isopropylidenediphenol (BPA) and a diamine) and fully cured to form solid materials. The distribution of the exfoliated silicate platelets in the matrix was analyzed by transmission electronic microscopy (TEM). Thermal gravimetric analysis (TGA) indicated an enhanced thermal stability for the HCP/clay epoxy nanocomposites, with a delayed weight-loss pattern (temperature of weight loss at 10% ( T 10 wt.% ) from 360 to 385 °C and temperature of weight loss at 85% ( T 85 wt.% ) from 598 to 696 °C), compared to the pristine epoxies. By comparing these epoxies with different amounts of phosphazene and/or silicates, the TGA revealed a synergistic effect for the presence of both phosphorous and silicate components. Furthermore, the epoxies had improved physical properties such as hardness (from 3H to 5H) and surface adhesion (observed by scanning electron microscope (SEM) on fracture surface).