I know this is super old but yes, I think the heat is maybe what did it and maybe not so much the chemical reaction. Hard to say! If I knew then what I know now...When you say you "poured" a bunch of epoxy to create a filler that's when things went south. The chemical reaction creates heat and the more heat you get the faster the reaction creating more heat and then you have a runaway epoxy reaction that usually ends up full of bubbles and if this happens on the glass matte it's brittle and useless as a structural repair.
And yes you will get a lot of toxic smoke...