Macro and Microgelation in the Homopolimerization of Diepoxides Initiated by Tertiary Amines

M.J .GALANTE; A.VAZQUEZ; R.J.J. WILLIAMS

POLYMER BULLETIN

SPRINGER

Lugar: Berlin; Año: 1991 vol. 27 p. 9 - 15

0170-0839

The homopolymerization of an epoxy resin based on diglycidylether of bisphenol A (DGEBA), initiated by benzyldimethylamine (BDMA), was analyzed in the 80°C?140°C temperature range. An heterogeneous network characterized by regions of different glass transition temperature, was obtained. Microgels appeared early in the polymerization while an increase in the reactivity of the second epoxy group of a DGEBA molecule after reaction of the first one, was inferred from size exclusion chromatograms (SEC), obtained at different overall conversions. Both experimental findings were qualitatively explained through an intramolecular chain transfer step that regenerates the initiator in the proximity of pendant epoxy groups. The increase in the polymerization temperature produced an increase in the macroscopic gel conversion and a decrease in the glass transition temperature of regions of high crosslink density. This was ascribed to the increase in the ratio of intramolecular chain transfer over propagation rates, leading to shorter primary chains.