Fluorescence probe-label methodology for in situ monitoring network forming reactions

The curing of the stoichiometric reaction mixture diglycidyl ether bisphenol A (DGEBA) with N-methylethylenediamine (MEDA) and BEPOX 1268 formulation was monitored by FTIR (in the near IR region) and by fluorescence spectroscopy. 5-Dimethylamino-1-naphthalenesulfonamide derivatives and 4-dialkylamino-4^′-nitrostilbene structural units were used as labels and/or probes. It has been proved that hardener in BEPOX 1268 formulation consists of amine containing the primary and secondary amino group. The rate constant for the addition reaction of the secondary amino hydrogen to epoxide is approximately two times larger than that of the primary amino group hydrogen in MEDA and several times (∼seven times) lower in the amine component of BEPOX 1268 formulation. The changes in the integrated fluorescence intensity of the label during the epoxy groups conversion indicate the most important changes in chemical transformations of the reaction mixture, i.e. primary reaction of the secondary amino groups, the gel point (DGEBA-MEDA) and entry of the system to the glassy state (for DGEBA-MEDA and BEPOX 1268). The change in slope of the fluorescence half bandwidth dependence on the epoxy groups conversion indicates the maximum concentration of the secondary amino groups in the reaction mixture (BEPOX 1268). It has been shown that the dependence of the first moment of the emission band vs. epoxy groups conversion can be used to determine the epoxy groups conversion in situ and in real time.     

Autoacceleration and inhibition: Free volume. Epoxy-amine kinetics

The epoxy-diamine cure process was studied. We found that the mechanism can be described in three steps: (i) initiation up to 20–25% of conversion. (ii) autoacceleration and (iii) inhibition. It has been observed that after the initiation there is a clear autoacceleration effect which has been explained in terms of free volume, considerations: the volume occupied by the products of reaction diminishes the available volume increasing the “local concentration” of the reactants and therefore the rate of reaction. The reaction was followed by FTIR (near infrared) as the main technique. We used a purified epoxy resin as well as phenyl glycidyl ether cured with m-xylenediamine. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1001–1016, 1998