The curing reaction of tetraglycidyl diaminodiphenyl methane (TGDDM) with diaminodiphenyl sulfone (DDS) has been investigated using differential scanning calorimetry, Fourier transform IR spectroscopy, and ESR spin trapping techniques. A mechanism has been proposed, and the cure kinetics has been obtained at 177°C. The major conclusion is that cure proceeds mainly through chain extension, while crosslinking occurs through the reaction of hydroxyl groups with epoxides, resulting in formation of ether linkages.
Thin films of spin‐probed and spin‐labeled poly(methyl methacrylate) (PMMA) have been examined by electron spin resonance (ESR) at X‐band frequency (9.2 GHz) and at various temperatures. Direct spectral evidence is presented to indicate that the composite ESR spectra observed in a certain temperature range originate from two states of distinctly different mobility, one with slow motions corresponding to a glassy state and the other with fast motions corresponding to a liquidlike state. The coexistence of these two states at temperatures considerably below the glass transition temperature can be explained as a result of the effect of free volume in a solid polymeric glass.
Superposition of the loss tangent curves could be achieved for the β‐transition of a series of homologous epoxy resins. It was found that both a vertical and horizontal shift were necessary to achieve superposition when the curves were plotted as the logarithm of the loss tangent versus reciprocal absolute temperature. Resins from the diglycidyl ether of bisphenol A (DGEBA) were prepared with five different curing agents and their loss tangent curves measured on a free‐oscillation torsion pendulum (ca. 1 cps). The β transition is caused by DGEBA, which was found via molecular models to contain a mobile group. The intensity of the loss for three of the resins was found to be proportional to the concentration of DGEBA, molecular models revealing that no additional mobile groups were introduced by these curatives. The remaining two curing agents introduced mobile groups into their systems and for these two, no separate transitions were identified but the intensity of the DGEBA β transition was increased. This may be caused by a coupling of the DGEBA mobile groups through the flexibility of the curative‐introduced mobile groups.
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